Rheological Characterization of Unusual DWPF Slurry Samples (U)

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

Koopman, D. C.

2005-09-01

A study was undertaken to identify and clarify examples of unusual rheological behavior in Defense Waste Processing Facility (DWPF) simulant slurry samples. Identification was accomplished by reviewing sludge, Sludge Receipt and Adjustment Tank (SRAT) product, and Slurry Mix Evaporator (SME) product simulant rheological results from the prior year. Clarification of unusual rheological behavior was achieved by developing and implementing new measurement techniques. Development of these new methods is covered in a separate report, WSRC-TR-2004-00334. This report includes a review of recent literature on unusual rheological behavior, followed by a summary of the rheological measurement results obtained on a set ofmore » unusual simulant samples. Shifts in rheological behavior of slurries as the wt. % total solids changed have been observed in numerous systems. The main finding of the experimental work was that the various unusual DWPF simulant slurry samples exhibit some degree of time dependent behavior. When a given shear rate is applied to a sample, the apparent viscosity of the slurry changes with time rather than remaining constant. These unusual simulant samples are more rheologically complex than Newtonian liquids or more simple slurries, neither of which shows significant time dependence. The study concludes that the unusual rheological behavior that has been observed is being caused by time dependent rheological properties in the slurries being measured. Most of the changes are due to the effect of time under shear, but SB3 SME products were also changing properties while stored in sample bottles. The most likely source of this shear-related time dependence for sludge is in the simulant preparation. More than a single source of time dependence was inferred for the simulant SME product slurries based on the range of phenomena observed. Rheological property changes were observed on the time-scale of a single measurement (minutes) as well as on a time scale of hours to weeks. The unusual shape of the slurry flow curves was not an artifact of the rheometric measurement. Adjusting the user-specified parameters in the rheometer measurement jobs can alter the shape of the flow curve of these time dependent samples, but this was not causing the unusual behavior. Variations in the measurement parameters caused the time dependence of a given slurry to manifest at different rates. The premise of the controlled shear rate flow curve measurement is that the dynamic response of the sample to a change in shear rate is nearly instantaneous. When this is the case, the data can be fitted to a time independent rheological equation, such as the Bingham plastic model. In those cases where this does not happen, interpretation of the data is difficult. Fitting time dependent data to time independent rheological equations, such as the Bingham plastic model, is also not appropriate.« less

Analysis of Braking Behavior of Train Drivers to Detect Unusual Driving

NASA Astrophysics Data System (ADS)

Marumo, Yoshitaka; Tsunashima, Hitoshi; Kojima, Takashi; Hasegawa, Yasushi

The safety devices for train systems are activated in emergency situations when a risk becomes obvious, and the emergency brake is applied. If such systems are faulty, the drivers' operating errors may cause immediate accidents. So it is necessary to evaluate potential risks by detecting improper driving behavior before overt risks appear. This study analyzes the driving behavior of train drivers using a train-driving simulator. We focus on braking behavior when approaching a station. Two methods for detecting unusual braking operation are examined by giving drivers mental calculation problems as a mental workload. The first is a method monitoring the driver's brake handle operation, and the second is a method measuring vehicle deceleration. These methods make it possible to detect unusual driving.

Static and kinetic frictional forces of silica-insert ceramic brackets with coated archwires in artificial saliva.

PubMed

Shahabi, Mostafa; Salari, Soheil; Poosti, Maryam; Abtahi, Mostafa

2017-01-01

During sliding mechanics, the frictional force (FF) is an important counterforce to orthodontic tooth movement. The purpose of this in vitro study was to investigate the static and kinetic FFs of S silica-insert ceramic (SIC) brackets with Teflon-coated (TC) and conventional S stainless steel (SS) archwires. The target group of this study included 80 maxillary canine 0.022 inch slot SIC brackets. Forty SS brackets were used as the control. TC and conventional uncoated SS archwires of different dimensions (0.016, 0.018, 0.016 × 0.022, and 0.018 × 0.025 inch) were examined. All tests were carried out under artificial saliva injected condition. Scanning Electron Micrographs were prepared for two samples of coated and uncoated archwires. Analysis of variance and Tukey post hoc tests were used for statistical purposes (level of significance P < 0.05). SIC brackets showed significantly lower levels of FFs than SS brackets. TC archwires had greater frictional values than conventional uncoated ones. They also exhibited an unusual behavior of increasing kinetic FFs with time. Indentation and delamination of coating were obvious under scanning electron microscopy observations. From the standpoint of friction, SIC brackets may serve well, even better than SS brackets, in sliding mechanics. The coating layer of the archwires may delaminate and lost, causing an impediment to tooth movement.

Static and kinetic frictional forces of silica-insert ceramic brackets with coated archwires in artificial saliva

PubMed Central

Shahabi, Mostafa; Salari, Soheil; Poosti, Maryam; Abtahi, Mostafa

2017-01-01

Background: During sliding mechanics, the frictional force (FF) is an important counterforce to orthodontic tooth movement. The purpose of this in vitro study was to investigate the static and kinetic FFs of S silica-insert ceramic (SIC) brackets with Teflon-coated (TC) and conventional S stainless steel (SS) archwires. Materials and Methods: The target group of this study included 80 maxillary canine 0.022 inch slot SIC brackets. Forty SS brackets were used as the control. TC and conventional uncoated SS archwires of different dimensions (0.016, 0.018, 0.016 × 0.022, and 0.018 × 0.025 inch) were examined. All tests were carried out under artificial saliva injected condition. Scanning Electron Micrographs were prepared for two samples of coated and uncoated archwires. Analysis of variance and Tukey post hoc tests were used for statistical purposes (level of significance P < 0.05). Results: SIC brackets showed significantly lower levels of FFs than SS brackets. TC archwires had greater frictional values than conventional uncoated ones. They also exhibited an unusual behavior of increasing kinetic FFs with time. Indentation and delamination of coating were obvious under scanning electron microscopy observations. Conclusion: From the standpoint of friction, SIC brackets may serve well, even better than SS brackets, in sliding mechanics. The coating layer of the archwires may delaminate and lost, causing an impediment to tooth movement. PMID:29238380

Characterizing Sexual Behavior in Frontotemporal Dementia.

PubMed

Ahmed, Rebekah M; Kaizik, Cassandra; Irish, Muireann; Mioshi, Eneida; Dermody, Nadene; Kiernan, Matthew C; Piguet, Olivier; Hodges, John R

2015-01-01

Frontotemporal dementia (FTD) is characterized by a number of prominent behavioral changes. While FTD has been associated with the presence of aberrant or unusual sexual behaviors in a proportion of patients, few studies have formally investigated changes in sexual function in this disease. We aimed to systematically quantify changes in sexual behavior, including current symptoms and changes from prior diagnoses, in behavioral-variant (bvFTD) and semantic dementia (SD), compared to Alzheimer's disease (AD). Carers of 49 dementia patients (21 bvFTD, 11 SD, 17 AD) were interviewed using the Sexual Behavior and Intimacy Questionnaire (SIQ), a survey designed to assess changes in sexual function across multiple domains including initiating, level of affection, and aberrant or unusual sexual behavior. BvFTD patients show prominent hyposexual behavior including decreased affection, initiation, and response to advances by partners, and decreased frequency of sexual relations, compared to AD and to SD patients. The greatest changes in sexual behavior compared to pre-diagnoses were found in the bvFTD group with a 90-100% decrease in initiation, response, and frequency of sexual relations. Notably, aberrant or unusual sexual behavior was reported in a minority of bvFTD and SD patients and occurred in patients who also showed hyposexual behavior toward their partner. Overall loss of affection, reduced initiation of sexual activity, and responsiveness is an overwhelming feature of bvFTD. In contrast, aberrant or unusual sexual behavior is observed in the minority of bvFTD patients. The underlying pathophysiology of these changes likely reflects structural and functional changes in frontoinsular and limbic regions including the hypothalamus.

A novel polyamine allosteric site of SpeG from Vibrio cholerae is revealed by its dodecameric structure

PubMed Central

Filippova, Ekaterina V.; Kuhn, Misty L.; Osipiuk, Jerzy; Kiryukhina, Olga; Joachimiak, Andrzej; Ballicora, Miguel A.

2015-01-01

Spermidine N-acetyltransferase, encoded by the gene speG, catalyzes the initial step in the degradation of polyamines and is a critical enzyme for determining the polyamine concentrations in bacteria. In Escherichia coli, studies have shown that SpeG is the enzyme responsible for acetylating spermidine under stress conditions and for preventing spermidine toxicity. Not all bacteria contain speG, and many bacterial pathogens have developed strategies to either acquire or silence it for pathogenesis. Here, we present thorough kinetic analyses combined with structural characterization of the VCA0947 SpeG enzyme from the important human pathogen Vibrio cholerae. Our studies revealed the unexpected presence of a previously unknown allosteric site and an unusual dodecameric structure for a member of the Gcn5-related N-acetyltransferase (GNAT) superfamily. We show that SpeG forms dodecamers in solution and in crystals and describe its three-dimensional structure in several ligand-free and liganded structures. Importantly, these structural data define the first view of a polyamine bound in an allosteric site of an N-acetyltransferase. Kinetic characterization of SpeG from V. cholerae showed that it acetylates spermidine and spermine. The behavior of this enzyme is complex and exhibits sigmoidal curves and substrate inhibition. We performed a detailed non-linear regression kinetic analysis to simultaneously fit families of substrate saturation curves to uncover a simple kinetic mechanism that explains the apparent complexity of this enzyme. Our results provide a fundamental understanding of the bacterial SpeG enzyme, which will be key towards understanding the regulation of polyamine levels in bacteria during pathogenesis. PMID:25623305

Learning To Fold Proteins Using Energy Landscape Theory

PubMed Central

Schafer, N.P.; Kim, B.L.; Zheng, W.; Wolynes, P.G.

2014-01-01

This review is a tutorial for scientists interested in the problem of protein structure prediction, particularly those interested in using coarse-grained molecular dynamics models that are optimized using lessons learned from the energy landscape theory of protein folding. We also present a review of the results of the AMH/AMC/AMW/AWSEM family of coarse-grained molecular dynamics protein folding models to illustrate the points covered in the first part of the article. Accurate coarse-grained structure prediction models can be used to investigate a wide range of conceptual and mechanistic issues outside of protein structure prediction; specifically, the paper concludes by reviewing how AWSEM has in recent years been able to elucidate questions related to the unusual kinetic behavior of artificially designed proteins, multidomain protein misfolding, and the initial stages of protein aggregation. PMID:25308991

Cluster Nucleation and Growth from a Highly Supersaturated Adatom Phase: Silver on Magnetite

PubMed Central

2014-01-01

The atomic-scale mechanisms underlying the growth of Ag on the (√2×√2)R45°-Fe3O4(001) surface were studied using scanning tunneling microscopy and density functional theory based calculations. For coverages up to 0.5 ML, Ag adatoms populate the surface exclusively; agglomeration into nanoparticles occurs only with the lifting of the reconstruction at 720 K. Above 0.5 ML, Ag clusters nucleate spontaneously and grow at the expense of the surrounding material with mild annealing. This unusual behavior results from a kinetic barrier associated with the (√2×√2)R45° reconstruction, which prevents adatoms from transitioning to the thermodynamically favorable 3D phase. The barrier is identified as the large separation between stable adsorption sites, which prevents homogeneous cluster nucleation and the instability of the Ag dimer against decay to two adatoms. Since the system is dominated by kinetics as long as the (√2×√2)R45° reconstruction exists, the growth is not well described by the traditional growth modes. It can be understood, however, as the result of supersaturation within an adsorption template system. PMID:24945923

Numerical modeling of the solar wind flow with observational boundary conditions

DOE PAGES

Pogorelov, N. V.; Borovikov, S. N.; Burlaga, L. F.; ...

2012-11-20

In this paper we describe our group efforts to develop a self-consistent, data-driven model of the solar wind (SW) interaction with the local interstellar medium. The motion of plasma in this model is described with the MHD approach, while the transport of neutral atoms is addressed by either kinetic or multi-fluid equations. The model and its implementation in the Multi-Scale Fluid-Kinetic Simulation Suite (MS-FLUKSS) are continuously tested and validated by comparing our results with other models and spacecraft measurements. In particular, it was successfully applied to explain an unusual SW behavior discovered by the Voyager 1 spacecraft, i.e., the developmentmore » of a substantial negative radial velocity component, flow turning in the transverse direction, while the latitudinal velocity component goes to very small values. We explain recent SW velocity measurements at Voyager 1 in the context of our 3-D, MHD modeling. We also present a comparison of different turbulence models in their ability to reproduce the SW temperature profile from Voyager 2 measurements. Lastly, the boundary conditions obtained at 50 solar radii from data-driven numerical simulations are used to model a CME event throughout the heliosphere.« less

Stereodirectional Origin of anti-Arrhenius Kinetics for a Tetraatomic Hydrogen Exchange Reaction: Born-Oppenheimer Molecular Dynamics for OH + HBr.

PubMed

Coutinho, Nayara D; Aquilanti, Vincenzo; Silva, Valter H C; Camargo, Ademir J; Mundim, Kleber C; de Oliveira, Heibbe C B

2016-07-14

Among four-atom processes, the reaction OH + HBr → H2O + Br is one of the most studied experimentally: its kinetics has manifested an unusual anti-Arrhenius behavior, namely, a marked decrease of the rate constant as the temperature increases, which has intrigued theoreticians for a long time. Recently, salient features of the potential energy surface have been characterized and most kinetic aspects can be considered as satisfactorily reproduced by classical trajectory simulations. Motivation of the work reported in this paper is the investigation of the stereodirectional dynamics of this reaction as the prominent reason for the peculiar kinetics: we started in a previous Letter ( J. Phys. Chem. Lett. 2015 , 6 , 1553 - 1558 ) a first-principles Born-Oppenheimer "canonical" molecular dynamics approach. Trajectories are step-by-step generated on a potential energy surface quantum mechanically calculated on-the-fly and are thermostatically equilibrated to correspond to a specific temperature. Here, refinements of the method permitted a major increase of the number of trajectories and the consideration of four temperatures -50, +200, +350, and +500 K, for which the sampling of initial conditions allowed us to characterize the stereodynamical effect. The role is documented of the adjustment of the reactants' mutual orientation to encounter the entrance into the "cone of acceptance" for reactivity. The aperture angle of this cone is dictated by a range of directions of approach compatible with the formation of the specific HOH angle of the product water molecule; and consistently the adjustment is progressively less effective the higher the kinetic energy. Qualitatively, this emerging picture corroborates experiments on this reaction, involving collisions of aligned and oriented molecular beams, and covering a range of energies higher than the thermal ones. The extraction of thermal rate constants from this molecular dynamics approach is discussed and the systematic sampling of the canonical ensemble is indicated as needed for quantitative comparison with the kinetic experiments.

Water sorption in microfibrillated cellulose (MFC): The effect of temperature and pretreatment.

PubMed

Meriçer, Çağlar; Minelli, Matteo; Giacinti Baschetti, Marco; Lindström, Tom

2017-10-15

Water sorption behavior of two different microfibrillated cellulose (MFC) films, produced by delamination of cellulose pulp after different pretreatment methods, is examined at various temperatures (16-65°C) and up to 70% RH. The effect of drying temperature of MFC films on the water uptake is also investigated. The obtained solubility isotherms showed the typical downward curvature at moderate RH, while no upturn is observed at higher RH; the uptakes are in line with characteristic values for cellulose fibers. Enzymatically pretreated MFC dispersion showed lower solubility than carboxymethylated MFC, likely due to the different material structure, which results from the different preparation methods The experimental results are analyzed by Park and GAB models, which proved suitable to describe the observed behaviors. Interestingly, while no significant thermal effect is detected on water solubility above 35°C, the uptake at 16 and 25°C, at a given RH, is substantially lower than that at higher temperature, indicating that, in such range, sorption process is endothermic. Such unusual behavior for a cellulose-based system seems to be related mainly to the structural characteristics of MFC films, and to relaxation phenomena taking place upon water sorption. The diffusion kinetics, indeed, showed a clear Fickian behavior at low temperature and RH, whereas a secondary process seems to occur at high temperature and higher RH, leading to anomalous diffusion behaviors. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Varied Variability of PKS 0736+017

NASA Astrophysics Data System (ADS)

Clements, S. D.; Cubides, L. A.; Greiwe, C. L.; Habermas, K. S.; Jenks, A. K.; Long, A. M.; Patel, J. A.; Torres, Y. V.

2003-05-01

The flat spectrum radio quasar PKS 0736+017 has been an exciting observing target, exhibiting diverse optical variability behaviors and even sharing its field one evening with a minor planet. The behavior of PKS 0736+017 has included persistently faint and quiescent periods, episodes of quasi-periodic microvariability, dramatic flaring events, and periods of unusual oscillations. These assorted behaviors are examined, with particular emphasis on the quasi-periodic variations and unusual oscillations that accompanied a dramatic flare.

A novel polyamine allosteric site of SpeG from Vibrio cholerae is revealed by Its dodecameric structure

DOE PAGES

Filippova, Ekaterina V.; Kuhn, Misty L.; Osipiuk, Jerzy; ...

2015-01-23

Spermidine N-acetyltransferase, encoded by the gene speG, catalyzes the initial step in the degradation of polyamines and is a critical enzyme for determining the polyamine concentrations in bacteria. In Escherichia coli, studies have shown that SpeG is the enzyme responsible for acetylating spermidine under stress conditions and for preventing spermidine toxicity. Not all bacteria contain speG, and many bacterial pathogens have developed strategies to either acquire or silence it for pathogenesis. Here, we present thorough kinetic analyses combined with structural characterization of the VCA0947 SpeG enzyme from the important human pathogen Vibrio cholerae. Our studies revealed the unexpected presence ofmore » a previously unknown allosteric site and an unusual dodecameric structure for a member of the Gcn5-related N-acetyltransferase superfamily. We show that SpeG forms dodecamers in solution and in crystals and describe its three-dimensional structure in several ligand-free and liganded structures. Importantly, these structural data define the first view of a polyamine bound in an allosteric site of an N-acetyltransferase. Kinetic characterization of SpeG from V. cholerae showed that it acetylates spermidine and spermine. The behavior of this enzyme is complex and exhibits sigmoidal curves and substrate inhibition. We performed a detailed non-linear regression kinetic analysis to simultaneously fit families of substrate saturation curves to uncover a simple kinetic mechanism that explains the apparent complexity of this enzyme. Our results provide a fundamental understanding of the bacterial SpeG enzyme, which will be key toward understanding the regulation of polyamine levels in bacteria during pathogenesis.« less

A novel polyamine allosteric site of SpeG from Vibrio cholerae is revealed by its dodecameric structure.

PubMed

Filippova, Ekaterina V; Kuhn, Misty L; Osipiuk, Jerzy; Kiryukhina, Olga; Joachimiak, Andrzej; Ballicora, Miguel A; Anderson, Wayne F

2015-03-27

Spermidine N-acetyltransferase, encoded by the gene speG, catalyzes the initial step in the degradation of polyamines and is a critical enzyme for determining the polyamine concentrations in bacteria. In Escherichia coli, studies have shown that SpeG is the enzyme responsible for acetylating spermidine under stress conditions and for preventing spermidine toxicity. Not all bacteria contain speG, and many bacterial pathogens have developed strategies to either acquire or silence it for pathogenesis. Here, we present thorough kinetic analyses combined with structural characterization of the VCA0947 SpeG enzyme from the important human pathogen Vibrio cholerae. Our studies revealed the unexpected presence of a previously unknown allosteric site and an unusual dodecameric structure for a member of the Gcn5-related N-acetyltransferase superfamily. We show that SpeG forms dodecamers in solution and in crystals and describe its three-dimensional structure in several ligand-free and liganded structures. Importantly, these structural data define the first view of a polyamine bound in an allosteric site of an N-acetyltransferase. Kinetic characterization of SpeG from V. cholerae showed that it acetylates spermidine and spermine. The behavior of this enzyme is complex and exhibits sigmoidal curves and substrate inhibition. We performed a detailed non-linear regression kinetic analysis to simultaneously fit families of substrate saturation curves to uncover a simple kinetic mechanism that explains the apparent complexity of this enzyme. Our results provide a fundamental understanding of the bacterial SpeG enzyme, which will be key toward understanding the regulation of polyamine levels in bacteria during pathogenesis. Copyright © 2015. Published by Elsevier Ltd.

A novel polyamine allosteric site of SpeG from Vibrio cholerae is revealed by Its dodecameric structure

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

Filippova, Ekaterina V.; Kuhn, Misty L.; Osipiuk, Jerzy

Spermidine N-acetyltransferase, encoded by the gene speG, catalyzes the initial step in the degradation of polyamines and is a critical enzyme for determining the polyamine concentrations in bacteria. In Escherichia coli, studies have shown that SpeG is the enzyme responsible for acetylating spermidine under stress conditions and for preventing spermidine toxicity. Not all bacteria contain speG, and many bacterial pathogens have developed strategies to either acquire or silence it for pathogenesis. Here, we present thorough kinetic analyses combined with structural characterization of the VCA0947 SpeG enzyme from the important human pathogen Vibrio cholerae. Our studies revealed the unexpected presence ofmore » a previously unknown allosteric site and an unusual dodecameric structure for a member of the Gcn5-related N-acetyltransferase superfamily. We show that SpeG forms dodecamers in solution and in crystals and describe its three-dimensional structure in several ligand-free and liganded structures. Importantly, these structural data define the first view of a polyamine bound in an allosteric site of an N-acetyltransferase. Kinetic characterization of SpeG from V. cholerae showed that it acetylates spermidine and spermine. The behavior of this enzyme is complex and exhibits sigmoidal curves and substrate inhibition. We performed a detailed non-linear regression kinetic analysis to simultaneously fit families of substrate saturation curves to uncover a simple kinetic mechanism that explains the apparent complexity of this enzyme. Our results provide a fundamental understanding of the bacterial SpeG enzyme, which will be key toward understanding the regulation of polyamine levels in bacteria during pathogenesis.« less

Unusual ferromagnetic critical behavior owing to short-range antiferromagnetic correlations in antiperovskite Cu1-xNMn3+x (0.1 ≤ x ≤ 0.4)

PubMed Central

Lin, Jianchao; Tong, Peng; Cui, Dapeng; Yang, Cheng; Yang, Jie; Lin, Shuai; Wang, Bosen; Tong, Wei; Zhang, Lei; Zou, Youming; Sun, Yuping

2015-01-01

For ferromagnets, varying from simple metals to strongly correlated oxides,the critical behaviors near the Curie temperature (TC) can be grouped into several universal classes. In this paper, we report an unusual critical behavior in manganese nitrides Cu1-xNMn3+x (0.1 ≤ x ≤ 0.4). Although the critical behavior below TC can be well described by mean field (MF) theory, robust critical fluctuations beyond the expectations of any universal classes are observed above TC in x = 0.1. The critical fluctuations become weaker when x increases, and the MF-like critical behavior is finally restored at x = 0.4. In addition, the paramagnetic susceptibility of all the samples deviates from the Curie-Weiss (CW) law just above TC. This deviation is gradually smeared as x increases. The short-range antiferromagnetic ordering above TC revealed by our electron spin resonance measurement explains both the unusual critical behavior and the breakdown of the CW law. PMID:25604754

Effect of Carrier Thermalization Dynamics on Light Emission and Amplification in Organometal Halide Perovskites.

PubMed

Chen, Kai; Barker, Alex J; Morgan, Francis L C; Halpert, Jonathan E; Hodgkiss, Justin M

2015-01-02

The remarkable rise of organometal halide perovskites as solar photovoltaic materials has been followed by promising developments in light-emitting devices, including lasers. Here we present unique insights into the processes leading to photon emission in these materials. We employ ultrafast broadband photoluminescence (PL) and transient absorption spectroscopies to directly link density dependent ultrafast charge dynamics to PL. We find that exceptionally strong PL at the band edge is preceded by thermalization of free charge carriers. Short-lived PL above the band gap is clear evidence of nonexcitonic emission from hot carriers, and ultrafast PL depolarization confirms that uncorrelated charge pairs are precursors to photon emission. Carrier thermalization has a profound effect on amplified stimulated emission at high fluence; the delayed onset of optical gain we resolve within the first 10 ps and the unusual oscillatory behavior are both consequences of the kinetic interplay between carrier thermalization and optical gain.

Coincidence of collective relaxation anomaly and specific heat peak in a bulk metallic glass-forming liquid

DOE PAGES

Jaiswal, Abhishek; Podlesynak, Andrey; Ehlers, Georg; ...

2015-07-21

The study of multicomponent metallic liquids' relaxational behavior is still the key to understanding and improving the glass-forming abilities of bulk metallic glasses. Here, we report measurements of the collective relaxation times in a melted bulk metallic glass (LM601Zr 51Cu 36Ni 4Al 9) in the kinetic regime (Q: 1.5–4.0Å –1) using quasielastic neutron scattering. The results reveal an unusual slope change in the Angell plots of this metallic liquid's collective relaxation time around 950°C, beyond the material's melting point. Measurement of specific heat capacity also reveals a peak around the same temperature. Adams-Gibbs theory is used to rationalize the coincidence,more » which motivates more careful experimental and computational studies of the metallic liquids in the future.« less

Glycerol acyl-transfer kinetics of a circular permutated Candida antarctica Lipase B

USDA-ARS?s Scientific Manuscript database

Triacylglycerols containing a high abundance of unusual fatty acids, such as y-linolenic acid, or novel arylaliphatic acids, such as ferulic acid, are useful in pharmaceutical and cosmeceutical applications. Candida antarctica lipase B (CALB) is quite often used for non-aqueous synthesis, although ...

Direct observation of a single nanoparticle-ubiquitin corona formation

NASA Astrophysics Data System (ADS)

Ding, Feng; Radic, Slaven; Chen, Ran; Chen, Pengyu; Geitner, Nicholas K.; Brown, Jared M.; Ke, Pu Chun

2013-09-01

The advancement of nanomedicine and the increasing applications of nanoparticles in consumer products have led to administered biological exposure and unintentional environmental accumulation of nanoparticles, causing concerns over the biocompatibility and sustainability of nanotechnology. Upon entering physiological environments, nanoparticles readily assume the form of a nanoparticle-protein corona that dictates their biological identity. Consequently, understanding the structure and dynamics of a nanoparticle-protein corona is essential for predicting the fate, transport, and toxicity of nanomaterials in living systems and for enabling the vast applications of nanomedicine. Here we combined multiscale molecular dynamics simulations and complementary experiments to characterize the silver nanoparticle-ubiquitin corona formation. Notably, ubiquitins competed with citrates for the nanoparticle surface, governed by specific electrostatic interactions. Under a high protein/nanoparticle stoichiometry, ubiquitins formed a multi-layer corona on the particle surface. The binding exhibited an unusual stretched-exponential behavior, suggesting a rich binding kinetics. Furthermore, the binding destabilized the α-helices while increasing the β-sheet content of the proteins. This study revealed the atomic and molecular details of the structural and dynamic characteristics of nanoparticle-protein corona formation.The advancement of nanomedicine and the increasing applications of nanoparticles in consumer products have led to administered biological exposure and unintentional environmental accumulation of nanoparticles, causing concerns over the biocompatibility and sustainability of nanotechnology. Upon entering physiological environments, nanoparticles readily assume the form of a nanoparticle-protein corona that dictates their biological identity. Consequently, understanding the structure and dynamics of a nanoparticle-protein corona is essential for predicting the fate, transport, and toxicity of nanomaterials in living systems and for enabling the vast applications of nanomedicine. Here we combined multiscale molecular dynamics simulations and complementary experiments to characterize the silver nanoparticle-ubiquitin corona formation. Notably, ubiquitins competed with citrates for the nanoparticle surface, governed by specific electrostatic interactions. Under a high protein/nanoparticle stoichiometry, ubiquitins formed a multi-layer corona on the particle surface. The binding exhibited an unusual stretched-exponential behavior, suggesting a rich binding kinetics. Furthermore, the binding destabilized the α-helices while increasing the β-sheet content of the proteins. This study revealed the atomic and molecular details of the structural and dynamic characteristics of nanoparticle-protein corona formation. Electronic supplementary information (ESI) available: Experimental and computational methods as well as supporting figures. See DOI: 10.1039/c3nr02147e

Crystal growth of intermetallic clathrates: Floating zone process and ultra rapid crystallization

NASA Astrophysics Data System (ADS)

Prokofiev, A.; Yan, X.; Ikeda, M.; Löffler, S.; Paschen, S.

2014-09-01

We studied the crystal growth process of type-I transition metal clathrates in two different regimes: a regime of moderate cooling rate, realized with the floating zone technique, and a regime of ultra rapid cooling, realized by the melt spinning technique. In the former regime, bulk Ba8AuxSi46-x and Ba8Cu4.8GaxGe41.2-x single crystals were grown. We investigated segregation effects of the constituting elements by measurements of the composition profiles along the growth direction. The compositional non-uniformity results in a spatial variation of the electrical resistivity which is discussed as well. Structural features of clathrates and their extremely low thermal conductivities imply specifics in growth behavior which manifest themselves most pronouncedly in a rapid crystallization process. Our melt spinning experiments on Ba8Au5Si41 and Ba8Ni3.5Si42.5 (and earlier on some other clathrates) have revealed surprisingly large grains of at least 1 μm. Because of the anomalously high growth rate of the clathrate phase the formation of impurity phases is considerably kinetically suppressed. We present our scanning and transmission electron microscopy investigations of melt spun samples and discuss structural, thermodynamic and kinetic aspects of the unusual clathrate nucleation and crystallization.

Carrageenan-grafted magnetite nanoparticles as recyclable sorbents for dye removal

NASA Astrophysics Data System (ADS)

Daniel-da-Silva, Ana L.; Salgueiro, Ana M.; Creaney, Bianca; Oliveira-Silva, Rui; Silva, Nuno J. O.; Trindade, Tito

2015-07-01

The efforts dedicated to improving water decontamination procedures have prompted the interest in the development of efficient, inexpensive, and reusable sorbents for the uptake of dye pollutants. In this work, novel sorbents consisting of carrageenan polysaccharides grafted to magnetic iron oxide nanoparticles were prepared. κ- and ι-carrageenan were first chemically modified by carboxymethylation and then covalently attached via amide bond to the surface of aminated silica-coated magnetite nanoparticles, both steps monitored using infrared spectroscopy (FTIR) analysis. The kinetics and the equilibrium behavior of the cationic dye methylene blue (MB) adsorption onto the carrageenan sorbents were investigated. ι-carrageenan sorbents displayed higher MB adsorption capacity that was ascribed to high content of sulfonate groups. Overall, the pseudo-second order equation provided a good description of the adsorption kinetics. The κ-carrageenan sorbents followed an unusual Z-type equilibrium adsorption isotherm whereas the isotherm of ι-carrageenan sorbents, although displaying a conventional shape, could not be successfully predicted by isotherm models commonly used. Noteworthy, both sorbents were long-term stable and could easily be recycled by simply rinsing with KCl aqueous solution. The removal efficiency of κ-carrageenan sorbents was 92 % in the first adsorption cycle and kept high (>80 %) even after six consecutive adsorption/desorption cycles.

Adhesion kinetics of viable Cryptosporidium parvum oocysts to quartz surfaces.

PubMed

Kuznar, Zachary A; Elimelech, Menachem

2004-12-15

The transport and deposition (adhesion) kinetics of viable Cryptosporidium parvum oocysts onto ultrapure quartz surfaces in a radial stagnation point flow system were investigated. Utilizing an optical microscope and an image-capturing device enabled real time observation of oocyst deposition behavior onto the quartz surface in solutions containing either monovalent (KCl) or divalent (CaCl2) salts. Results showed a significantly lower oocyst deposition rate in the presence of a monovalent salt compared to a divalent salt. With a monovalent salt, oocyst deposition rates and corresponding attachment efficiencies were relatively low, even at high KCl concentrations where Derjaguin-Landau-Verwey-Overbeek (DLVO) theory predicts the absence of an electrostatic energy barrier. On the other hand, in the presence of a divalent salt, oocyst deposition rates increased continuously as the salt concentration was increased over the entire range of ionic strengths investigated. The unusually low deposition rate in a monovalent salt solution is attributed to "electrosteric" repulsion between the Cryptosporidium oocyst and the quartz surface, most likely due to proteins on the oocyst surface that extend into the solution. It is further proposed that specific binding of calcium ions to the oocyst surface functional groups results in charge neutralization and conformational changes of surface proteins that significantly reduce electrosteric repulsion.

Free Energy Landscape - Settlements of Key Residues.

NASA Astrophysics Data System (ADS)

Aroutiounian, Svetlana

2007-03-01

FEL perspective in studies of protein folding transitions reflects notion that since there are ˜10^N conformations to scan in search of lowest free energy state, random search is beyond biological timescale. Protein folding must follow certain fel pathways and folding kinetics of evolutionary selected proteins dominates kinetic traps. Good model for functional robustness of natural proteins - coarse-grained model protein is not very accurate but affords bringing simulations closer to biological realm; Go-like potential secures the fel funnel shape; biochemical contacts signify the funnel bottleneck. Boltzmann-weighted ensemble of protein conformations and histogram method are used to obtain from MC sampling of protein conformational space the approximate probability distribution. The fel is F(rmsd) = -1/βLn[Hist(rmsd)], β=kBT and rmsd is root-mean-square-deviation from native conformation. The sperm whale myoglobin has rich dynamic behavior, is small and large - on computational scale, has a symmetry in architecture and unusual sextet of residue pairs. Main idea: there is a mathematical relation between protein fel and a key residues set providing stability to folding transition. Is the set evolutionary conserved also for functional reasons? Hypothesis: primary sequence determines the key residues positions conserved as stabilizers and the fel is the battlefield for the folding stability. Preliminary results: primary sequence - not the architecture, is the rule settler, indeed.

Increased Prevalence of Unusual Sensory Behaviors in Infants at Risk For, and Teens With, Autism Spectrum Disorder

ERIC Educational Resources Information Center

Van Etten, Hannah M.; Kaur, Maninderjit; Srinivasan, Sudha M.; Cohen, Shereen J.; Bhat, Anjana; Dobkins, Karen R.

2017-01-01

The current study investigated the prevalence and pattern of unusual sensory behaviors (USBs) in teens with Autism Spectrum Disorder (ASD) and infants (3-36 months) at risk for ASD. From two different sites (UCSD and UConn), caregivers of infants at high (n = 32) and low risk (n = 33) for ASD, and teenagers with (n = 12) and without ASD (n = 11),…

A Statistical Procedure for Testing Unusually Frequent Exactly Matching Responses and Nearly Matching Responses. Research Report. ETS RR-17-23

ERIC Educational Resources Information Center

Haberman, Shelby J.; Lee, Yi-Hsuan

2017-01-01

In investigations of unusual testing behavior, a common question is whether a specific pattern of responses occurs unusually often within a group of examinees. In many current tests, modern communication techniques can permit quite large numbers of examinees to share keys, or common response patterns, to the entire test. To address this issue,…

Unusual reversal of enantioselectivity in the proline-mediated alpha-amination of aldehydes induced by tertiary amine additives.

PubMed

Blackmond, Donna G; Moran, Antonio; Hughes, Matthew; Armstrong, Alan

2010-06-09

An intriguing reversal in product enantioselectivity accompanied by a change in the kinetic profile is observed in the alpha-amination of aldehydes catalyzed by proline in the presence of organic bases. Implications for the prevailing stereochemical models for proline and related aminocatalytic transformations are discussed.

TRANSITION FROM KINETIC TO MHD BEHAVIOR IN A COLLISIONLESS PLASMA

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

Parashar, Tulasi N.; Matthaeus, William H.; Shay, Michael A.

The study of kinetic effects in heliospheric plasmas requires representation of dynamics at sub-proton scales, but in most cases the system is driven by magnetohydrodynamic (MHD) activity at larger scales. The latter requirement challenges available computational resources, which raises the question of how large such a system must be to exhibit MHD traits at large scales while kinetic behavior is accurately represented at small scales. Here we study this implied transition from kinetic to MHD-like behavior using particle-in-cell (PIC) simulations, initialized using an Orszag–Tang Vortex. The PIC code treats protons, as well as electrons, kinetically, and we address the questionmore » of interest by examining several different indicators of MHD-like behavior.« less

Unusual behavior in the parental care of a house wren (Troglodytes aedon): Post fledging use of an old nest during cold nights

USGS Publications Warehouse

Scholer, Micah N.

2015-01-01

I report on the unusual behavior of an adult House Wren (Troglodytes aedon) leading recently fledged young back to the nest for two consecutive nights. The ambient temperature reached below 0°C during both nights. Despite disadvantages associated with remaining in the nest, this observation suggests that adult birds may assess trade-offs between perceived risks versus the benefits of engaging in other activities, in this case roosting communally for thermoregulation.

Association between Psychopathic Disorder and Serum Antibody to Herpes Simplex Virus (Type 1)

PubMed Central

Cleobury, J. F.; Skinner, G. R. B.; Thouless, M. E.; Wildy, P.

1971-01-01

The sera of a small of patients has been examined for herpes simplex virus antibody. Three clinically-defined groups of patients were compared: (a) aggressive psychopaths, (b) psychiatric controls, and (c) general hospital patients. The first group had an unusually high average kinetic neutralization constant against type 1 herpes simplex virus. PMID:5543996

Association between psychopathic disorder and serum antibody to herpes simplex virus (type 1).

PubMed

Cleobury, J F; Skinner, G R; Thouless, M E; Wildy, P

1971-02-20

The sera of a small of patients has been examined for herpes simplex virus antibody. Three clinically-defined groups of patients were compared: (a) aggressive psychopaths, (b) psychiatric controls, and (c) general hospital patients. The first group had an unusually high average kinetic neutralization constant against type 1 herpes simplex virus.

Spectroscopic optimization of all-solid-state electrochromic devices using PANI

NASA Astrophysics Data System (ADS)

Hugot-Le Goff, Anne; Bernard, Marie-Claude; Bich, Vu T.; Binh, Nguyen T.; Zeng, Wen

1997-12-01

The interesting optical properties of polyaniline (PANI) allowed its utilization in all solid-state electrochromic devices. Using a sulfonic acid polymer as solid electrolyte gave to PANI an unusual optical behavior leading to electrochromic properties very superior to the properties that it has in any liquid inorganic electrolyte. The improved conductivity of PANI doped with AMP-sulfonate is displayed by the presence of a free-carriers tail even at pH as high as 4.5. The free-carriers tail is studied using UV/vis/near IR spectroscopy, and the kinetics of coloration/bleaching are studied using Optical Multichannel Analysis in the 1.5 - 3 eV range. The modifications of the PANI optical features by solid-state doping are examined. The possibility to still improve the performances of these devices--in particular their rate of color change--by using `secondarily doped' PANI is investigated, which requires a preliminary spectrochemical analysis of PANI films doped with camphorsulfonic acid and treated in m-cresol during their electrochemical polarization.

Steady-state kinetics of substrate binding and iron release in tomato ACC oxidase.

PubMed

Thrower, J S; Blalock, R; Klinman, J P

2001-08-14

1-Aminocyclopropane-1-carboxylate oxidase (ACC oxidase) catalyzes the last step in the biosynthetic pathway of the plant hormone, ethylene. This unusual reaction results in the oxidative ring cleavage of 1-aminocyclopropane carboxylate (ACC) into ethylene, cyanide, and CO2 and requires ferrous ion, ascorbate, and molecular oxygen for catalysis. A new purification procedure and assay method have been developed for tomato ACC oxidase that result in greatly increased enzymatic activity. This method allowed us to determine the rate of iron release from the enzyme and the effect of the activator, CO2, on this rate. Initial velocity studies support an ordered kinetic mechanism where ACC binds first followed by O2; ascorbate can bind after O2 or possibly before ACC. This kinetic mechanism differs from one recently proposed for the ACC oxidase from avocado.

Ropinirole

MedlinePlus

... people who took medications such as ropinirole developed gambling problems or other intense urges or behaviors that ... even if you do not realize that your gambling or any other intense urges or unusual behaviors ...

Amantadine

MedlinePlus

... medications used to treat Parkinson's disease, have developed gambling problems or had other intense urges or behaviors ... even if you do not realize that your gambling or any other intense urges or unusual behaviors ...

Safinamide

MedlinePlus

... people who took medications such as safinamide developed gambling problems or other intense urges or behaviors that ... even if you do not realize that your gambling or any other intense urges or unusual behaviors ...

Experimental and theoretical kinetics for the H2O+ + H2/D2 → H3O+/H2DO+ + H/D reactions: observation of the rotational effect in the temperature dependence.

PubMed

Ard, Shaun G; Li, Anyang; Martinez, Oscar; Shuman, Nicholas S; Viggiano, Albert A; Guo, Hua

2014-12-11

Thermal rate coefficients for the title reactions computed using a quasi-classical trajectory method on an accurate global potential energy surface fitted to ∼81,000 high-level ab initio points are compared with experimental values measured between 100 and 600 K using a variable temperature selected ion flow tube instrument. Excellent agreement is found across the entire temperature range, showing a subtle, but unusual temperature dependence of the rate coefficients. For both reactions the temperature dependence has a maximum around 350 K, which is a result of H2O(+) rotations increasing the reactivity, while kinetic energy is decreasing the reactivity. A strong isotope effect is found, although the calculations slightly overestimate the kinetic isotope effect. The good experiment-theory agreement not only validates the accuracy of the potential energy surface but also provides more accurate kinetic data over a large temperature range.

Kinetic-Dominated Charging Mechanism within Representative Aqueous Electrolyte-based Electric Double-Layer Capacitors.

PubMed

Yang, Huachao; Yang, Jinyuan; Bo, Zheng; Chen, Xia; Shuai, Xiaorui; Kong, Jing; Yan, Jianhua; Cen, Kefa

2017-08-03

The chemical nature of electrolytes has been demonstrated to play a pivotal role in the charge storage of electric double-layer capacitors (EDLCs), whereas primary mechanisms are still partially resolved but controversial. In this work, a systematic exploration into EDL structures and kinetics of representative aqueous electrolytes is performed with numerical simulation and experimental research. Unusually, a novel charging mechanism exclusively predominated by kinetics is recognized, going beyond traditional views of manipulating capacitances preferentially via interfacial structural variations. Specifically, strikingly distinctive EDL structures stimulated by diverse ion sizes, valences, and mixtures manifest a virtually identical EDL capacitance, where the dielectric nature of solvents attenuates ionic effects on electrolyte redistributions, in stark contradiction with solvent-free counterpart and traditional Helmholtz theory. Meanwhile, corresponding kinetics evolve conspicuously with ionic species, intimately correlated with ion-solvent interactions. The achieved mechanisms are subsequently illuminated by electrochemical measurements, highlighting the crucial interplay between ions and solvents in regulating EDLC performances.

Kinetic mechanism of non-muscle myosin IIB: functional adaptations for tension generation and maintenance.

PubMed

Wang, Fei; Kovacs, Mihaly; Hu, Aihua; Limouze, John; Harvey, Estelle V; Sellers, James R

2003-07-25

Besides driving contraction of various types of muscle tissue, conventional (class II) myosins serve essential cellular functions and are ubiquitously expressed in eukaryotic cells. Three different isoforms in the human myosin complement have been identified as non-muscle class II myosins. Here we report the kinetic characterization of a human non-muscle myosin IIB subfragment-1 construct produced in the baculovirus expression system. Transient kinetic data show that most steps of the actomyosin ATPase cycle are slowed down compared with other class II myosins. The ADP affinity of subfragment-1 is unusually high even in the presence of actin filaments, and the rate of ADP release is close to the steady-state ATPase rate. Thus, non-muscle myosin IIB subfragment-1 spends a significantly higher proportion of its kinetic cycle strongly attached to actin than do the muscle myosins. This feature is even more pronounced at slightly elevated ADP levels, and it may be important in carrying out the cellular functions of this isoform working in small filamentous assemblies.

Kinetics of the LOV domain of ZEITLUPE determine its circadian function in Arabidopsis

PubMed Central

Pudasaini, Ashutosh; Shim, Jae Sung; Song, Young Hun; Shi, Hua; Kiba, Takatoshi; Somers, David E; Imaizumi, Takato; Zoltowski, Brian D

2017-01-01

A LOV (Light, Oxygen, or Voltage) domain containing blue-light photoreceptor ZEITLUPE (ZTL) directs circadian timing by degrading clock proteins in plants. Functions hinge upon allosteric differences coupled to the ZTL photocycle; however, structural and kinetic information was unavailable. Herein, we tune the ZTL photocycle over two orders of magnitude. These variants reveal that ZTL complexes with targets independent of light, but dictates enhanced protein degradation in the dark. In vivo experiments definitively show photocycle kinetics dictate the rate of clock component degradation, thereby impacting circadian period. Structural studies demonstrate that photocycle dependent activation of ZTL depends on an unusual dark-state conformation of ZTL. Crystal structures of ZTL LOV domain confirm delineation of structural and kinetic mechanisms and identify an evolutionarily selected allosteric hinge differentiating modes of PAS/LOV signal transduction. The combined biochemical, genetic and structural studies provide new mechanisms indicating how PAS/LOV proteins integrate environmental variables in complex networks. DOI: http://dx.doi.org/10.7554/eLife.21646.001 PMID:28244872

Unusual kinetics of thermal decay of dim-light photoreceptors in vertebrate vision

PubMed Central

Guo, Ying; Sekharan, Sivakumar; Liu, Jian; Batista, Victor S.; Tully, John C.; Yan, Elsa C. Y.

2014-01-01

We present measurements of rate constants for thermal-induced reactions of the 11-cis retinyl chromophore in vertebrate visual pigment rhodopsin, a process that produces noise and limits the sensitivity of vision in dim light. At temperatures of 52.0–64.6 °C, the rate constants fit well to an Arrhenius straight line with, however, an unexpectedly large activation energy of 114 ± 8 kcal/mol, which is much larger than the 60-kcal/mol photoactivation energy at 500 nm. Moreover, we obtain an unprecedentedly large prefactor of 1072±5 s−1, which is roughly 60 orders of magnitude larger than typical frequencies of molecular motions! At lower temperatures, the measured Arrhenius parameters become more normal: Ea = 22 ± 2 kcal/mol and Apref = 109±1 s−1 in the range of 37.0–44.5 °C. We present a theoretical framework and supporting calculations that attribute this unusual temperature-dependent kinetics of rhodopsin to a lowering of the reaction barrier at higher temperatures due to entropy-driven partial breakup of the rigid hydrogen-bonding network that hinders the reaction at lower temperatures. PMID:25002518

Unusual kinetics of thermal decay of dim-light photoreceptors in vertebrate vision.

PubMed

Guo, Ying; Sekharan, Sivakumar; Liu, Jian; Batista, Victor S; Tully, John C; Yan, Elsa C Y

2014-07-22

We present measurements of rate constants for thermal-induced reactions of the 11-cis retinyl chromophore in vertebrate visual pigment rhodopsin, a process that produces noise and limits the sensitivity of vision in dim light. At temperatures of 52.0-64.6 °C, the rate constants fit well to an Arrhenius straight line with, however, an unexpectedly large activation energy of 114 ± 8 kcal/mol, which is much larger than the 60-kcal/mol photoactivation energy at 500 nm. Moreover, we obtain an unprecedentedly large prefactor of 10(72±5) s(-1), which is roughly 60 orders of magnitude larger than typical frequencies of molecular motions! At lower temperatures, the measured Arrhenius parameters become more normal: Ea = 22 ± 2 kcal/mol and Apref = 10(9±1) s(-1) in the range of 37.0-44.5 °C. We present a theoretical framework and supporting calculations that attribute this unusual temperature-dependent kinetics of rhodopsin to a lowering of the reaction barrier at higher temperatures due to entropy-driven partial breakup of the rigid hydrogen-bonding network that hinders the reaction at lower temperatures.

Unusual Thermoelectric Behavior Indicating a Hopping to Bandlike Transport Transition in Pentacene

NASA Astrophysics Data System (ADS)

Germs, W. Chr.; Guo, K.; Janssen, R. A. J.; Kemerink, M.

2012-07-01

An unusual increase in the Seebeck coefficient with increasing charge carrier density is observed in pentacene thin film transistors. This behavior is interpreted as being due to a transition from hopping transport in static localized states to bandlike transport, occurring at temperatures below ˜250K. Such a transition can be expected for organic materials in which both static energetic disorder and dynamic positional disorder are important. While clearly visible in the temperature and density dependent Seebeck coefficient, the transition hardly shows up in the charge carrier mobility.

Unusual solvent effect on a SN2 reaction. A quantum-mechanical and kinetic study of the Menshutkin reaction between 2-amino-1-methylbenzimidazole and iodomethane in the gas phase and in acetonitrile.

PubMed

Melo, André; Alfaia, António J I; Reis, João Carlos R; Calado, António R T

2006-02-02

The quaternization reaction between 2-amino-1-methylbenzimidazole and iodomethane was investigated in the gas phase and in liquid acetonitrile. Both experimental and theoretical techniques were used in this study. In the experimental part of this work, accurate second-order rate constants were obtained for this reaction in acetonitrile from conductivity data in the 293-323 K temperature range and at ambient pressure. From two different empirical equations describing the effect of temperature on reaction rates, thermodynamic functions of activation were calculated. In the theoretical part of this work, the mechanism of this reaction was investigated in the gas phase and in acetonitrile. Two different quantum levels (B3LYP/[6-311++G(3df,3pd)/LanL2DZ]//B3LYP/[6-31G(d)/LanL2DZ] and B3LYP/[6-311++G(3df,3pd)/LanL2DZ]//B3LYP/[6-31+G(d)/LanL2DZ]) were used in the calculations, and the acetonitrile environment was modeled using the polarized continuum model (PCM). In addition, an atoms in molecules (AIM) analysis was made aiming to characterize possible hydrogen bonding. The results obtained by both techniques are in excellent agreement and lead to new insight into the mechanism of the reaction under examination. These include the identification and thermodynamic characterization of the relevant stationary species, the rationalization of the mechanistic role played by the solvent and the amine group adjacent to the nucleophile nitrogen atom, the proposal of alternative paths on the modeled potential energy surfaces, and the origin of the marked non-Arrhenius behavior of the kinetic data in solvent acetonitrile. In particular, the AIM analysis confirmed the operation of intermolecular hydrogen bonds between reactants and between products, both in the gas phase and in solution. It is also concluded that the unusual solvent effect on this Menshutkin reaction stems from the conjunction of a nucleophile possessing a relatively complex chemical structure with a dipolar aprotic solvent that is protophobic.

Prolonged intensive dominance behavior between gray wolves, Canis lupus

USGS Publications Warehouse

Mech, L. David; Cluff, H. Dean

2010-01-01

Dominance is one of the most pervasive and important behaviors among wolves in a pack, yet its significance in free-ranging packs has been little studied. Insights into a behavior can often be gained by examining unusual examples of it. In the High Arctic near Eureka, Nunavut, Canada, we videotaped and described an unusually prolonged and intensive behavioral bout between an adult male Gray Wolf (Canis lupus) and a male member of his pack, thought to be a maturing son. With tail raised, the adult approached a male pack mate about 50 m from us and pinned and straddled this packmate repeatedly over 6.5 minutes, longer than we had ever seen in over 50 years of studying wolves. We interpreted this behavior as an extreme example of an adult wolf harassing a maturing offspring, perhaps in prelude to the offspring?s dispersal.

10 CFR 712.17 - Instructional requirements.

Code of Federal Regulations, 2010 CFR

2010-01-01

... responding to behavioral change and aberrant or unusual behavior that may result in a risk to national... supervisors and managers responsible for HRP positions with the knowledge described in paragraph (b)(1) of...

Unusual Electrical Transport Driven by the Competition between Antiferromagnetism and Ferromagnetism in Antiperovskite Mn3Zn1−xCoxN

PubMed Central

Chu, Lihua; Wang, Cong; Guo, Yanjiao; Liu, Zhuohai

2018-01-01

The magnetic, electrical transport and thermal expansion properties of Mn3Zn1−xCoxN (x = 0.2, 0.4, 0.5, 0.7, 0.9) have been systematically investigated. Co-doping in Mn3ZnN complicates the magnetic interactions, leading to a competition between antiferromagnetism and ferromagnetism. Abrupt resistivity jump phenomenon and negative thermal expansion behavior, both associated with the complex magnetic transition, are revealed in all studied cases. Furthermore, semiconductor-like transport behavior is found in sample x = 0.7, distinct from the metallic behavior in other samples. Below 50 K, resistivity minimum is observed in samples x = 0.4, 0.7, and 0.9, mainly caused by e-e scattering mechanism. We finally discussed the strong correlation among unusual electrical transport, negative thermal expansion and magnetic transition in Mn3Zn1−xCoxN, which allows us to conclude that the observed unusual electrical transport properties are attributed to the shift of the Fermi energy surface entailed by the abrupt lattice contraction. PMID:29439522

Stereodynamical Origin of Anti-Arrhenius Kinetics: Negative Activation Energy and Roaming for a Four-Atom Reaction.

PubMed

Coutinho, Nayara D; Silva, Valter H C; de Oliveira, Heibbe C B; Camargo, Ademir J; Mundim, Kleber C; Aquilanti, Vincenzo

2015-05-07

The OH + HBr → H2O + Br reaction, prototypical of halogen-atom liberating processes relevant to mechanisms for atmospheric ozone destruction, attracted frequent attention of experimental chemical kinetics: the nature of the unusual reactivity drop from low to high temperatures eluded a variety of theoretical efforts, ranking this one among the most studied four-atom reactions. Here, inspired by oriented molecular-beams experiments, we develop a first-principles stereodynamical approach. Thermalized sets of trajectories, evolving on a multidimensional potential energy surface quantum mechanically generated on-the-fly, provide a map of most visited regions at each temperature. Visualizations of rearrangements of bonds along trajectories and of the role of specific angles of reactants' mutual approach elucidate the mechanistic change from the low kinetic energy regime (where incident reactants reorient to find the propitious alignment leading to reaction) to high temperature (where speed hinders adjustment of directionality and roaming delays reactivity).

Kinetically-controlled template-free synthesis of hollow silica micro-/nanostructures with unusual morphologies

NASA Astrophysics Data System (ADS)

Zhang, An-Qi; Li, Hui-Jun; Qian, Dong-Jin; Chen, Meng

2014-04-01

We report a kinetically-controlled template-free room-temperature production of hollow silica materials with various novel morphologies, including tubes, crutches, ribbons, bundles and bells. The obtained products, which grew in a well-controlled manner, were monodispersed in shape and size. The role of ammonia, sodium citrate, polyvinylpyrrolidone, chloroauric acid and NaCl in shape control is discussed in detail. The oriented growth of these micro-/nanostructures directed by reverse micelles followed a solution-solution-solid (SSS) mechanism, similar to the classic vapor-liquid-solid mechanism. The evolution processes of silica rods, tubes, crutches, bundles and bells were recorded using transmission electron microscopy to prove the SSS mechanism.

Another Demo of the Unusual Thermal Properties of Rubber

ERIC Educational Resources Information Center

Liff, Mark I.

2010-01-01

The unusual thermal behavior of rubbers, though discovered a long time ago, can still be mind-boggling for students and teachers who encounter this class of polymeric systems. Unlike other solids, stretched elastic polymers shrink upon heating. This is a manifestation of the Gough-Joule (G-J) effect. Joule in the 1850s studied the thermal behavior…

Harnessing out-of-plane deformation to design 3D architected lattice metamaterials with tunable Poisson's ratio.

PubMed

Li, Tiantian; Hu, Xiaoyi; Chen, Yanyu; Wang, Lifeng

2017-08-21

Auxetic materials exhibiting a negative Poisson's ratio are of great research interest due to their unusual mechanical responses and a wide range of potential deployment. Efforts have been devoted to exploring novel 2D and 3D auxetic structures through rational design, optimization, and taking inspiration from nature. Here we report a 3D architected lattice system showing a negative Poisson's ratio over a wide range of applied uniaxial stretch. 3D printing, experimental tests, numerical simulation, and analytical modeling are implemented to quantify the evolution of the Poisson's ratio and reveal the underlying mechanisms responsible for this unusual behavior. We further show that the auxetic behavior can be controlled by tailoring the geometric features of the ligaments. The findings reported here provide a new routine to design architected metamaterial systems exhibiting unusual properties and having a wide range of potential applications.

The Nonlinear Magnetosphere: Expressions in MHD and in Kinetic Models

NASA Technical Reports Server (NTRS)

Hesse, Michael; Birn, Joachim

2011-01-01

Like most plasma systems, the magnetosphere of the Earth is governed by nonlinear dynamic evolution equations. The impact of nonlinearities ranges from large scales, where overall dynamics features are exhibiting nonlinear behavior, to small scale, kinetic, processes, where nonlinear behavior governs, among others, energy conversion and dissipation. In this talk we present a select set of examples of such behavior, with a specific emphasis on how nonlinear effects manifest themselves in MHD and in kinetic models of magnetospheric plasma dynamics.

Adenine phosphoribosyltransferase from Sulfolobus solfataricus is an enzyme with unusual kinetic properties and a crystal structure that suggests it evolved from a 6-oxopurine phosphoribosyltransferase.

PubMed

Jensen, Kaj Frank; Hansen, Michael Riis; Jensen, Kristine Steen; Christoffersen, Stig; Poulsen, Jens-Christian Navarro; Mølgaard, Anne; Kadziola, Anders

2015-04-14

The adenine phosphoribosyltransferase (APRTase) encoded by the open reading frame SSO2342 of Sulfolobus solfataricus P2 was subjected to crystallographic, kinetic, and ligand binding analyses. The enzyme forms dimers in solution and in the crystals, and binds one molecule of the reactants 5-phosphoribosyl-α-1-pyrophosphate (PRPP) and adenine or the product adenosine monophosphate (AMP) or the inhibitor adenosine diphosphate (ADP) in each active site. The individual subunit adopts an overall structure that resembles a 6-oxopurine phosphoribosyltransferase (PRTase) more than known APRTases implying that APRT functionality in Crenarchaeotae has its evolutionary origin in this family of PRTases. Only the N-terminal two-thirds of the polypeptide chain folds as a traditional type I PRTase with a five-stranded β-sheet surrounded by helices. The C-terminal third adopts an unusual three-helix bundle structure that together with the nucleobase-binding loop undergoes a conformational change upon binding of adenine and phosphate resulting in a slight contraction of the active site. The inhibitor ADP binds like the product AMP with both the α- and β-phosphates occupying the 5'-phosphoribosyl binding site. The enzyme shows activity over a wide pH range, and the kinetic and ligand binding properties depend on both pH and the presence/absence of phosphate in the buffers. A slow hydrolysis of PRPP to ribose 5-phosphate and pyrophosphate, catalyzed by the enzyme, may be facilitated by elements in the C-terminal three-helix bundle part of the protein.

Exploration of near the origin and the asymptotic behaviors of the Kohn-Sham kinetic energy density for two-dimensional quantum dot systems with parabolic confinement

NASA Astrophysics Data System (ADS)

Jana, Subrata; Samal, Prasanjit

2018-01-01

The behaviors of the positive definite Kohn-Sham kinetic energy density near the origin and at the asymptotic region play a major role in designing meta-generalized gradient approximations (meta-GGAs) for exchange in low-dimensional quantum systems. It is shown that near the origin of the parabolic quantum dot, the Kohn-Sham kinetic energy differs from its von Weizsäcker counterpart due to the p orbital contributions, whereas in the asymptotic region, the difference between the above two kinetic energy densities goes as ˜ρ/(r ) r2 . All these behaviors have been explored using the two-dimensional isotropic quantum harmonic oscillator as a test case. Several meta-GGA ingredients are then studied by making use of the above findings. Also, the asymptotic conditions for the exchange energy density and the potential at the meta-GGA level are proposed using the corresponding behaviors of the two kinetic energy densities.

Exploration of near the origin and the asymptotic behaviors of the Kohn-Sham kinetic energy density for two-dimensional quantum dot systems with parabolic confinement.

PubMed

Jana, Subrata; Samal, Prasanjit

2018-01-14

The behaviors of the positive definite Kohn-Sham kinetic energy density near the origin and at the asymptotic region play a major role in designing meta-generalized gradient approximations (meta-GGAs) for exchange in low-dimensional quantum systems. It is shown that near the origin of the parabolic quantum dot, the Kohn-Sham kinetic energy differs from its von Weizsäcker counterpart due to the p orbital contributions, whereas in the asymptotic region, the difference between the above two kinetic energy densities goes as ∼ρ(r)r 2 . All these behaviors have been explored using the two-dimensional isotropic quantum harmonic oscillator as a test case. Several meta-GGA ingredients are then studied by making use of the above findings. Also, the asymptotic conditions for the exchange energy density and the potential at the meta-GGA level are proposed using the corresponding behaviors of the two kinetic energy densities.

P-I class metalloproteinase from Bothrops moojeni venom is a post-proline cleaving peptidase with kininogenase activity: insights into substrate selectivity and kinetic behavior.

PubMed

Okamoto, Débora N; Kondo, Marcia Y; Oliveira, Lilian C G; Honorato, Rodrigo V; Zanphorlin, Leticia M; Coronado, Monika A; Araújo, Mariana S; da Motta, Guacyara; Veronez, Camila L; Andrade, Sheila S; Oliveira, Paulo S L; Arni, Raghuvir K; Cintra, Adelia C O; Sampaio, Suely V; Juliano, Maria A; Juliano, Luiz; Murakami, Mário T; Gouvea, Iuri E

2014-03-01

Snake venom metalloproteinases (SVMPs) belonging to P-I class are able to hydrolyze extracellular matrix proteins and coagulation factors triggering local and systemic reactions by multiple molecular mechanisms that are not fully understood. BmooMPα-I, a P-I class SMVP from Bothrops moojeni venom, was active upon neuro- and vaso-active peptides including angiotensin I, bradykinin, neurotensin, oxytocin and substance P. Interestingly, BmooMPα-I showed a strong bias towards hydrolysis after proline residues, which is unusual for most of characterized peptidases. Moreover, the enzyme showed kininogenase activity similar to that observed in plasma and cells by kallikrein. FRET peptide assays indicated a relative promiscuity at its S2-S'2 subsites, with proline determining the scissile bond. This unusual post-proline cleaving activity was confirmed by the efficient hydrolysis of the synthetic combinatorial library MCA-GXXPXXQ-EDDnp, described as resistant for canonical peptidases, only after Pro residues. Structural analysis of the tripeptide LPL complexed with BmooMPα-I, generated by molecular dynamics simulations, assisted in defining the subsites and provided the structural basis for subsite preferences such as the restriction of basic residues at the S2 subsite due to repulsive electrostatic effects and the steric impediment for large aliphatic or aromatic side chains at the S1 subsite. These new functional and structural findings provided a further understanding of the molecular mechanisms governing the physiological effects of this important class of enzymes in envenomation process. Copyright © 2014 Elsevier B.V. All rights reserved.

Structural Changes in PEO-PPO-PEO Gels Induced by Methylparaben and Dexamethasone Observed Using Time-Resolved SAXS

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

Meznarich, Norman A.K.; Juggernauth, K Anne; Batzli, Kiersten M

2011-11-17

Aqueous solutions of polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblock copolymers (commercially available as Pluronic surfactants) micellize and structurally arrange into cubic quasicrystalline lattices as their temperature is raised. This structural evolution is seen macroscopically as a gelation, and the presence of these ordered phases can be controlled through both polymer concentration and temperature. The presence of added solutes within the dispersions can also affect the onset and kinetics of structure formation. Here we investigate the structures formed in Pluronic F127 solutions ranging from 20 to 30% with two pharmaceutical additives [methylparaben (MP) and dexamethasone (DX)] using small-angle X-ray scattering (SAXS). We observe bothmore » the progressive evolution and breakdown of these structures as the temperature is increased from 0 to 80 °C. Additionally, we conducted time-resolved SAXS measurements to elucidate the kinetics of the structural evolution. On the basis of the evolution of scattering peaks as the samples were being heated, we suggest that added MP changes the nucleation behavior of fcc phases within the sample from a heterogeneous process to a more homogeneous distribution of nucleated species. MP and DX also stabilize the micelle lattices, allowing them to persevere at higher temperatures. We observed the unusual result that the presence of DX caused the primary peaks of the structure factor to be suppressed, while preserving the higher order peaks. The primary peaks reappeared at the highest temperatures tested.« less

The Lunar dusty plasmas -levitation and transport.

NASA Astrophysics Data System (ADS)

Atamaniuk, Barbara; Rothkaehl, Hanna

Lunar dust can exhibit unusual behavior -due to electron photoemission via solar-UV radiation the lunar surface represents a complex plasma -"dusty plasma". The dust grains and lunar surface are electrostatically charged by the Moon's interaction with the local plasma environ-ment and the photoemission of electrons due to solar UV and X-rays. This effect causes the like-charged surface and dust particles to repel each other, and creates a near-surface electric field. Lunar dust must be treated as a dusty plasma. Using analytic (kinetic (Vlasov) and magnetohydrodynamic theory ) and numerical modeling we show physical processes related to levitation and transport dusty plasma on the Moon. These dust grains could affect the lunar environment for radio wave and plasma diagnostics and interfere with exploration activities. References: 1. Wilson T.L. (1992), in Analysis of Interplanetary Dust, M. Zolensky et al. AIP Conf.Proc. 310, 33-44 (AIP, NY), 2.Wilson T.L."LUNAR DUST AND DUSTY PLASMA PHYSICS".40th Lunar and Planetary Science Conference (2009), 3. Grün E., et al.(1993),Nature 363, 144. 4. Morfill G. and Grün E.(1979), Planet. Space Sci.. 27, 1269, 1283, 5. Manka R. and Michel F. (1971), Proc. 2nd Lun. Sci. Conf. 2, 1717 (MIT Press, Cambridge). 6. Manka R. et al.(1973), Lun. Sci.-III, 504. 7. Barbara Atamaniuk "Kinetic Description of Localized Plasma Structure in Dusty Plasmas". Czechoslovak Journal of Physics Vol.54 C 2004

Diagnostic Utility of Wireless Video-Electroencephalography in Unsedated Dogs.

PubMed

James, F M K; Cortez, M A; Monteith, G; Jokinen, T S; Sanders, S; Wielaender, F; Fischer, A; Lohi, H

2017-09-01

Poor agreement between observers on whether an unusual event is a seizure drives the need for a specific diagnostic tool provided by video-electroencephalography (video-EEG) in human pediatric epileptology. That successful classification of events would be positively associated with increasing EEG recording length and higher event frequency reported before video-EEG evaluation; that a novel wireless video-EEG technique would clarify whether unusual behavioral events were seizures in unsedated dogs. Eighty-one client-owned dogs of various breeds undergoing investigation of unusual behavioral events at 4 institutions. Retrospective case series: evaluation of wireless video-EEG recordings in unsedated dogs performed at 4 institutions. Electroencephalography achieved/excluded diagnosis of epilepsy in 58 dogs (72%); 25 dogs confirmed with epileptic seizures based on ictal/interictal epileptiform discharges, and 33 dogs with no EEG abnormalities associated with their target events. As reported frequency of the target events decreased (annually, monthly, weekly, daily, hourly, minutes, seconds), EEG was less likely to achieve diagnosis (P < 0.001). Every increase in event frequency increased the odds of achieving diagnosis by 2.315 (95% confidence interval: 1.36-4.34). EEG recording length (mean = 3.69 hours, range: 0.17-22.5) was not associated (P = 0.2) with the likelihood of achieving a diagnosis. Wireless video-EEG in unsedated dogs had a high success for diagnosis of unusual behavioral events. This technique offered a reliable clinical tool to investigate the epileptic origin of behavioral events in dogs. Copyright © 2017 The Authors. Journal of Veterinary Internal Medicine published by Wiley Periodicals, Inc. on behalf of the American College of Veterinary Internal Medicine.

Kinetics Study on the Effect of NaCl on the CaSO4 Dissolution Behavior

NASA Astrophysics Data System (ADS)

Song, Jingyao; Shi, Peiyang; Wang, Yeguang; Jiang, Maofa

2018-01-01

The study of the dissolution kinetics of CaSO4 is essential for the control of the dissolution and recrystallization behavior of CaSO4. In this work, the kinetic behavior of CaSO4 dissolved in NaCl solution was investigated by means of conductivity meter. The results show that with the increase of concentration of NaCl, the temperature rise and the time prolonged, the dissolution rate of dihydrate CaSO4 gradually increases, and the dissolved apparent activation energy is gradually decreased. When the NaCl concentration is 1.8%, the dissolution kinetic equation is 1-(1-α) 1/3=5.46*10-4exp (-9147/RT) t; When the NaCl concentration is 3.0%, the dissolution kinetic equation is 1-(1-α) 1/3=2.81×10-4 exp (-6753/RT)t; When the NaCl concentration is 3.6%, the dissolution kinetic equation is 1-(1-α) 1/3=3.07×l0-4exp(-6103/RT)t.

Timing Behavior of the Magnetically Active Rotation-Powered Pulsar in the Supernova Remnant Kesteven 75

NASA Technical Reports Server (NTRS)

Livingstone, Margaret A.; Gavriil, Fotis P.; Kaspi, Victoria M.

2009-01-01

We report a large spin-up glitch in PSR J1846-0258 which coincided with the onset of magnetar-like behavior on 2006 May 31. We show that the pulsar experienced an unusually large glitch recovery, with a recovery fraction of Q = 5.9+/-0.3, resulting in a net decrease of the pulse frequency. Such a glitch recovery has never before been observed in a rotation-powered pulsar, however, similar but smaller glitch over-recovery has been recently reported in the magnetar AXP 4U 0142+61 and may have occurred in the SGR 1900+14. We discuss the implications of the unusual timing behavior in PSR J1846-0258 on its status as the first identified magnetically active rotation-powered pulsar.

Probing the remarkable thermal kinetics of visual rhodopsin with E181Q and S186A mutants

NASA Astrophysics Data System (ADS)

Guo, Ying; Hendrickson, Heidi P.; Videla, Pablo E.; Chen, Ya-Na; Ho, Junming; Sekharan, Sivakumar; Batista, Victor S.; Tully, John C.; Yan, Elsa C. Y.

2017-06-01

We recently reported a very unusual temperature dependence of the rate of thermal reaction of wild type bovine rhodopsin: the Arrhenius plot exhibits a sharp "elbow" at 47 °C and, in the upper temperature range, an unexpectedly large activation energy (114 ± 8 kcal/mol) and an enormous prefactor (1072±5 s-1). In this report, we present new measurements and a theoretical model that establish convincingly that this behavior results from a collective, entropy-driven breakup of the rigid hydrogen bonding networks (HBNs) that hinder the reaction at lower temperatures. For E181Q and S186A, two rhodopsin mutants that disrupt the HBNs near the binding pocket of the 11-cis retinyl chromophore, we observe significant decreases in the activation energy (˜90 kcal/mol) and prefactor (˜1060 s-1), consistent with the conclusion that the reaction rate is enhanced by breakup of the HBN. The results provide insights into the molecular mechanism of dim-light vision and eye diseases caused by inherited mutations in the rhodopsin gene that perturb the HBNs.

Two-sided block of a dual-topology F- channel.

PubMed

Turman, Daniel L; Nathanson, Jacob T; Stockbridge, Randy B; Street, Timothy O; Miller, Christopher

2015-05-05

The Fluc family is a set of small membrane proteins forming F(-)-specific electrodiffusive ion channels that rescue microorganisms from F(-) toxicity during exposure to weakly acidic environments. The functional channel is built as a dual-topology homodimer with twofold symmetry parallel to the membrane plane. Fluc channels are blocked by nanomolar-affinity fibronectin-domain monobodies originally selected from phage-display libraries. The unusual symmetrical antiparallel dimeric architecture of Flucs demands that the two chemically equivalent monobody-binding epitopes reside on opposite ends of the channel, a double-sided blocking situation that has never before presented itself in ion channel biophysics. However, it is not known if both sites can be simultaneously occupied, and if so, whether monobodies bind independently or cooperatively to their transmembrane epitopes. Here, we use direct monobody-binding assays and single-channel recordings of a Fluc channel homolog to reveal a novel trimolecular blocking behavior that reveals a doubly occupied blocked state. Kinetic analysis of single-channel recordings made with monobody on both sides of the membrane shows substantial negative cooperativity between the two blocking sites.

Atypical kinetic behavior of chloroperoxidase-mediated oxidative halogenation of polycyclic aromatic hydrocarbons.

PubMed

Aburto, Jorge; Correa-Basurto, Jose; Torres, Eduardo

2008-12-01

We have identified an atypical kinetic behavior for the oxidative halogenation of several polycyclic aromatic hydrocarbons (PAHs) by chloroperoxidase (CPO) from Caldariomyces fumago. This behavior resembles the capacity of some members of the P450 family to simultaneously recognize several substrate molecules at their active sites. Indeed, fluorometric studies showed that PAHs exist in solution as monomers and pi-pi dimers that interact to different extents with CPO. The dissociation constants of dimerization were evaluated for every single PAH by spectrofluorometry. Furthermore, docking studies also suggest that CPO might recognize either one or two substrate molecules in its active site. The atypical sigmoidal kinetic behavior of CPO in the oxidative halogenation of PAHs is explained in terms of different kinetic models for non-heteroatomic PAHs (naphthalene, anthracene and pyrene). The results suggest that the actual substrate for CPO in this study was the pi-pi dimer for all evaluated PAHs.

Structural metatransition of energetically tangled crystalline phases.

PubMed

Zhou, Dan; Li, Quan; Zheng, Weitao; Ma, Yanming; Chen, Changfeng

2017-02-08

We solve the longstanding puzzle of pressure induced structural evolution of SnSe using a swarm structure search method combined with first-principles phonon and kinetic barrier calculations. Our results identify a dynamic set of nearly degenerate crystalline SnSe phases that are separated by low kinetic barriers and undergo an unusual type of structural transitions characterized by a dynamically changing mix of the constituent phases. We introduce a new concept of structural metatransition to highlight the transitional nature of such phase transitions. Our theoretical prediction is corroborated by X-ray diffraction measurements, and this intriguing phenomenon offers insights into the enigmatic property variations of SnSe under pressure. This work raises prospects of considerably improving characterization and understanding of intrinsic multiphase crystals and their dynamic evolution.

The Young Offender.

ERIC Educational Resources Information Center

MacLeod, Hinson

1979-01-01

Looks at delinquency from the viewpoint of a training school chaplain and outlines factors believed to contribute to the development of delinquent behavior. Signs of maladjustment include overactivity, acute anxiety and fear, depression, psychosomatic disorders, unusual behavior, negative attitudes toward others and themselves, and resistance to…

Unusual terahertz spectral weight and conductivity dynamics of the insulator-metal transition in Pr0.5Nd0.5NiO3 thin films

NASA Astrophysics Data System (ADS)

Santhosh Kumar, K.; Das, Sarmistha; Eswara Phanindra, V.; Rana, D. S.

2017-12-01

The metal-insulator transition (MIT) in correlated systems is a central phenomenon that possesses potential for several emerging technologies. We investigate the kinetics of such MIT in perovskite nickelates by studying the terahertz (THz) low-energy charge dynamics in orthorhombic and tetragonal symmetries of Pr0.5Nd0.5NiO3 thin films. The THz conductivity of the orthorhombic thin film is dominated by Drude behavior in the entire temperature range, albeit a dominant anomaly at and around the MIT region. The tetragonal thin film exhibits different overall THz conductivity dynamics though, i.e. of a Drude-Smith (DS) type in the entire temperature range, the DS coefficient signifying dominant backscattering peaks in the MIT region. While the overall THz dynamics profile is different for the two films, a unique yet similar sensitivity of the I-M transition regions of both films to THz frequencies underlines the fundamental origin of the bi-critical phase around MIT of the nickelates. The peculiar behavior around the I-M transition, as evaluated in the framework of a percolative path approximation based Dyre expression, emphasizes the importance of critical metallic volume fraction (f c) for the percolation conduction, as an f c of ~0.645 obtained for the present case, along with evidence for the absence of super-heating.

The phenomenon of claimed memories of previous lives: possible interpretations and importance.

PubMed

Stevenson, I

2000-04-01

Several disorders or abnormalities observed in medicine and psychology are not explicable (or not fully explicable) by genetics and environmental influences, either alone or together. These include phobias and philias observed in early infancy, unusual play in childhood, homosexuality, gender identity disorder, a child's idea of having parents other than its own, differences in temperament manifested soon after birth, unusual birthmarks and their correspondence with wounds on a deceased person, unusual birth defects, and differences (physical and behavioral) between monozygotic twins. The hypothesis of previous lives can contribute to the further understanding of these phenomena. Copyright 2000 Harcourt Publishers Ltd.

Buoyant production and consumption of turbulence kinetic energy in cloud-topped mixed layers

NASA Technical Reports Server (NTRS)

Randall, D. A.

1984-01-01

It is pointed out that studies of the entraining planetary boundary layer (PBL) have generally emphasized the role of buoyancy fluxes in driving entrainment. The buoyancy flux is proportional to the rate of conversion of the potential energy of the mean flow into the kinetic energy of the turbulence. It is not unusual for conversion to proceed in both directions simultaneously. This occurs, for instance, in both clear and cloudy convective mixed layers which are capped by inversions. A partitioning of the net conversion into positive parts, generating turbulence kinetic energy (TKE), and negative parts (TKE-consuming), would make it possible to include the positive part in the gross production rate, and closure would be achieved. Three different approaches to partitioning have been proposed. The present investigation is concerned with a comparison of the three partitioning theories. Particular attention is given to the cloud-topped mixed layer because in this case the differences between two partitioning approaches are most apparent.

Modeling Temporal Behavior in Large Networks: A Dynamic Mixed-Membership Model

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

Rossi, R; Gallagher, B; Neville, J

Given a large time-evolving network, how can we model and characterize the temporal behaviors of individual nodes (and network states)? How can we model the behavioral transition patterns of nodes? We propose a temporal behavior model that captures the 'roles' of nodes in the graph and how they evolve over time. The proposed dynamic behavioral mixed-membership model (DBMM) is scalable, fully automatic (no user-defined parameters), non-parametric/data-driven (no specific functional form or parameterization), interpretable (identifies explainable patterns), and flexible (applicable to dynamic and streaming networks). Moreover, the interpretable behavioral roles are generalizable, computationally efficient, and natively supports attributes. We applied ourmore » model for (a) identifying patterns and trends of nodes and network states based on the temporal behavior, (b) predicting future structural changes, and (c) detecting unusual temporal behavior transitions. We use eight large real-world datasets from different time-evolving settings (dynamic and streaming). In particular, we model the evolving mixed-memberships and the corresponding behavioral transitions of Twitter, Facebook, IP-Traces, Email (University), Internet AS, Enron, Reality, and IMDB. The experiments demonstrate the scalability, flexibility, and effectiveness of our model for identifying interesting patterns, detecting unusual structural transitions, and predicting the future structural changes of the network and individual nodes.« less

Catastrophic Disruption Threshold and Maximum Deflection from Kinetic Impact

NASA Astrophysics Data System (ADS)

Cheng, A. F.

2017-12-01

The use of a kinetic impactor to deflect an asteroid on a collision course with Earth was described in the NASA Near-Earth Object Survey and Deflection Analysis of Alternatives (2007) as the most mature approach for asteroid deflection and mitigation. The NASA DART mission will demonstrate asteroid deflection by kinetic impact at the Potentially Hazardous Asteroid 65803 Didymos in October, 2022. The kinetic impactor approach is considered to be applicable with warning times of 10 years or more and with hazardous asteroid diameters of 400 m or less. In principle, a larger kinetic impactor bringing greater kinetic energy could cause a larger deflection, but input of excessive kinetic energy will cause catastrophic disruption of the target, leaving possibly large fragments still on collision course with Earth. Thus the catastrophic disruption threshold limits the maximum deflection from a kinetic impactor. An often-cited rule of thumb states that the maximum deflection is 0.1 times the escape velocity before the target will be disrupted. It turns out this rule of thumb does not work well. A comparison to numerical simulation results shows that a similar rule applies in the gravity limit, for large targets more than 300 m, where the maximum deflection is roughly the escape velocity at momentum enhancement factor β=2. In the gravity limit, the rule of thumb corresponds to pure momentum coupling (μ=1/3), but simulations find a slightly different scaling μ=0.43. In the smaller target size range that kinetic impactors would apply to, the catastrophic disruption limit is strength-controlled. A DART-like impactor won't disrupt any target asteroid down to significantly smaller size than the 50 m below which a hazardous object would not penetrate the atmosphere in any case unless it is unusually strong.

Disturbed mouse circadian rhythm before the Kobe EQ in 1995

NASA Astrophysics Data System (ADS)

Yokoi, Sayoko

2013-04-01

Legends of macro-anomalies before large earthquakes have been passed down for generations in Asia. Most of the statements on earthquake precursors are considered unreliable afterthoughts by traditional scientists. However, disturbed biological rhythms in mice were observed before the Kobe EQ in 1995 (Yokoi et al, 2003). The records of unusual mouse behavior before the earthquake were obtained to study biological clock at Institute for Protein Research, Osaka University. It is clarified that the disturbance was very rare phenomena statistically. Similar phenomenon was observed before the Wenchuan earthquake in 2008, too (Li et al, 2009). In the presentation, I will discuss the phenomena as one example of preseismic unusual animal behaviors.

Unusual raptor nests around the world

USGS Publications Warehouse

Ellis, D.H.; Craig, T.; Craig, E.; Postupalsky, S.; LaRue, C.T.; Nelson, R.W.; Anderson, D.W.; Henny, C.J.; Watson, J.; Millsap, B.A.; Dawson, J.W.; Cole, K.L.; Martin, E.M.; Margalida, A.; Kung, P.

2009-01-01

From surveys in many countries, we report raptors using unusual nesting materials (e.g., paper money, rags, metal, antlers, and large bones) and unusual nesting situations. For example, we documented nests of Steppe Eagles Aquila nipalensis and Upland Buzzards Buteo hemilasius on the ground beside well-traveled roads, Saker Falcon Falco cherrug eyries in attics and a cistern, and Osprey Pandion haliaetus nests on the masts of boats and on a suspended automobile. Other records include a Golden Eagle A. chrysaetos nest 7.0 m in height, believed to be the tallest nest ever described, and, for the same species, we report nesting in rudimentary nests. Some nest sites are within a few meters of known predators or competitors. These unusual observations may be important in revealing the plasticity of a species' behavioral repertoire. ?? 2009 The Raptor Research Foundation, Inc.

Mechanisms and kinetic profiles of superoxide-stimulated nitrosative processes in cells using a diaminofluorescein probe.

PubMed

Damasceno, Fernando Cruvinel; Facci, Rômulo Rodrigues; da Silva, Thalita Marques; Toledo, José Carlos

2014-12-01

In this study, we examined the mechanisms and kinetic profiles of intracellular nitrosative processes using diaminofluorescein (DAF-2) as a target in RAW 264.7 cells. The intracellular formation of the fluorescent, nitrosated product diaminofluorescein triazol (DAFT) from both endogenous and exogenous nitric oxide (NO) was prevented by deoxygenation and by cell membrane-permeable superoxide (O2(-)) scavengers but not by extracellular bovine Cu,Zn-SOD. In addition, the DAFT formation rate decreased in the presence of cell membrane-permeable Mn porphyrins that are known to scavenge peroxynitrite (ONOO(-)) but was enhanced by HCO3(-)/CO2. Together, these results indicate that nitrosative processes in RAW 264.7 cells depend on endogenous intracellular O2(-) and are stimulated by ONOO(-)/CO2-derived radical oxidants. The N2O3 scavenger sodium azide (NaN3) only partially attenuated the DAFT formation rate and only with high NO (>120 nM), suggesting that DAFT formation occurs by nitrosation (azide-susceptible DAFT formation) and predominantly by oxidative nitrosylation (azide-resistant DAFT formation). Interestingly, the DAFT formation rate increased linearly with NO concentrations of up to 120-140 nM but thereafter underwent a sharp transition and became insensitive to NO. This behavior indicates the sudden exhaustion of an endogenous cell substrate that reacts rapidly with NO and induces nitrosative processes, consistent with the involvement of intracellular O2(-). On the other hand, intracellular DAFT formation stimulated by a fixed flux of xanthine oxidase-derived extracellular O2(-) that also occurs by nitrosation and oxidative nitrosylation increased, peaked, and then decreased with increasing NO, as previously observed. Thus, our findings complementarily show that intra- and extracellular O2(-)-dependent nitrosative processes occurring by the same chemical mechanisms do not necessarily depend on NO concentration and exhibit different unusual kinetic profiles with NO dynamics, depending on the biological compartment in which NO and O2(-) interact. Copyright © 2014 Elsevier Inc. All rights reserved.

Response of the Pre-Oriented Goal-Directed Attention to Usual and Unusual Distractors: A Preliminary Study

PubMed Central

Baghdadi, Golnaz; Towhidkhah, Farzad; Rostami, Reza; Raza, Mohsen

2017-01-01

Introduction: In this study, we investigated the distraction power of the unusual and usual images on the attention of 20 healthy primary school children. Methods: Our study was different from previous ones in that the participants were asked to fix the initial position of their attention on a predefined location after being presented with unusual images as distractors. The goals were presented in locations, which were far from the attraction basin of distractors. We expected that the pre-orienting of the attention to the position of targets would reduce the attractive effect of unusual images compared to the usual ones. The percentage of correct responses and the reaction time were measured as behavioral indicators of attention performance. Results: Results showed that using the goal-directed attention, subjects ignored both kinds of distractors nearly the same way. Conclusion: With regard to previous reports about more attraction towards the unusual images, it is suggested that the dynamics of the visual attention system be sensitive to the initial condition. That is, changing the initial position of the attention can lead to the decrement of the unusual images effects. However, several other possibilities such as a probable delay in processing unusual features could explain this observation, too. PMID:28540000

Kinetics of Cd(ii) adsorption and desorption on ferrihydrite: experiments and modeling.

PubMed

Liang, Yuzhen; Tian, Lei; Lu, Yang; Peng, Lanfang; Wang, Pei; Lin, Jingyi; Cheng, Tao; Dang, Zhi; Shi, Zhenqing

2018-05-15

The kinetics of Cd(ii) adsorption/desorption on ferrihydrite is an important process affecting the fate, transport, and bioavailability of Cd(ii) in the environment, which was rarely systematically studied and understood at quantitative levels. In this work, a combination of stirred-flow kinetic experiments, batch adsorption equilibrium experiments, high-resolution transmission electron microscopy (HR-TEM), and mechanistic kinetic modeling were used to study the kinetic behaviors of Cd(ii) adsorption/desorption on ferrihydrite. HR-TEM images showed the open, loose, and sponge-like structure of ferrihydrite. The batch adsorption equilibrium experiments revealed that higher pH and initial metal concentration increased Cd(ii) adsorption on ferrihydrite. The stirred-flow kinetic results demonstrated the increased adsorption rate and capacity as a result of the increased pH, influent concentration, and ferrihydrite concentration. The mechanistic kinetic model successfully described the kinetic behaviors of Cd(ii) during the adsorption and desorption stages under various chemistry conditions. The model calculations showed that the adsorption rate coefficients varied as a function of solution chemistry, and the relative contributions of the weak and strong ferrihydrite sites for Cd(ii) binding varied with time at different pH and initial metal concentrations. Our model is able to quantitatively assess the contributions of each individual ferrihydrite binding site to the overall Cd(ii) adsorption/desorption kinetics. This study provided insights into the dynamic behavior of Cd(ii) and a predictive modeling tool for Cd(ii) adsorption/desorption kinetics when ferrihydrite is present, which may be helpful for the risk assessment and management of Cd contaminated sites.

Biphasic Kinetic Behavior of Nitrate Reductase from Heterocystous, Nitrogen-Fixing Cyanobacteria 1

PubMed Central

Martin-Nieto, José; Flores, Enrique; Herrero, Antonia

1992-01-01

Nitrate reductase activity from filamentous, heterocyst-forming cyanobacteria showed a biphasic kinetic behavior with respect to nitrate as the variable substrate. Two kinetic components were detected, the first showing a higher affinity for nitrate (Km, 0.05-0.25 mm) and a lower catalytic activity and the second showing a lower affinity for nitrate (Km, 5-25 mm) and a higher (3- to 5-fold) catalytic activity. In contrast, among unicellular cyanobacteria, most representatives studied exhibited a monophasic, Michaelis-Menten kinetic pattern for nitrate reductase activity. Biphasic kinetics remained unchanged with the use of different assay conditions (i.e. cell disruption or permeabilization, two different electron donors) or throughout partial purification of the enzyme. PMID:16652939

Kinetics of proton transfer from tetra(4-nitro-5- tert-butyl)phthalocyanine to nitrogen-containing bases in benzene

NASA Astrophysics Data System (ADS)

Petrov, O. A.; Kuzmina, E. L.; Maizlish, V. E.; Rodionov, A. V.

2014-01-01

The acid-basic interaction between tetra(4-nitro-5- tert-butyl)phthalocyanine and pyridine, 2-methylpyridine, morpholine, piperidine, n-butylamine, diethylamine, and triethylamine in benzene is studied. It is found that the intermolecular transfer of protons of NH groups from tetra(4-nitro-5- tert-butyl)phthalocyanine to morpholine and diethylamine is characterized by unusually low values of the reaction constant rates. The effect of the structure of tetra(4-nitro-5- tert-butyl)phthalocyanine and tetra(3-nitro-5- tert-butyl)phthalocyanine, and of the nature of the base on the kinetic parameters of acid-base interaction is demonstrated. A structure is proposed for complexes with the transfer of displaced phthalocyanines' protons. It is found that they undergo decomposition over time.

Ligand-hole localization in oxides with unusual valence Fe

PubMed Central

Chen, Wei-Tin; Saito, Takashi; Hayashi, Naoaki; Takano, Mikio; Shimakawa, Yuichi

2012-01-01

Unusual high-valence states of iron are stabilized in a few oxides. A-site-ordered perovskite-structure oxides contain such iron cations and exhibit distinct electronic behaviors at low temperatures, e.g. charge disproportionation (4Fe4+ → 2Fe3+ + 2Fe5+) in CaCu3Fe4O12 and intersite charge transfer (3Cu2+ + 4Fe3.75+ → 3Cu3+ + 4Fe3+) in LaCu3Fe4O12. Here we report the synthesis of solid solutions of CaCu3Fe4O12 and LaCu3Fe4O12 and explain how the instabilities of their unusual valence states of iron are relieved. Although these behaviors look completely different from each other in simple ionic models, they can both be explained by the localization of ligand holes, which are produced by the strong hybridization of iron d and oxygen p orbitals in oxides. The localization behavior in the charge disproportionation of CaCu3Fe4O12 is regarded as charge ordering of the ligand holes, and that in the intersite charge transfer of LaCu3Fe4O12 is regarded as a Mott transition of the ligand holes. PMID:22690318

Childhood and Current Autistic Features in Adolescents with Schizotypal Personality Disorder

PubMed Central

Esterberg, Michelle L.; Trotman, Hanan D.; Brasfield, Joy L.; Compton, Michael T.; Walker, Elaine F.

2008-01-01

The diagnostic boundaries between autistic- and schizophrenia-spectrum disorders have varied over the years, and some overlap in diagnostic criteria persists. The present study examined childhood and current signs of autistic disorder (AD) in adolescents with schizotypal personality disorder (SPD) or other personality disorders, as well as healthy controls. A structured interview was administered to rate participants’ current symptoms. Participants’ guardians were interviewed with the Autism Diagnostic Inventory-Revised (ADI-R), a clinical assessment of childhood and current autistic signs. Compared to both the other personality-disordered and healthy groups, adolescents with SPD were rated as having significantly more impairment on childhood and current social functioning, and having more unusual interests and behaviors. For the entire sample, impaired childhood social functioning and unusual interests and behaviors were associated with higher negative symptom scores. Current impairments in social functioning, unusual interests and behaviors, and communication were also linked with greater negative symptoms. However, neither childhood nor current autistic features significantly predicted later conversion to an Axis I psychotic disorder over the course of three years of follow-up. The findings indicate that past and current autistic signs are more common in adolescents with SPD, but neither current nor childhood autistic features are linked with conversion to psychosis. PMID:18554872

Cyber for the Middleweight Fighter: Recommendations for Cyberspace Capabilities for the United States Marine Corps

DTIC Science & Technology

2013-02-14

L acts to “provided resources for national and joint kinetic attack requirements.”24 Additionally, the Marine Corps Force Structure Review Group...for unusual system activity and searching for signs of known malware, unlike what is depicted in movies such as Hackers, where opposing cyber...never admitted involvement but the attacks originated in Russia. The FBI code name for the inquiry was Moonlight Maze. 29. Jeffrey Carr, Inside Cyber

Rapid kinetics of dehalogenation promoted by iodotyrosine deiodinase from human thyroid.

PubMed

Bobyk, Kostyantyn D; Ballou, David P; Rokita, Steven E

2015-07-28

Reductive dehalogenation such as that catalyzed by iodotyrosine deiodinase (IYD) is highly unusual in aerobic organisms but necessary for iodide salvage from iodotyrosine generated during thyroxine biosynthesis. Equally unusual is the dependence of this process on flavin. Rapid kinetics have now been used to define the basic processes involved in IYD catalysis. Time-dependent quenching of flavin fluorescence was used to monitor halotyrosine association to IYD. The substrates chloro-, bromo-, and iodotyrosine bound with similar rate constants (kon) ranging from 1.3 × 10(6) to 1.9 × 10(6) M(-1) s(-1). Only the inert substrate analogue fluorotyrosine exhibited a significantly (5-fold) slower kon (0.3 × 10(6) M(-1) s(-1)). All data fit a standard two-state model and indicated that no intermediate complex accumulated during closure of the active site lid induced by substrate. Subsequent halide elimination does not appear to limit reactions of bromo- and iodotyrosine since both fully oxidized the reduced enzyme with nearly equivalent second-order rate constants (7.3 × 10(3) and 8.6 × 10(3) M(-1) s(-1), respectively) despite the differing strength of their carbon-halogen bonds. In contrast to these substrates, chlorotyrosine reacted with the reduced enzyme approximately 20-fold more slowly and revealed a spectral intermediate that formed at approximately the same rate as the bromo- and iodotyrosine reactions.

Rapid Kinetics of Dehalogenation Promoted by Iodotyrosine Deiodinase from Human Thyroid

PubMed Central

2015-01-01

Reductive dehalogenation such as that catalyzed by iodotyrosine deiodinase (IYD) is highly unusual in aerobic organisms but necessary for iodide salvage from iodotyrosine generated during thyroxine biosynthesis. Equally unusual is the dependence of this process on flavin. Rapid kinetics have now been used to define the basic processes involved in IYD catalysis. Time-dependent quenching of flavin fluorescence was used to monitor halotyrosine association to IYD. The substrates chloro-, bromo-, and iodotyrosine bound with similar rate constants (kon) ranging from 1.3 × 106 to 1.9 × 106 M–1 s–1. Only the inert substrate analogue fluorotyrosine exhibited a significantly (5-fold) slower kon (0.3 × 106 M–1 s–1). All data fit a standard two-state model and indicated that no intermediate complex accumulated during closure of the active site lid induced by substrate. Subsequent halide elimination does not appear to limit reactions of bromo- and iodotyrosine since both fully oxidized the reduced enzyme with nearly equivalent second-order rate constants (7.3 × 103 and 8.6 × 103 M–1 s–1, respectively) despite the differing strength of their carbon–halogen bonds. In contrast to these substrates, chlorotyrosine reacted with the reduced enzyme approximately 20-fold more slowly and revealed a spectral intermediate that formed at approximately the same rate as the bromo- and iodotyrosine reactions. PMID:26151430

Quasiperiodic energy dependence of exciton relaxation kinetics in the sexithiophene crystal.

PubMed

Petelenz, Piotr; Zak, Emil

2014-10-16

Femtosecond kinetics of fluorescence rise in the sexithiophene crystal is studied on a microscopic model of intraband relaxation, where exciton energy is assumed to be dissipated by phonon-accompanied scattering, with the rates calculated earlier. The temporal evolution of the exciton population is described by a set of kinetic equations, solved numerically to yield the population buildup at the band bottom. Not only the time scale but also the shape of the rise curves is found to be unusually sensitive to excitation energy, exhibiting unique quasiperiodic dependence thereon, which is rationalized in terms of the underlying model. Further simulations demonstrate that the main conclusions are robust with respect to experimental factors such as finite temperature and inherent spectral broadening of the exciting pulse, while the calculated fluorescence rise times are found to be in excellent agreement with experimental data available to date. As the rise profiles are composed of a number of exponential contributions, which varies with excitation energy, the common practice of characterizing the population buildup in the emitting state by a single value of relaxation time turns out to be an oversimplification. New experiments giving further insight into the kinetics and mechanism of intraband exciton relaxation are suggested.

Ingestion Reiterada de Cuerpos Extranos. Forma Inusual de Presentacion del Sindrome de Munchausen por Poderes (Reiterated Ingestion of Foreign Bodies. Unusual Form of Presentation of Munchausen Syndrome by Proxy).

ERIC Educational Resources Information Center

Terreros, I. Gomez de; And Others

1996-01-01

An unusual case of Munchausen syndrome by proxy is reported. A mother with a psychiatric record of behavior disorders and family dysfunction perpetrated the ingestion of foreign bodies (for example, earrings, a screw, sewing needles) on a 10-month-old infant with a history of prematurity, repeated visits to emergency rooms, and nonjustified…

Electron nematic fluid in a strained S r3R u2O7 film

NASA Astrophysics Data System (ADS)

Marshall, Patrick B.; Ahadi, Kaveh; Kim, Honggyu; Stemmer, Susanne

2018-04-01

S r3R u2O7 belongs to the family of layered strontium ruthenates and exhibits a range of unusual emergent properties, such as electron nematic behavior and metamagnetism. Here, we show that epitaxial film strain significantly modifies these phenomena. In particular, we observe enhanced magnetic interactions and an electron nematic phase that extends to much higher temperatures and over a larger magnetic-field range than in bulk single crystals. Furthermore, the films show an unusual anisotropic non-Fermi-liquid behavior that is controlled by the direction of the applied magnetic field. At high magnetic fields, the metamagnetic transition to a ferromagnetic phase recovers isotropic Fermi-liquid behavior. The results support the interpretation that these phenomena are linked to the special features of the Fermi surface, which can be tuned by both film strain and an applied magnetic field.

Older Adults and Mental Health

MedlinePlus

... Join A Study News & Events News & Events Home Science News Meetings and Events Multimedia Social Media Press Resources Newsletters NIMH News Feeds About ... or behaviors that interfere with work, family, or social life Unusual thinking or behaviors that ... 2016 • Science Update An individualized program of follow-up treatment ...

Changes in Illness-Related Behavior and Dysphoria Accompanying Behavioral Treatment of Recurrent Headache.

ERIC Educational Resources Information Center

Rains, Jeanetta C.; Lohr, Jeffrey M.

Psychophysiologic research indicates that muscle-contraction headache often is not characterized by excessive or unusual muscular activity, and muscular changes seldom accompany headache improvement resulting from treatment. Multidimensional models have been proposed, which emphasize the interdependence of physiological and psychological systems…

Understanding Williams Syndrome: Behavioral Patterns and Interventions.

ERIC Educational Resources Information Center

Semel, Eleanor; Rosner, Sue R.

This guide to Williams syndrome (WS), a congenital disorder characterized by developmental/cognitive limitations but relatively high verbal and social skills, explains the strengths, difficulties and variations found among individuals with the condition and offers guidelines for intervention in the unusual properties of the WS behavioral profile.…

10 CFR 712.17 - Instructional requirements.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10 Energy 4 2011-01-01 2011-01-01 false Instructional requirements. 712.17 Section 712.17 Energy DEPARTMENT OF ENERGY HUMAN RELIABILITY PROGRAM Establishment of and Procedures for the Human Reliability... responding to behavioral change and aberrant or unusual behavior that may result in a risk to national...

10 CFR 712.17 - Instructional requirements.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 10 Energy 4 2012-01-01 2012-01-01 false Instructional requirements. 712.17 Section 712.17 Energy DEPARTMENT OF ENERGY HUMAN RELIABILITY PROGRAM Establishment of and Procedures for the Human Reliability... responding to behavioral change and aberrant or unusual behavior that may result in a risk to national...

10 CFR 712.17 - Instructional requirements.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 10 Energy 4 2013-01-01 2013-01-01 false Instructional requirements. 712.17 Section 712.17 Energy DEPARTMENT OF ENERGY HUMAN RELIABILITY PROGRAM Establishment of and Procedures for the Human Reliability... responding to behavioral change and aberrant or unusual behavior that may result in a risk to national...

10 CFR 712.17 - Instructional requirements.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 10 Energy 4 2014-01-01 2014-01-01 false Instructional requirements. 712.17 Section 712.17 Energy DEPARTMENT OF ENERGY HUMAN RELIABILITY PROGRAM Establishment of and Procedures for the Human Reliability... responding to behavioral change and aberrant or unusual behavior that may result in a risk to national...

Possible Electromagnetic Effects on Abnormal Animal Behavior Before an Earthquake

PubMed Central

Hayakawa, Masashi

2013-01-01

Simple Summary Possible electromagnetic effects on abnormal animal behavior before earthquakes. Abstract The former statistical properties summarized by Rikitake (1998) on unusual animal behavior before an earthquake (EQ) have first been presented by using two parameters (epicentral distance (D) of an anomaly and its precursor (or lead) time (T)). Three plots are utilized to characterize the unusual animal behavior; (i) EQ magnitude (M) versus D, (ii) log T versus M, and (iii) occurrence histogram of log T. These plots are compared with the corresponding plots for different seismo-electromagnetic effects (radio emissions in different frequency ranges, seismo-atmospheric and -ionospheric perturbations) extensively obtained during the last 15–20 years. From the results of comparisons in terms of three plots, it is likely that lower frequency (ULF (ultra-low-frequency, f ≤ 1 Hz) and ELF (extremely-low-frequency, f ≤ a few hundreds Hz)) electromagnetic emissions exhibit a very similar temporal evolution with that of abnormal animal behavior. It is also suggested that a quantity of field intensity multiplied by the persistent time (or duration) of noise would play the primary role in abnormal animal behavior before an EQ. PMID:26487307

Simulations of thermodynamics and kinetics on rough energy landscapes with milestoning.

PubMed

Bello-Rivas, Juan M; Elber, Ron

2016-03-05

We investigated by computational means the kinetics and stationary behavior of stochastic dynamics on an ensemble of rough two-dimensional energy landscapes. There are no obvious separations of temporal scales in these systems, which constitute a simple model for the behavior of glasses and some biomaterials. Even though there are significant computational challenges present in these systems due to the large number of metastable states, the Milestoning method is able to compute their kinetic and thermodynamic properties exactly. We observe two clearly distinguished regimes in the overall kinetics: one in which diffusive behavior dominates and another that follows an Arrhenius law (despite the absence of a dominant barrier). We compare our results with those obtained with an exactly-solvable one-dimensional model, and with the results from the rough one-dimensional energy model introduced by Zwanzig. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

Assessment and Management of Unusual Auditory Behavior in Infants and Toddlers.

ERIC Educational Resources Information Center

Kile, Jack E.; And Others

1994-01-01

This article describes assessment and management strategies for infants and toddlers with normal hearing or fluctuating conductive hearing loss, who are identified as having central auditory impairment and/or judged to have abnormal auditory behavior. Management strategies include audiologic, medical, and speech and language management. Three case…

Kinetics, bioavailability, and metabolism of RRR-alpha-tocopherol in humans supports lower requirement for vitamin E

USDA-ARS?s Scientific Manuscript database

Kinetic models enable nutrient needs and kinetic behaviors to be quantified and provide mechanistic insights into metabolism. Therefore, we modeled and quantified the kinetics, bioavailability and metabolism of RRR-alpha-tocopherol in 12 healthy adults. Six men and six women, aged 27 ± 6 y, each i...

Urologic sequelae of childhood genitourinary trauma and abuse in men: principles of recognition with fifteen case illustrations.

PubMed

McCarty, T; Roberts, L W; Hendrickson, K

1996-05-01

Providing urologic care to men who have been traumatized during childhood may be especially challenging because of the extent, severity, and unusual character of their urogenital problems. Recognition of past trauma entails attentiveness to patients' background and behaviors. As illustrated through these 15 cases, patients who present with too many past surgeries, too many unremitting urologic complaints, too little sexual function and too few genital parts, sexual impulses that are too strong, sexualized conduct in clinical settings, and self-destructive behaviors surrounding sexuality may have experienced trauma in the past. While empirical studies are necessary to demonstrate the ultimate utility of these categories, appreciation of these clinical indications improves the urologic care provided to traumatized men in four ways: by elucidating unusual and unusually recalcitrant urologic complaints, thereby clarifying clinical decisions; by allowing for appropriate use of psychiatric consultation; by promoting a better understanding of the sequelae of trauma in men; and by alleviating the discomfort naturally felt by urologists and their staff when caring for these difficult, multiproblem patients.

Units of analysis and kinetic structure of behavioral repertoires

PubMed Central

Thompson, Travis; Lubinski, David

1986-01-01

It is suggested that molar streams of behavior are constructed of various arrangements of three elementary constituents (elicited, evoked, and emitted response classes). An eight-cell taxonomy is elaborated as a framework for analyzing and synthesizing complex behavioral repertoires based on these functional units. It is proposed that the local force binding functional units into a smoothly articulated kinetic sequence arises from temporally arranged relative response probability relationships. Behavioral integration is thought to reflect the joint influence of the organism's hierarchy of relative response probabilities, fluctuating biological states, and the arrangement of environmental and behavioral events in time. PMID:16812461

Unusual tremor syndromes: know in order to recognise.

PubMed

Ure, Robert J; Dhanju, Sanveer; Lang, Anthony E; Fasano, Alfonso

2016-11-01

Tremor is a common neurological condition in clinical practice; yet, few syndromes are widely recognised and discussed in the literature. As a result, there is an overdiagnosis of well-known causes, such as essential tremor. Many important unusual syndromes should be considered in the differential diagnosis of patients with tremor. The objective of this review is to provide broad clinical information to aid in the recognition and treatment of various unusual tremor syndromes in the adult and paediatric populations. The review comprised of a comprehensive online search using PubMed, Ovid database and Google Scholar to identify the available literature for each unusual tremor syndrome. The review includes fragile X-associated tremor/ataxia syndrome, spinocerebellar ataxia type 12, tremors caused by autosomal recessive cerebellar ataxias, myorhythmia, isolated tongue tremor, Wilson's disease, slow orthostatic tremor, peripheral trauma-induced tremor, tardive tremor and rabbit syndrome, paroxysmal tremors (hereditary chin tremor, bilateral high-frequency synchronous discharges, head tremor, limb-shaking transient ischaemic attack), bobble-head doll syndrome, spasmus nutans and shuddering attacks. Rare tremors generally present with an action tremor and a variable combination of postural and kinetic components with resting tremors less frequently seen. The phenomenology of myorhythmia is still vague and a clinical definition is proposed. The recognition of these entities should facilitate the correct diagnosis and guide the physician to a prompt intervention. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

An unusual temperature dependence in the oxidation of oxycarbide layers on uranium

NASA Astrophysics Data System (ADS)

Ellis, Walton P.

1981-09-01

An anomalous temperature dependence has been observed for the oxidation kinetics of outermost oxycarbide layers on polycrystalline uranium metal. Normally, oxidation or corrosion reactions are expected to proceed more rapidly as the temperature is elevated. Thus, it came as a surprise when we observed that the removal of the outermost atomic layers of carbon from uranium oxycarbide by O 2 reproducibly proceeds at a much faster rate at 25°C than at 280°C.

An unusual temperature dependence in the oxidation of oxycarbide layers on uranium

NASA Astrophysics Data System (ADS)

Ellis, Walton P.

An anomalous temperature dependence has been observed for the oxidation kinetics of outermost oxycarbide layers on polycrystalline uranium metal. Normally, oxidation or corrosion reactions are expected to proceed more rapidly as the temperature is elevated. Thus, it came as a surprise when we observed that the removal of the outermost atomic layers of carbon from uranium oxycarbide by O 2 reproducibly proceeds at a much faster rate at 25°C than at 280°C.

40 CFR 797.1400 - Fish acute toxicity test.

Code of Federal Regulations, 2013 CFR

2013-07-01

... appearance or physiology such as discoloration, excessive mucous production, hyperventilation, opaque eyes... showing signs of stress, such as discoloration, hemorrhaging, disorientation or other unusual behavior...

40 CFR 797.1400 - Fish acute toxicity test.

Code of Federal Regulations, 2014 CFR

2014-07-01

... appearance or physiology such as discoloration, excessive mucous production, hyperventilation, opaque eyes... showing signs of stress, such as discoloration, hemorrhaging, disorientation or other unusual behavior...

40 CFR 797.1400 - Fish acute toxicity test.

Code of Federal Regulations, 2012 CFR

2012-07-01

... appearance or physiology such as discoloration, excessive mucous production, hyperventilation, opaque eyes... showing signs of stress, such as discoloration, hemorrhaging, disorientation or other unusual behavior...

Reduced Mu Power in Response to Unusual Actions Is Context-Dependent in 1-Year-Olds

PubMed Central

Langeloh, Miriam; Buttelmann, David; Matthes, Daniel; Grassmann, Susanne; Pauen, Sabina; Hoehl, Stefanie

2018-01-01

During social interactions infants predict and evaluate other people’s actions. Previous behavioral research found that infants’ imitation of others’ actions depends on these evaluations and is context-dependent: 1-year-olds predominantly imitated an unusual action (turning on a lamp with one’s forehead) when the model’s hands were free compared to when the model’s hands were occupied or restrained. In the present study, we adapted this behavioral paradigm to a neurophysiological study measuring infants’ brain activity while observing usual and unusual actions via electroencephalography. In particular, we measured differences in mu power (6 – 8 Hz) associated with motor activation. In a between-subjects design, 12- to 14-month-old infants watched videos of adult models demonstrating that their hands were either free or restrained. Subsequent test frames showed the models turning on a lamp or a soundbox by using their head or their hand. Results in the hands-free condition revealed that 12- to 14-month-olds displayed a reduction of mu power in frontal regions in response to unusual and thus unexpected actions (head touch) compared to usual and expected actions (hand touch). This may be explained by increased motor activation required for updating prior action predictions in response to unusual actions though alternative explanations in terms of general attention or cognitive control processes may also be considered. In the hands-restrained condition, responses in mu frequency band did not differ between action outcomes. This implies that unusual head-touch actions compared to hand-touch actions do not necessarily evoke a reduction of mu power. Thus, we conclude that reduction of mu frequency power is context-dependent during infants’ action perception. Our results are interpreted in terms of motor system activity measured via changes in mu frequency band as being one important neural mechanism involved in action prediction and evaluation from early on. PMID:29441034

Chiral Sugars Drive Enantioenrichment in Prebiotic Amino Acid Synthesis.

PubMed

Wagner, Alexander J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán; Blackmond, Donna G

2017-04-26

Chiral pentose sugars mediate the enantioselective synthesis of amino acid precursors, with the magnitude of the chiral induction dictated by a subtle cooperativity between sugar hydroxyl groups. Ribose and lyxose give opposite chiral preferences, and theoretical calculations reveal the pseudoenantiomeric nature of transition state structures from the two sugars. Prebiotically plausible mixtures of natural d-sugars lead to enantioenrichment of natural l-amino acid precursors. Temporal monitoring and kinetic modeling of the reaction reveal an unusual dynamic kinetic resolution that shifts toward an enantioselective pathway over time, providing an amplification mechanism for the transfer of chiral information. This work adds to growing evidence for synergy in the etiology of the single chirality of the two most important classes of biological molecules, the sugars that make up DNA and RNA and the amino acids that form proteins.

Nitriding kinetics of Si-SiC powder mixtures as simulations of reaction bonded Si3N4-SiC composites

NASA Technical Reports Server (NTRS)

Lightfoot, A.; Sheldon, B. W.; Flint, J. H.; Haggerty, J. S.

1989-01-01

The nitriding kinetics of Si and Si plus SiC powder mixtures were studied to simulate the fabrication of RBSN-SiC ceramic matrix composites. Very clean, assynthesized, and solvent-exposed powders were studied; C-rich and Si-rich SiC 0.04-0.05 micron diameter powders were mixed in varying concentrations with SiH4-derived 0.2-0.3 micron diameter Si powder. Complete nitridation is achieved with C-rich SiC powders in 140 min at 1250 C, and in the centers of Si-rich SiC powders in 15 min. The effects on the incubation periods, fast reaction periods, and slow reaction periods that characterize these nitriding processes were studied to explain unusual reverse reaction gradients and other effects of contamination.

Chiral Sugars Drive Enantioenrichment in Prebiotic Amino Acid Synthesis

PubMed Central

2017-01-01

Chiral pentose sugars mediate the enantioselective synthesis of amino acid precursors, with the magnitude of the chiral induction dictated by a subtle cooperativity between sugar hydroxyl groups. Ribose and lyxose give opposite chiral preferences, and theoretical calculations reveal the pseudoenantiomeric nature of transition state structures from the two sugars. Prebiotically plausible mixtures of natural d-sugars lead to enantioenrichment of natural l-amino acid precursors. Temporal monitoring and kinetic modeling of the reaction reveal an unusual dynamic kinetic resolution that shifts toward an enantioselective pathway over time, providing an amplification mechanism for the transfer of chiral information. This work adds to growing evidence for synergy in the etiology of the single chirality of the two most important classes of biological molecules, the sugars that make up DNA and RNA and the amino acids that form proteins. PMID:28470050

Stochastic lumping analysis for linear kinetics and its application to the fluctuation relations between hierarchical kinetic networks.

PubMed

Deng, De-Ming; Chang, Cheng-Hung

2015-05-14

Conventional studies of biomolecular behaviors rely largely on the construction of kinetic schemes. Since the selection of these networks is not unique, a concern is raised whether and under which conditions hierarchical schemes can reveal the same experimentally measured fluctuating behaviors and unique fluctuation related physical properties. To clarify these questions, we introduce stochasticity into the traditional lumping analysis, generalize it from rate equations to chemical master equations and stochastic differential equations, and extract the fluctuation relations between kinetically and thermodynamically equivalent networks under intrinsic and extrinsic noises. The results provide a theoretical basis for the legitimate use of low-dimensional models in the studies of macromolecular fluctuations and, more generally, for exploring stochastic features in different levels of contracted networks in chemical and biological kinetic systems.

Clonazepam

MedlinePlus

... to your doctor, even if you experience side effects such as unusual changes in behavior or mood, ... constant movement) that may occur as a side effect of treatment with antipsychotic medications (medications for mental ...

Brivaracetam

MedlinePlus

... the medication works for you, and the side effects you experience. Be sure to tell your doctor ... to your doctor, even if you experience side effects such as unusual changes in behavior or mood. ...

Aripiprazole

MedlinePlus

... a mental illness that causes disturbed or unusual thinking, loss of interest in life, and strong or ... people who took medications such as aripiprazole developed gambling problems or other intense urges or behaviors that ...

Unusual reaction paths of SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-: Quantum chemical calculations

NASA Astrophysics Data System (ADS)

Minyaev, Ruslan M.; Quapp, Wolfgang; Schmidt, Benjamin; Getmanskii, Ilya V.; Koval, Vitaliy V.

2013-11-01

Quantum chemical (CCSD(full)/6-311++G(3df,3pd), CCSD(T)(full)/6-311++G(3df,3pd)) and density function theory (B3LYP/6-311++G(3df,3pd)) calculations were performed for the SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-. The calculated gradient reaction pathways for both reactions have an unusual behavior. An unusual stationary point of index 2 lies on the gradient reaction path. Using Newton trajectories for the reaction path, we can detect VRI point at which the reaction path branches.

Characteristics of challenging behaviours in adults with autistic disorder, PDD-NOS, and intellectual disability.

PubMed

Matson, Johnny L; Rivet, Tessa T

2008-12-01

Challenging behaviours are frequently a problem for people with autism spectrum disorders (ASD) and intellectual disability (ID). A better understanding of which individuals display which behaviours, at what rates, and the relationship of these behaviours to comorbid psychopathology would have important implications. A group of 161 adults with ASD (autistic disorder or Pervasive Developmental Disorder--Not Otherwise Specified [PDD-NOS]) and 159 matched controls with ID only residing in two large residential facilities in Southeastern United States, were studied using the Autism Spectrum Disorders--Behavior Problems for Adults (ASD-BPA). In all four categories of challenging behaviour measured by the ASD-BPA (Aggression/Destruction, Stereotypy, Self-Injurious Behavior, and Disruptive Behavior), frequency of challenging behaviours increased with severity of autistic symptoms. The greatest group differences were found for Stereotypy (repeated/unusual vocalisations/body movements and unusual object play), Self-Injurious Behavior (harming self and mouthing/swallowing objects), Aggression/Destruction (banging on objects), and Disruptive Behavior (elopement). Challenging behaviours in people with ASD and ID are barriers to effective education, training, and social development, and often persist throughout adulthood. Thus, programs designed to remediate such behaviours should continue across the life-span of these individuals.

Observation of a pretransitional effect near a virtual smectic-A--smectic-C* transition.

PubMed

Shibahara, S; Takanishi, Y; Yamamoto, J; Ogasawara, T; Ishikawa, K; Yokoyama, H; Takezoe, H

2001-06-01

Unusual softening of the layer compression modulus B has been observed near the phase boundary where the smectic-C* phase vanishes in a naphtalene-based liquid crystal mixture. From the systematic study of x-ray and layer compression measurements, this unusual effect is attributed to the pretransitional softening near a virtual smectic-A-smectic-C* phase transition in the smectic-A phase, which no longer appears on the thermoequilibrium phase diagram. This phenomenon is similar but not equivalent to supercritical behavior.

Being vs. Appearing Socially Uninterested: Challenging Assumptions about Social Motivation in Autism.

PubMed

Jaswal, Vikram K; Akhtar, Nameera

2018-06-19

Progress in psychological science can be limited by a number of factors, not least of which are the starting assumptions of scientists themselves. We believe that some influential accounts of autism rest on a questionable assumption that many of its behavioral characteristics indicate a lack of social interest-an assumption that is flatly contradicted by the testimony of many autistic people themselves. In this paper, we challenge this assumption by describing alternative explanations for four such behaviors: (a) low levels of eye contact, (b) infrequent pointing, (c) motor stereotypies, and (d) echolalia. The assumption that autistic people's unusual behaviors indicate diminished social motivation has had profound and often negative effects on the ways they are studied and treated. We argue that understanding and supporting autistic individuals will require interrogating this assumption, taking autistic testimony seriously, considering alternative explanations for unusual behaviors, and investigating unconventional-even idiosyncratic-ways that autistic individuals may express their social interest. These steps are crucial, we believe, for creating a more accurate, humane, and useful science of autism.

Unusual Stiffening and Elastic Response of Polyisobutylene Nanometric Thin Films

NASA Astrophysics Data System (ADS)

Yoon, Heedong; Wigham, Caleb; McKenna, Gregory

The TTU bubble inflation technique was used to study the elastic response and unusual stiffening behavior of nanometirc polyisobutylene (PIB) films. Mechanical properties and surface tension of PIB films were measured through the strain-stress response for film thicknesses ranging from 13 nm to 126 nm. The tests were performed at room temperature, far above the glass transition temperature of PIB. It is found that the stiffening increases with decreasing film thickness, while the surface tension is independent of the film thickness. Similar to the prior bubble inflation measurements in polymeric thin films, the thickness dependence of the stiffening followed a power law behavior in this case of Ds h1.5. These results are consistent with the Ngai et al proposition that rubbery stiffening is related to the separation of the α relaxation and Rouse modes. In addition, we compare stiffening index (S) with fragility (m) based on our prior observation that the S follows a linear behavior with dynamic m. Unlike other polymeric materials seen in prior bubble inflation measurements, the S of PIB does not follow the linear behavior with m.

The logic of kinetic regulation in the thioredoxin system

PubMed Central

2011-01-01

Background The thioredoxin system consisting of NADP(H), thioredoxin reductase and thioredoxin provides reducing equivalents to a large and diverse array of cellular processes. Despite a great deal of information on the kinetics of individual thioredoxin-dependent reactions, the kinetic regulation of this system as an integrated whole is not known. We address this by using kinetic modeling to identify and describe kinetic behavioral motifs found within the system. Results Analysis of a realistic computational model of the Escherichia coli thioredoxin system revealed several modes of kinetic regulation in the system. In keeping with published findings, the model showed that thioredoxin-dependent reactions were adaptable (i.e. changes to the thioredoxin system affected the kinetic profiles of these reactions). Further and in contrast to other systems-level descriptions, analysis of the model showed that apparently unrelated thioredoxin oxidation reactions can affect each other via their combined effects on the thioredoxin redox cycle. However, the scale of these effects depended on the kinetics of the individual thioredoxin oxidation reactions with some reactions more sensitive to changes in the thioredoxin cycle and others, such as the Tpx-dependent reduction of hydrogen peroxide, less sensitive to these changes. The coupling of the thioredoxin and Tpx redox cycles also allowed for ultrasensitive changes in the thioredoxin concentration in response to changes in the thioredoxin reductase concentration. We were able to describe the kinetic mechanisms underlying these behaviors precisely with analytical solutions and core models. Conclusions Using kinetic modeling we have revealed the logic that underlies the functional organization and kinetic behavior of the thioredoxin system. The thioredoxin redox cycle and associated reactions allows for a system that is adaptable, interconnected and able to display differential sensitivities to changes in this redox cycle. This work provides a theoretical, systems-biological basis for an experimental analysis of the thioredoxin system and its associated reactions. PMID:21266044

Reverse Mössbauer effect as a possible source of “hot” molecules absorbed in crystalline solids at low temperature

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

Demontis, Pierfranco; Suffritti, Giuseppe B., E-mail: pino@uniss.it

2016-09-07

As an attempt to explain some of the many anomalies and unresolved problems which have been reported about the dynamic behavior of particles and molecules absorbed in crystalline solids, the “reverse Mössbauer effect” (RME) is proposed. RME theory posits that a particle in non-equilibrium state with respect to a crystal (colliding with the crystal or absorbed in it, but set out of thermal equilibrium by some external cause) is scattered by the whole crystal with a momentum proportional to a vector representing a reciprocal lattice point. The scattering is expected to occur with a well-defined probability and the momentum transferablemore » to the particle is expected to follow a predictable distribution. The RME theory, in practice, is an extension of the Bragg–von Laue scattering law to high-energy colliding particles, in general, and can be applied to any particle or molecule colliding with the surface of a crystalline solid or absorbed in it, but not in thermal equilibrium with the crystal lattice. We verified the RME theory by considering a well-defined unresolved problem. In an experimental study about methane adsorbed in the zeolite Na-ZSM-5 [H. Jobic, Chem. Phys. Lett. 170, 217 (1990)] reporting neutron inelastic-scattering spectra (recoiled bands) at 10 K, the translational kinetic energy of methane resulted to be much higher than equilibrium expected value, namely, about 85 K (or 7.3 meV). The author concluded that “the interpretation of this unusual behavior has yet to be found.” In the present study, on the basis of the RME, an explanation of this behavior is put forward.« less

Phenytoin

MedlinePlus

... talking to your doctor, even if you experience side effects such as unusual changes in behavior or mood. ... acid (Depakene); methadone (Dolophine, Methadose); methotrexate (Otrexup, Rasuvo); methylphenidate (Daytrana, Concerta, Metadate, Ritalin); mexiletine; nifedipine (Adalat, Afeditab), ...

Aripiprazole Injection

MedlinePlus

... a mental illness that causes disturbed or unusual thinking, loss of interest in life, and strong or ... aripiprazole injection and aripiprazole extended-release injection developed gambling problems or other intense urges or behaviors that ...

Kinetic Contributions to Gating by Interactions Unique to N-methyl-d-aspartate (NMDA) Receptors*

PubMed Central

Borschel, William F.; Cummings, Kirstie A.; Tindell, LeeAnn K.; Popescu, Gabriela K.

2015-01-01

Among glutamate-gated channels, NMDA receptors produce currents that subside with unusually slow kinetics, and this feature is essential to the physiology of central excitatory synapses. Relative to the homologous AMPA and kainate receptors, NMDA receptors have additional intersubunit contacts in the ligand binding domain that occur at both conserved and non-conserved sites. We examined GluN1/GluN2A single-channel currents with kinetic analyses and modeling to probe these class-specific intersubunit interactions for their role in glutamate binding and receptor gating. We found that substitutions that eliminate such interactions at non-conserved sites reduced stationary gating, accelerated deactivation, and imparted sensitivity to aniracetam, an AMPA receptor-selective positive modulator. Abolishing unique contacts at conserved sites also reduced stationary gating and accelerated deactivation. These results show that contacts specific to NMDA receptors, which brace the heterodimer interface within the ligand binding domain, stabilize actively gating receptor conformations and result in longer bursts and slower deactivations. They support the view that the strength of the heterodimer interface modulates gating in both NMDA and non-NMDA receptors and that unique interactions at this interface are responsible in part for basic differences between the kinetics of NMDA and non-NMDA currents at glutamatergic synapses. PMID:26370091

A kinetic and thermodynamic understanding of O2 tolerance in [NiFe]-hydrogenases

PubMed Central

Cracknell, James A.; Wait, Annemarie F.; Lenz, Oliver; Friedrich, Bärbel; Armstrong, Fraser A.

2009-01-01

In biology, rapid oxidation and evolution of H2 is catalyzed by metalloenzymes known as hydrogenases. These enzymes have unusual active sites, consisting of iron complexed by carbonyl, cyanide, and thiolate ligands, often together with nickel, and are typically inhibited or irreversibly damaged by O2. The Knallgas bacterium Ralstonia eutropha H16 (Re) uses H2 as an energy source with O2 as a terminal electron acceptor, and its membrane-bound uptake [NiFe]-hydrogenase (MBH) is an important example of an “O2-tolerant” hydrogenase. The mechanism of O2 tolerance of Re MBH has been probed by measuring H2 oxidation activity in the presence of O2 over a range of potential, pH and temperature, and comparing with the same dependencies for individual processes involved in the attack by O2 and subsequent reactivation of the active site. Most significantly, O2 tolerance increases with increasing temperature and decreasing potentials. These trends correlate with the trends observed for reactivation kinetics but not for H2 affinity or the kinetics of O2 attack. Clearly, the rate of recovery is a crucial factor. We present a kinetic and thermodynamic model to account for O2 tolerance in Re MBH that may be more widely applied to other [NiFe]-hydrogenases. PMID:19934053

Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

PubMed

Easter, Quinn T; Blum, Suzanne A

2018-02-05

Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Collective behaviours: from biochemical kinetics to electronic circuits.

PubMed

Agliari, Elena; Barra, Adriano; Burioni, Raffaella; Di Biasio, Aldo; Uguzzoni, Guido

2013-12-10

In this work we aim to highlight a close analogy between cooperative behaviors in chemical kinetics and cybernetics; this is realized by using a common language for their description, that is mean-field statistical mechanics. First, we perform a one-to-one mapping between paradigmatic behaviors in chemical kinetics (i.e., non-cooperative, cooperative, ultra-sensitive, anti-cooperative) and in mean-field statistical mechanics (i.e., paramagnetic, high and low temperature ferromagnetic, anti-ferromagnetic). Interestingly, the statistical mechanics approach allows a unified, broad theory for all scenarios and, in particular, Michaelis-Menten, Hill and Adair equations are consistently recovered. This framework is then tested against experimental biological data with an overall excellent agreement. One step forward, we consistently read the whole mapping from a cybernetic perspective, highlighting deep structural analogies between the above-mentioned kinetics and fundamental bricks in electronics (i.e. operational amplifiers, flashes, flip-flops), so to build a clear bridge linking biochemical kinetics and cybernetics.

Collective behaviours: from biochemical kinetics to electronic circuits

NASA Astrophysics Data System (ADS)

Agliari, Elena; Barra, Adriano; Burioni, Raffaella; di Biasio, Aldo; Uguzzoni, Guido

2013-12-01

In this work we aim to highlight a close analogy between cooperative behaviors in chemical kinetics and cybernetics; this is realized by using a common language for their description, that is mean-field statistical mechanics. First, we perform a one-to-one mapping between paradigmatic behaviors in chemical kinetics (i.e., non-cooperative, cooperative, ultra-sensitive, anti-cooperative) and in mean-field statistical mechanics (i.e., paramagnetic, high and low temperature ferromagnetic, anti-ferromagnetic). Interestingly, the statistical mechanics approach allows a unified, broad theory for all scenarios and, in particular, Michaelis-Menten, Hill and Adair equations are consistently recovered. This framework is then tested against experimental biological data with an overall excellent agreement. One step forward, we consistently read the whole mapping from a cybernetic perspective, highlighting deep structural analogies between the above-mentioned kinetics and fundamental bricks in electronics (i.e. operational amplifiers, flashes, flip-flops), so to build a clear bridge linking biochemical kinetics and cybernetics.

Influence of kinetic effects on the resonance behavior of the Multipole Resonance Probe

NASA Astrophysics Data System (ADS)

Oberrath, Jens; Mussenbrock, Thomas; Brinkmann, Ralf Peter

2012-10-01

Active plasma resonance spectroscopy is a well known diagnostic method. Many concepts of this method are theoretically investigated and realized as a diagnostic tool. One of these tools is the multipole resonance probe (MRP) [1]. The application of such a probe in plasmas with pressures of only a few Pa raises the question whether kinetic effects have to be taken into account or not. To address this question a kinetic model is necessary. A general kinetic model for an electrostatic concept of active plasma resonance spectroscopy has already been presented by the authors [2]. This model can be used to describe the dynamical behavior of the MRP, which is interpretable as a special case of the general model. Neglecting electron-neutral collisions, this model can be solved analytically. Based on this solution we derive an approximated expression for the admittance of the system to investigate the influence of kinetic effects on the resonance behavior of the MRP. [4pt] [1] M. Lapke et al., Plasma Sources Sci. Technol. 20, 2011, 042001[0pt] [2] J. Oberrath et al., Proceedings of the 30th International Conference on Phenomena in Ionized Gases, 28th August - 2nd September, 2011

Kinetic analysis of overlapping multistep thermal decomposition comprising exothermic and endothermic processes: thermolysis of ammonium dinitramide.

PubMed

Muravyev, Nikita V; Koga, Nobuyoshi; Meerov, Dmitry B; Pivkina, Alla N

2017-01-25

This study focused on kinetic modeling of a specific type of multistep heterogeneous reaction comprising exothermic and endothermic reaction steps, as exemplified by the practical kinetic analysis of the experimental kinetic curves for the thermal decomposition of molten ammonium dinitramide (ADN). It is known that the thermal decomposition of ADN occurs as a consecutive two step mass-loss process comprising the decomposition of ADN and subsequent evaporation/decomposition of in situ generated ammonium nitrate. These reaction steps provide exothermic and endothermic contributions, respectively, to the overall thermal effect. The overall reaction process was deconvoluted into two reaction steps using simultaneously recorded thermogravimetry and differential scanning calorimetry (TG-DSC) curves by considering the different physical meanings of the kinetic data derived from TG and DSC by P value analysis. The kinetic data thus separated into exothermic and endothermic reaction steps were kinetically characterized using kinetic computation methods including isoconversional method, combined kinetic analysis, and master plot method. The overall kinetic behavior was reproduced as the sum of the kinetic equations for each reaction step considering the contributions to the rate data derived from TG and DSC. During reproduction of the kinetic behavior, the kinetic parameters and contributions of each reaction step were optimized using kinetic deconvolution analysis. As a result, the thermal decomposition of ADN was successfully modeled as partially overlapping exothermic and endothermic reaction steps. The logic of the kinetic modeling was critically examined, and the practical usefulness of phenomenological modeling for the thermal decomposition of ADN was illustrated to demonstrate the validity of the methodology and its applicability to similar complex reaction processes.

Nucleation and Crystallization of Globular Proteins: What we Know and What is Missing

NASA Technical Reports Server (NTRS)

Rosenberger, F.; Vekilov, P. G.; Muschol, M.; Thomas, B. R.

1996-01-01

Recently. much progress has been made in understanding the nucleation and crystallization of globular proteins, including the formation of compositional and structural crystal defects, Insight into the interactions of (screened) protein macro-ions in solution, obtained from light scattering, small angle X-ray scattering and osmotic pressure studies. can guide the search for crystallization conditions. These studies show that the nucleation of globular proteins is governed by the same principles as that of small molecules. However, failure to account for direct and indirect (hydrodynamic) protein interactions in the solutions results in unrealistic aggregation scenarios. Microscopic studies of numerous proteins reveal that crystals grow by the attachment of growth units through the same layer-spreading mechanisms as inorganic crystals. Investigations of the growth kinetics of hen-egg-white lysozyme (HEWL) reveal non-steady behavior under steady external conditions. Long-term variations in growth rates are due to changes in step-originating dislocation groups. Fluctuations on a shorter timescale reflect the non-linear dynamics of layer growth that results from the interplay between interfacial kinetics and bulk transport. Systematic gel electrophoretic analyses suggest that most HEWL crystallization studies have been performed with material containing other proteins at percent levels. Yet, sub-percent levels of protein impurities impede growth step propagation and play a role in the formation of structural/compositional inhomogeneities. In crystal growth from highly purified HEWL solutions, however, such inhomogeneities are much weaker and form only in response to unusually large changes in growth conditions. Equally important for connecting growth conditions to crystal perfection and diffraction resolution are recent advances in structural characterization through high-resolution Bragg reflection profiling and X-ray topography.

13C ENDOR Spectroscopy of Lipoxygenase-Substrate Complexes Reveals the Structural Basis for C-H Activation by Tunneling.

PubMed

Horitani, Masaki; Offenbacher, Adam R; Carr, Cody A Marcus; Yu, Tao; Hoeke, Veronika; Cutsail, George E; Hammes-Schiffer, Sharon; Klinman, Judith P; Hoffman, Brian M

2017-02-08

In enzymatic C-H activation by hydrogen tunneling, reduced barrier width is important for efficient hydrogen wave function overlap during catalysis. For native enzymes displaying nonadiabatic tunneling, the dominant reactive hydrogen donor-acceptor distance (DAD) is typically ca. 2.7 Å, considerably shorter than normal van der Waals distances. Without a ground state substrate-bound structure for the prototypical nonadiabatic tunneling system, soybean lipoxygenase (SLO), it has remained unclear whether the requisite close tunneling distance occurs through an unusual ground state active site arrangement or by thermally sampling conformational substates. Herein, we introduce Mn 2+ as a spin-probe surrogate for the SLO Fe ion; X-ray diffraction shows Mn-SLO is structurally faithful to the native enzyme. 13 C ENDOR then reveals the locations of 13 C10 and reactive 13 C11 of linoleic acid relative to the metal; 1 H ENDOR and molecular dynamics simulations of the fully solvated SLO model using ENDOR-derived restraints give additional metrical information. The resulting three-dimensional representation of the SLO active site ground state contains a reactive (a) conformer with hydrogen DAD of ∼3.1 Å, approximately van der Waals contact, plus an inactive (b) conformer with even longer DAD, establishing that stochastic conformational sampling is required to achieve reactive tunneling geometries. Tunneling-impaired SLO variants show increased DADs and variations in substrate positioning and rigidity, confirming previous kinetic and theoretical predictions of such behavior. Overall, this investigation highlights the (i) predictive power of nonadiabatic quantum treatments of proton-coupled electron transfer in SLO and (ii) sensitivity of ENDOR probes to test, detect, and corroborate kinetically predicted trends in active site reactivity and to reveal unexpected features of active site architecture.

Unusual Sleep Experiences, Dissociation, and Schizotypy: Evidence for a Common Domain

PubMed Central

Koffel, Erin; Watson, David

2009-01-01

This paper reviews studies that have examined associations between unusual sleep experiences (including nightmares, vivid dreaming, narcolepsy symptoms, and complex nighttime behaviors) and dissociation and schizotypy. Using correlational studies and structural analyses, evidence is provided that unusual sleep experiences, dissociation, and schizotypy belong to a common domain. It is demonstrated that unusual sleep experiences show specificity to dissociation and schizotypy compared to other daytime symptoms (e.g., anxiety, depression, substance use) and other sleep disturbances (e.g., insomnia, lassitude/fatigue). The paper also outlines the methodological limitations of the existing evidence and makes suggestions for future research. Finally, three models for the overlap of daytime and nighttime symptoms are reviewed, including biological abnormalities, trauma, and personality traits. Although further research is needed, it is suggested that daytime and nighttime symptoms result from problems with sleep-wake state boundaries, which may be precipitated by stress or trauma. In addition, association between daytime and nighttime symptoms can be attributed to the higher order personality trait of Oddity. PMID:19581031

Kinetic Control of Aqueous Hydrolysis: Modulating Structure/Property Relationships in Inorganic Crystals

NASA Astrophysics Data System (ADS)

Neilson, James R.

2011-12-01

A grand challenge in materials science and chemistry revolves around the preparation of materials with desired properties by controlling structure on multiple length scales. Biology approaches this challenge by evolving tactics to transform soluble precursors into materials and composites with macro-scale and atomic precision. Studies of biomineralization in siliceous sponges led to the discovery of slow, catalytic hydrolysis of molecular precursors in the biogenesis of silica skeletal elements with well defined micro- and nano-scale architectures. However, the role of aqueous hydrolysis in the limit of kinetic control is not well understood; this allows us to form a central hypothesis: that the kinetics of hydrolysis modulate the structures of materials and their properties. As a model system, the diffusion of a simple hydrolytic catalyst (such as ammonia) across an air-water interface into a metal salt solution reproduces some aspects of the chemistry found in biomineralization, namely kinetic and vectorial control. Variation of the catalyst concentration modulates the hydrolysis rate, and thus alters the resulting structure of the inorganic crystals. Using aqueous solutions of cobalt(II) chloride, each product (cobalt hydroxide chloride) forms with a unique composition, despite being prepared from identical mother liquors. Synchrotron X-ray total scattering methods are needed to locate the atomic positions in the material, which are not aptly described by a traditional crystallographic unit cell due to structural disorder. Detailed definition of the structure confirms that the hydrolysis conditions systematically modulate the arrangement of atoms in the lattice. This tightly coupled control of crystal formation and knowledge of local and average structures of these materials provides insight into the unusual magnetic properties of these cobalt hydroxides. The compounds studied show significant and open magnetization loops with little variation with composition or structure, yet subtle and systematic changes in the mean-field spin interaction strength and spin entropy loss. Meanwhile, neutron powder diffraction reveals a fully compensated Ńeel state; a detailed analysis of the local structure defines the aperiodic clusters of polyhedra responsible for magnetic order. The rate of hydrolysis of metal precursors modulates the disposition of these polyhedral clusters. The strategy of kinetically controlling aqueous hydrolysis also extends to the formation of stoichiometrically ordered bimetallic crystals [MSn(OH)6], where the hydrolysis behavior for dissimilar metal cations must be controlled via counteranions or precursor selection. In the formation of these ordered double perovskite hydroxides, the rate of hydrolysis is held constant in the limit of kinetic control. Instead, the propensities of different cations to undergo controlled hydrolysis are probed by their ability to form ordered crystals. Collectively, these studies demonstrate how systematic variation in the kinetic conditions of materials preparation and the character of each solute control the structure and properties of materials, with a precision not attainable through traditional or near-equilibrium approaches.

Toddlers and Sexual Behavior

MedlinePlus

... children their body parts). Children are curious about naked bodies. They may be interested in watching their ... because it feels good. Children are curious about naked bodies. It is not unusual for toddlers to ...

The Psychometric Properties of a New Measure of Sensory Behaviors in Autistic Children

ERIC Educational Resources Information Center

Neil, Louise; Green, Dido; Pellicano, Elizabeth

2017-01-01

Unusual reactions to sensory input became part of the diagnostic criteria for autism spectrum disorder in the DSM-5. Measures accurately assessing these symptoms are important for clinical decisions. This study examined the reliability and validity of the Sensory Behavior Questionnaire, a parent-report scale designed to assess frequency and impact…

The nature of unusual luminescence in natural calcite, CaCO3

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

Gaft, M.; Nagli, L.; Panczer, G.

2008-11-01

The unusual luminescence of particular varieties of natural pink calcite (CaCO{sub 3}) samples was studied by laser-induced time-resolved luminescence spectroscopy at different temperatures. The luminescence is characterized by intense blue emission under short-wave UV lamp excitation with an extremely long decay time, accompanied by pink-orange luminescence under long wave UV excitation. Our investigation included optical absorption, natural thermostimulated luminescence (NTL) and Laser-Induced Breakdown Spectroscopy (LIBS) studies. Two luminescence centers were detected: a narrow violet band, with {lambda}{sub max} = 412 nm, {Delta} = 45 nm, two decay components of {tau}{sub 1} = 5 ns and {tau}{sub 2} = 7.2 ms,more » accompanied by very long afterglow, and an orange emission band with {lambda}{sub max} = 595 nm, {Delta} = 90 nm and {tau} = 5 ns. Both luminescence centers are thermally unstable with the blue emission disappearing after heating at 500 C, and the orange emission disappearing after heating at different temperatures starting from 230 C, although sometimes it is stable up to 500 C in different samples. Both centers have spectral-kinetic properties very unusual for mineral luminescence, which in combination with extremely low impurity concentrations, prevent their identification with specific impurity related emission. The most likely explanation of these observations may be the presence of radiation-induced luminescence centers. The long violet afterglow is evidently connected with trapped charge carrier liberation, with their subsequent migration through the valence band and ultimate recombination with a radiation-induced center responsible for the unusual violet luminescence.« less

Forced-rupture of cell-adhesion complexes reveals abrupt switch between two brittle states

NASA Astrophysics Data System (ADS)

Toan, Ngo Minh; Thirumalai, D.

2018-03-01

Cell adhesion complexes (CACs), which are activated by ligand binding, play key roles in many cellular functions ranging from cell cycle regulation to mediation of cell extracellular matrix adhesion. Inspired by single molecule pulling experiments using atomic force spectroscopy on leukocyte function-associated antigen-1 (LFA-1), expressed in T-cells, bound to intercellular adhesion molecules (ICAM), we performed constant loading rate (rf) and constant force (F) simulations using the self-organized polymer model to describe the mechanism of ligand rupture from CACs. The simulations reproduce the major experimental finding on the kinetics of the rupture process, namely, the dependence of the most probable rupture forces (f*s) on ln rf (rf is the loading rate) exhibits two distinct linear regimes. The first, at low rf, has a shallow slope, whereas the slope at high rf is much larger, especially for a LFA-1/ICAM-1 complex with the transition between the two occurring over a narrow rf range. Locations of the two transition states (TSs) extracted from the simulations show an abrupt change from a high value at low rf or constant force, F, to a low value at high rf or F. This unusual behavior in which the CACs switch from one brittle (TS position is a constant over a range of forces) state to another brittle state is not found in forced-rupture in other protein complexes. We explain this novel behavior by constructing the free energy profiles, F(Λ)s, as a function of a collective reaction coordinate (Λ), involving many key charged residues and a critical metal ion (Mg2+). The TS positions in F(Λ), which quantitatively agree with the parameters extracted using the Bell-Evans model, change abruptly at a critical force, demonstrating that it, rather than the molecular extension, is a good reaction coordinate. Our combined analyses using simulations performed in both the pulling modes (constant rf and F) reveal a new mechanism for the two loading regimes observed in the rupture kinetics in CACs.

A mechanistic investigation on copolymerization of ethylene with polar monomers using a cyclophane-based Pd(II) alpha-diimine catalyst.

PubMed

Popeney, Chris S; Guan, Zhibin

2009-09-02

A detailed mechanistic investigation of the copolymerization of ethylene and methyl acrylate (MA) by a Pd(II) cyclophane-based alpha-diimine catalyst is reported. Our previous observations of unusually high incorporations of acrylates in copolymerization using this catalyst (J. Am. Chem. Soc. 2007, 129, 10062) prompted us to conduct a full mechanistic study on ethylene/MA copolymerization, which indicates a dramatic departure from normal Curtin-Hammett kinetic behavior as observed in copolymerization using the normal Brookhart type of Pd(II) alpha-diimine catalysts. Further investigation reveals that this contrasting behavior originates from the axial blocking effect of the cyclophane ligand hindering olefin substitution and equilibration. In equilibrium studies of ethylene with nitriles, the cyclophane catalyst was found to more strongly favor the linearly binding nitrile ligands as compared to the standard acyclic Pd(II) alpha-diimine catalysts. Ethylene exchange rates in the complexes [(N--N)PdMe(C(2)H(4))](+) (N--N = diimine) were measured by 2D EXSY NMR spectroscopy and found to be over 100 times slower in the cyclophane case. Measurement of the slow equilibration of ethylene, methyl acrylate, and 4-methoxystyrene in cyclophane-based Pd(II) olefin complexes by (1)H NMR and fitting of the obtained kinetic plots allowed for the estimation of exchange rates and equilibrium constants of the olefins. After extrapolation to typical polymerization temperature, DeltaG(double dagger) = 20.6 and 16.4 kcal/mol for ethylene-methyl acrylate exchange in the forward (ethylene displacement by methyl acrylate) and reverse directions, respectively. These values are of similar magnitude to the previously determined migratory insertion barriers of ethylene (DeltaG(double dagger) = 18.9 kcal/mol) and methyl acrylate (DeltaG(double dagger) = 16.3 kcal/mol) under equivalent conditions, but contrast strongly to the rapid olefin exchange seen in the Brookhart acyclic catalyst. The large barrier to olefin exchange hinders olefin pre-equilibrium, decreasing the cyclophane catalyst's ability to preferentially incorporate one monomer (in this case ethylene) over the other, thus giving rise to high comonomer incorporations.

Graph Learning for Anomaly Detection using Psychological Context GLAD-PC

DTIC Science & Technology

2015-08-03

comparison study of user behavior on Facebook and Gmail, ArXiv: 1305.6082, (11 2013): 0. doi: 10.1016/j.chb.2013.06.043 TOTAL: 1 Received Paper...Fournelle, Steve Gaffigan, Oliver Brdiczka, Jianqiang Shen, Juan Liu, Kendra E. Moore. Characterizing user behavior and information propagation on a...media data; and c) detecting unusual and anomalous behavior from on-line activities. (5) Summary of the most important results With regard to

The unusual chemical bonding and thermoelectric properties of a new type Zintl phase compounds Ba3Al2As4

NASA Astrophysics Data System (ADS)

Yang, Gui; Zhang, Guangbiao; Wang, Chao; Wang, Yuanxu

2016-07-01

Ba3Al2As4 exhibits an unusual anisotropic electrical conductivity, that is, the electrical conductivity along the chain is smaller than those along other two directions. The results is conflict with previous conclusion for Ca5M2Pn6. Earlier studies on Ca5M2Pn6 showed that a higher electrical conductivity could be obtained along the chain. The band decomposed charge density is used to explain such unusual behavior. Our calculations indicate the existence of a conductive pathway near the Fermi level is responsible for the electrons transport. Further, the Ba-As bonding of Ba3Al2As4 has some degree covalency which is novel for the Zintl compounds.

Studies of ClO and BrO reactions important in the polar stratosphere: Kinetics and mechanism of the ClO+BrO and ClO+ClO reactions

NASA Technical Reports Server (NTRS)

Friedl, Randall R.; Sander, Stanley P.

1988-01-01

The reactions, BrO + ClO yields Br + ClOO (1a) yields Br + OClO (1b) yields BrCl + O2 (1c) and ClO + ClO yields Cl + CiOO (2a) yields Cl + OClO (2b) yields Cl2 + O2 (2c) yields (ClO)2 (2d) have assumed new importance in explaining the unusual springtime depletion of ozone observed in the Antarctic stratosphere. The mechanisms of these reactions involve the formation of metastable intermediates which subsequently decompose through several energetically allowed products providing the motivation to study these reactions using both the discharge flow-mass spectrometric and flash photolysis - ultraviolet absorption techniques. These methods have also been used to explore aspects of the kinetics and spectroscopy of the ClO dimer.

Intracarotid Delivery of Drugs: The Potential and the Pitfalls

PubMed Central

Joshi, Shailendra; Meyers, Phillip M.; Ornstein, Eugene

2014-01-01

The major efforts to selectively deliver drugs to the brain in the last decade have relied on smart molecular techniques to penetrate the blood brain barrier while intraarterial drug delivery has drawn relatively little attention. In the last decade there have been rapid advances in endovascular techniques. Modern endovascular procedures can permit highly targeted drug delivery by intracarotid route. Intracarotid drug delivery can be the primary route of drug delivery or it could be used to facilitate the delivery of smart-neuropharmaceuticals. There have been few attempts to systematically understand the kinetics of intracarotid drugs. Anecdotal data suggests that intracarotid drug delivery is effective in the treatment of cerebral vasospasm, thromboembolic strokes, and neoplasms. Neuroanesthesiologists are frequently involved in the care of such high-risk patients. Therefore, it is necessary to understand the applications of intracarotid drug delivery and the unusual kinetics of intracarotid drugs. PMID:18719453

The unusual dynamics of parasite actin result from isodesmic polymerization

PubMed Central

Skillman, Kristen M.; Ma, Christopher I.; Fremont, Daved H.; Diraviyam, Karthikeyan; Cooper, John A.; Sept, David; Sibley, L. David

2013-01-01

Previous reports have indicated that parasite actins are short and inherently unstable, despite being required for motility. Here, we re-examine the polymerization properties of actin in Toxoplasma gondii (TgACTI), unexpectedly finding that it exhibits isodesmic polymerization in contrast to the conventional nucleation-elongation process of all previously studied actins from both eukaryotes and bacteria. TgACTI polymerization kinetics lacks both a lag phase and critical concentration, normally characteristic of actins. Unique among actins, the kinetics of assembly can be fit with a single set of rate constants for all subunit interactions, without need for separate nucleation and elongation rates. This isodesmic model accurately predicts the assembly, disassembly, and the size distribution of TgACTI filaments in vitro, providing a mechanistic explanation for actin dynamics in vivo. Our findings expand the repertoire of mechanisms by which actin polymerization is governed and offer clues about the evolution of self-assembling, stabilized protein polymers. PMID:23921463

Atom-efficient regioselective 1,2-dearomatization of functionalized pyridines by an earth-abundant organolanthanide catalyst

NASA Astrophysics Data System (ADS)

Dudnik, Alexander S.; Weidner, Victoria L.; Motta, Alessandro; Delferro, Massimiliano; Marks, Tobin J.

2014-12-01

Developing earth-abundant, non-platinum metal catalysts for high-value chemical transformations is a critical challenge to contemporary chemical synthesis. Dearomatization of pyridine derivatives is an important transformation to access a wide range of valuable nitrogenous natural products, pharmaceuticals and materials. Here, we report an efficient 1,2-regioselective organolanthanide-catalysed pyridine dearomatization process using pinacolborane, which is compatible with a broad range of pyridines and functional groups and employs equimolar reagent stoichiometry. Regarding the mechanism, derivation of the rate law from NMR spectroscopic and kinetic measurements suggests first order in catalyst concentration, fractional order in pyridine concentration and inverse first order in pinacolborane concentration, with C=N insertion into the La-H bond as turnover-determining. An energetic span analysis affords a more detailed understanding of experimental activity trends and the unusual kinetic behaviour, and proposes the catalyst ‘resting’ state and potential deactivation pathways.

["Piggyback" shot: ballistic parameters of two simultaneously discharged airgun pellets].

PubMed

Frank, Matthias; Schönekess, Holger C; Grossjohann, Rico; Ekkernkamp, Axel; Bockholdt, Britta

2014-01-01

Green and Good reported an uncommon case of homicide committed with an air rifle in 1982 (Am. J. Forensic Med. Pathol. 3: 361-365). The fatal wound was unusual in that two airgun pellets were loaded in so-called "piggyback" fashion into a single shot air rifle. Lack of further information on the ballistic characteristics of two airgun pellets as opposed to one conventionally loaded projectile led to this investigation. The mean kinetic energy (E) of the two pellets discharged in "piggyback" fashion was E = 3.6 J and E = 3.4 J, respectively. In comparison, average kinetic energy values of E = 12.5 J were calculated for conventionally discharged single diabolo pellets. Test shots into ballistic soap confirmed the findings of a single entrance wound as reported by Green and Good. While the ballistic background of pellets discharged in "piggyback" fashion could be clarified, the reason behind this mode of shooting remains unclear.

A Highly Stable Porphyrinic Zirconium Metal–Organic Framework with shp-a Topology

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

Feng, Dawei; Gu, Zhi-Yuan; Chen, Ying-Pin

2014-12-24

Through a kinetically controlled synthetic process, we synthesized PCN-223, a new porphyrinic Zr-MOF constructed from the newly reported hexagonal prismatic 12-connected Zr6 cluster through an unusual disordered arrangement, giving rise to the first example of the shp-a network in MOFs. With its extremely high connectivity, PCN-223 shows high stability in aqueous solutions with a wide range of pH. Cationic PCN-223(Fe) formed by postsynthetic treatment is an excellent recyclable heterogeneous catalyst for the hetero-Diels–Alder reaction.

Dramatic response to levetiracetam in post-ischaemic Holmes’ tremor

PubMed Central

Striano, P; Elefante, Andrea; Coppola, Antonietta; Tortora, Fabio; Zara, Federico; Minetti, Carlo

2009-01-01

Holmes’ tremor refers to an unusual combination of rest, postural and kinetic tremor of extremities. Common causes of Holmes’ tremor include stroke, trauma, vascular malformations and multiple sclerosis, with lesions involving the thalamus, brain stem or cerebellum. Although some drugs (eg, levodopa and dopaminergic drugs, clonazepam and propranolol) have been occasionally reported to give some benefit, medical treatment of Holmes’ tremor is unsatisfactory, and many patients require thalamic surgery to achieve satisfactory control. We report a patient in whom post-ischaemic Holmes’ tremor dramatically responded to levetiracetam treatment. PMID:21686707

Dancing partners at the synapse: auxiliary subunits that shape kainate receptor function

PubMed Central

Copits, Bryan A.; Swanson, Geoffrey T.

2012-01-01

Kainate receptors are a family of ionotropic glutamate receptors whose physiological roles differ from those of other subtypes of glutamate receptors in that they predominantly serve as modulators, rather than mediators, of synaptic transmission. Neuronal kainate receptors exhibit unusually slow kinetic properties that have been difficult to reconcile with the behaviour of recombinant kainate receptors. Recently, however, the neuropilin and tolloid-like 1 (NETO1) and NETO2 proteins were identified as auxiliary kainate receptor subunits that shape both the biophysical properties and synaptic localization of these receptors. PMID:22948074

Entropic factors provide unusual reactivity and selectivity in epoxide-opening reactions promoted by water

PubMed Central

Byers, Jeffery A.; Jamison, Timothy F.

2013-01-01

Despite the myriad of selective enzymatic reactions that occur in water, chemists have rarely capitalized on the unique properties of this medium to govern selectivity in reactions. Here we report detailed mechanistic investigations of a water-promoted reaction that displays high selectivity for what is generally a disfavored product. A combination of structural and kinetic data indicates not only that synergy between substrate and water suppresses undesired pathways but also that water promotes the desired pathway by stabilizing charge in the transition state, facilitating proton transfer, doubly activating the substrate for reaction, and perhaps most remarkably, reorganizing the substrate into a reactive conformation that leads to the observed product. This approach serves as an outline for a general strategy of exploiting solvent-solute interactions to achieve unusual reactivity in chemical reactions. These findings may also have implications in the biosynthesis of the ladder polyether natural products, such as the brevetoxins and ciguatoxins. PMID:24046369

Does assisted driving behavior lead to safety-critical encounters with unequipped vehicles' drivers?

PubMed

Preuk, Katharina; Stemmler, Eric; Schießl, Caroline; Jipp, Meike

2016-10-01

With Intelligent Transport Systems (e.g., traffic light assistance systems) assisted drivers are able to show driving behavior in anticipation of upcoming traffic situations. In the years to come, the penetration rate of such systems will be low. Therefore, the majority of vehicles will not be equipped with these systems. Unequipped vehicles' drivers may not expect the driving behavior of assisted drivers. However, drivers' predictions and expectations can play a significant role in their reaction times. Thus, safety issues could arise when unequipped vehicles' drivers encounter driving behavior of assisted drivers. This is why we tested how unequipped vehicles' drivers (N=60) interpreted and reacted to the driving behavior of an assisted driver. We used a multi-driver simulator with three drivers. The three drivers were driving in a line. The lead driver in the line was a confederate who was followed by two unequipped vehicles' drivers. We varied the equipment of the confederate with an Intelligent Transport System: The confederate was equipped either with or without a traffic light assistance system. The traffic light assistance system provided a start-up maneuver before a light turned green. Therefore, the assisted confederate seemed to show unusual deceleration behavior by coming to a halt at an unusual distance from the stop line at the red traffic light. The unusual distance was varied as we tested a moderate (4m distance from the stop line) and an extreme (10m distance from the stop line) parameterization of the system. Our results showed that the extreme parametrization resulted in shorter minimal time-to-collision of the unequipped vehicles' drivers. One rear-end crash was observed. These results provided initial evidence that safety issues can arise when unequipped vehicles' drivers encounter assisted driving behavior. We recommend that future research identifies counteractions to prevent these safety issues. Moreover, we recommend that system developers discuss the best parameterizations of their systems to ensure benefits but also the safety in encounters with unequipped vehicles' drivers. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reprint Characteristics of Non-Silver Films.

ERIC Educational Resources Information Center

Microform Review, 1990

1990-01-01

Describes reprint characteristics of diazo and vesicular films. Use with microform reader-printers and autogeneration of copies are discussed, and methods of dealing with the unusual reprint behavior of these films are outlined. (MES)

New theoretical framework for designing nonionic surfactant mixtures that exhibit a desired adsorption kinetics behavior.

PubMed

Moorkanikkara, Srinivas Nageswaran; Blankschtein, Daniel

2010-12-21

How does one design a surfactant mixture using a set of available surfactants such that it exhibits a desired adsorption kinetics behavior? The traditional approach used to address this design problem involves conducting trial-and-error experiments with specific surfactant mixtures. This approach is typically time-consuming and resource-intensive and becomes increasingly challenging when the number of surfactants that can be mixed increases. In this article, we propose a new theoretical framework to identify a surfactant mixture that most closely meets a desired adsorption kinetics behavior. Specifically, the new theoretical framework involves (a) formulating the surfactant mixture design problem as an optimization problem using an adsorption kinetics model and (b) solving the optimization problem using a commercial optimization package. The proposed framework aims to identify the surfactant mixture that most closely satisfies the desired adsorption kinetics behavior subject to the predictive capabilities of the chosen adsorption kinetics model. Experiments can then be conducted at the identified surfactant mixture condition to validate the predictions. We demonstrate the reliability and effectiveness of the proposed theoretical framework through a realistic case study by identifying a nonionic surfactant mixture consisting of up to four alkyl poly(ethylene oxide) surfactants (C(10)E(4), C(12)E(5), C(12)E(6), and C(10)E(8)) such that it most closely exhibits a desired dynamic surface tension (DST) profile. Specifically, we use the Mulqueen-Stebe-Blankschtein (MSB) adsorption kinetics model (Mulqueen, M.; Stebe, K. J.; Blankschtein, D. Langmuir 2001, 17, 5196-5207) to formulate the optimization problem as well as the SNOPT commercial optimization solver to identify a surfactant mixture consisting of these four surfactants that most closely exhibits the desired DST profile. Finally, we compare the experimental DST profile measured at the surfactant mixture condition identified by the new theoretical framework with the desired DST profile and find good agreement between the two profiles.

Review of the genus Hemistola Warren, 1893 in Taiwan with notes on an unusual conifer-feeding larva and descriptions of three new species (Lepidoptera, Geometridae, Geometrinae).

PubMed

Chang, Wei-Chun; Wu, Shipher

2013-11-29

The genus Hemistola Warren, 1893 in Taiwan is reviewed. Seven species are confirmed, with descriptions of three new species provided: H. piceacola sp. nov., H. fui sp. nov. and H. taiwanensis sp. nov. The immature stages and unusual conifer-feeding behavior of H. piceacola on Taiwan spruce (Picea morrisonicola) are reported. The distribution of H. tenuilinea (Alphéraky, 1897) is discussed and this species is omitted from the Taiwanese fauna.

A Physiologically-Based Description of the Inhalation Pharmacokinetics of Styrene in Rats and Humans

DTIC Science & Technology

1983-01-01

model for rat were scaled to give a description of human kinetics and the predictions agreed closely with available data from the literature (Fig. 4...for predicting human kinetics from a data base in other mammalian species. The ability to anticipate kinetic behavior in humans could very much improve

Antipsychotic polypharmacy prescribing patterns and costs in the Florida adult and child Medicaid populations.

PubMed

Becker, Edmund R; Constantine, Robert J; McPherson, Marie A; Jones, Mary Elizabeth

2013-01-01

The rapid growth in the use of antipsychotic medications and their related costs have resulted in states developing programs to measure, monitor, and insure their beneficial relevance to public program populations. One such program developed in the state of Florida has adopted an evidence-based approach to identify prescribers with unusual psychotherapeutic prescription patterns and track their utilization and costs among Florida Medicaid patients. This study reports on the prescriber prescription and cost patterns for adults and children using three measures of unusual antipsychotic prescribing patterns: (1) two antipsychotics for 60 days (2AP60), (2) three antipsychotics for 60 days (3AP60), and (2) two antipsychotics for 90 or more days (2AP90). We find that over the four-year study period there were substantial increases in several aspects of the Florida Medicaid behavioral drug program. Overall, for adults and children, patient participation increased by 29 percent, the number of prescriptions grew by 30 percent, and the number of prescribers that wrote at least one prescription grew 48.5 percent, while Medicaid costs for behavioral drugs increased by 32 percent. But the results are highly skewed. We find that a relatively small number of prescribers account for a disproportionately large share of prescriptions and costs of the unusual antipsychotic prescriptions. In general, the top 350 Medicaid prescribers accounted for more than 70 percent of the unusual antipsychotic prescriptions, and we find that this disparity in unusual prescribing patterns appears to be substantially more pronounced in adults than in children prescribers. For just the top 13 adult and children prescribers, their practice patterns accounted for 11 percent to 21 percent of the unusual prescribing activity and, overall, these 13 top prescribers accounted for 13 percent of the total spent on antipsychotics by the Florida Medicaid program and 9.3 percent of the total expenditure by the state for all drugs. Our findings suggest that a strategy to monitor and ensure patient safety and prescribing patterns that targets a relatively small number of Medicaid providers could have a substantial benefit and prove to be cost effective.

A Methodology for Evaluating the Hygroscopic Behavior of Wood in Adaptive Building Skins using Motion Grammar

NASA Astrophysics Data System (ADS)

El-Dabaa, Rana; Abdelmohsen, Sherif

2018-05-01

The challenge in designing kinetic architecture lies in the lack of applying computational design and human computer interaction to successfully design intelligent and interactive interfaces. The use of ‘programmable materials’ as specifically fabricated composite materials that afford motion upon stimulation is promising for low-cost low-tech systems for kinetic facades in buildings. Despite efforts to develop working prototypes, there has been no clear methodological framework for understanding and controlling the behavior of programmable materials or for using them for such purposes. This paper introduces a methodology for evaluating the motion acquired from programmed material – resulting from the hygroscopic behavior of wood – through ‘motion grammar’. Motion grammar typically allows for the explanation of desired motion control in a computationally tractable method. The paper analyzed and evaluated motion parameters related to the hygroscopic properties and behavior of wood, and introduce a framework for tracking and controlling wood as a programmable material for kinetic architecture.

Low-temperature behavior of the quark-meson model

NASA Astrophysics Data System (ADS)

Tripolt, Ralf-Arno; Schaefer, Bernd-Jochen; von Smekal, Lorenz; Wambach, Jochen

2018-02-01

We revisit the phase diagram of strong-interaction matter for the two-flavor quark-meson model using the functional renormalization group. In contrast to standard mean-field calculations, an unusual phase structure is encountered at low temperatures and large quark chemical potentials. In particular, we identify a regime where the pressure decreases with increasing temperature and discuss possible reasons for this unphysical behavior.

Relationship Between Unusual High-Temperature Fatigue Crack Growth Threshold Behavior in Superalloys and Sudden Failure Mode Transitions

NASA Technical Reports Server (NTRS)

Telesman, J.; Smith, T. M.; Gabb, T. P.; Ring, A. J.

2017-01-01

An investigation of high temperature cyclic fatigue crack growth (FCG) threshold behavior of two advanced nickel disk alloys was conducted. The focus of the study was the unusual crossover effect in the near-threshold region of these type of alloys where conditions which produce higher crack growth rates in the Paris regime, produce higher resistance to crack growth in the near threshold regime. It was shown that this crossover effect is associated with a sudden change in the fatigue failure mode from a predominant transgranular mode in the Paris regime to fully intergranular mode in the threshold fatigue crack growth region. This type of a sudden change in the fracture mechanisms has not been previously reported and is surprising considering that intergranular failure is typically associated with faster crack growth rates and not the slow FCG rates of the near-threshold regime. By characterizing this behavior as a function of test temperature, environment and cyclic frequency, it was determined that both the crossover effect and the onset of intergranular failure are caused by environmentally driven mechanisms which have not as yet been fully identified. A plausible explanation for the observed behavior is proposed.

Intramantle Inking: A Stress Behavior in Octopus bimaculoides (Mollusca: Cephalopoda)

PubMed Central

Toll, Ronald B

2011-01-01

Several Pacific 2-spot octopuses (Octopus bimaculoides) shipped from California and held in a recirculating seawater system at Illinois College exhibited an unusual postshipping stress behavior not previously documented in the literature. Ink, normally ejected into the surrounding seawater, was uncharacteristically retained in the mantle cavity. We describe the resulting behaviors, discuss successful resuscitation efforts, and briefly consider the possible role(s) that ink may have played in the death of one octopus. PMID:22330791

On-Line Analysis and Kinetic Behavior of Arsenic Release during Coal Combustion and Pyrolysis.

PubMed

Shen, Fenghua; Liu, Jing; Zhang, Zhen; Dai, Jinxin

2015-11-17

The kinetic behavior of arsenic (As) release during coal combustion and pyrolysis in a fluidized bed was investigated by applying an on-line analysis system of trace elements in flue gas. This system, based on inductively coupled plasma optical emission spectroscopy (ICP-OES), was developed to measure trace elements concentrations in flue gas quantitatively and continuously. Obvious variations of arsenic concentration in flue gas were observed during coal combustion and pyrolysis, indicating strong influences of atmosphere and temperature on arsenic release behavior. Kinetic laws governing the arsenic release during coal combustion and pyrolysis were determined based on the results of instantaneous arsenic concentration in flue gas. A second-order kinetic law was determined for arsenic release during coal combustion, and the arsenic release during coal pyrolysis followed a fourth-order kinetic law. The results showed that the arsenic release rate during coal pyrolysis was faster than that during coal combustion. Thermodynamic calculations were carried out to identify the forms of arsenic in vapor and solid phases during coal combustion and pyrolysis, respectively. Ca3(AsO4)2 and Ca(AsO2)2 are the possible species resulting from As-Ca interaction during coal combustion. Ca(AsO2)2 is the most probable species during coal pyrolysis.

Collective behaviours: from biochemical kinetics to electronic circuits

PubMed Central

Agliari, Elena; Barra, Adriano; Burioni, Raffaella; Di Biasio, Aldo; Uguzzoni, Guido

2013-01-01

In this work we aim to highlight a close analogy between cooperative behaviors in chemical kinetics and cybernetics; this is realized by using a common language for their description, that is mean-field statistical mechanics. First, we perform a one-to-one mapping between paradigmatic behaviors in chemical kinetics (i.e., non-cooperative, cooperative, ultra-sensitive, anti-cooperative) and in mean-field statistical mechanics (i.e., paramagnetic, high and low temperature ferromagnetic, anti-ferromagnetic). Interestingly, the statistical mechanics approach allows a unified, broad theory for all scenarios and, in particular, Michaelis-Menten, Hill and Adair equations are consistently recovered. This framework is then tested against experimental biological data with an overall excellent agreement. One step forward, we consistently read the whole mapping from a cybernetic perspective, highlighting deep structural analogies between the above-mentioned kinetics and fundamental bricks in electronics (i.e. operational amplifiers, flashes, flip-flops), so to build a clear bridge linking biochemical kinetics and cybernetics. PMID:24322327

Needs Assessment for Behavioral Health Workforce: a State-Level Analysis.

PubMed

Nayar, Preethy; Apenteng, Bettye; Nguyen, Anh T; Shaw-Sutherland, Kelly; Ojha, Diptee; Deras, Marlene

2017-07-01

This study describes trends in the supply and the need for behavioral health professionals in Nebraska. A state-level health workforce database was used to estimate the behavioral health workforce supply and need. Compared with national estimates, Nebraska has a lower proportion of all categories of behavioral health professionals. The majority of Nebraska counties have unusually high needs for mental health professionals, with rural areas experiencing a decline in the supply of psychiatrists over the last decade. Availability of robust state-level health workforce data can assist in crafting effective policy for successful systems change, particularly for behavioral health.

Kinetic Methods for Understanding Linker Exchange in Metal-Organic Frameworks

NASA Astrophysics Data System (ADS)

Morabito, Joseph V.

Exchange reactions have enabled a new level of control in the rational, stepwise preparation of metal-organic framework (MOF) materials. However, their full potential is limited by a lack of understanding of the molecular mechanisms by which they occur. This dissertation describes our efforts to understand this important class of reactions in two parts. The first reports our use of a linker exchange process to encapsulate guest molecules larger than the limiting pore aperture of the MOF. The concept is demonstrated, along with evidence for guest encapsulation and its relation to a dissociative linker exchange process. The second part describes our development of the first quantitative kinetic method for studying MOF linker exchange reactions and our application of this method to understand the solvent dependence of the reaction of ZIF-8 with imidazole. This project involved the collection of the largest set of rate data available on any MOF linker exchange reaction. The combination of this dataset with small molecule encapsulation experiments allowed us to formulate a mechanistic model that could account for all the observed kinetic and structural data. By comparison with the kinetic behavior of complexes in solution, we were able to fit the kinetic behavior of ZIF-8 into the broader family of coordination compounds. Aside from the specific use that our kinetic data may have in predicting the reactivity of ZIF linker exchange, we hope that the conceptual bridges made between MOFs and related metal?organic compounds can help reveal underlying patterns in behavior and advance the field.

Unusual masturbatory practice as an etiological factor in the diagnosis and treatment of sexual dysfunction in young men.

PubMed

Bronner, Gila; Ben-Zion, Itzhak Z

2014-07-01

Masturbation is a common sexual activity among people of all ages throughout life. It has been traditionally prohibited and judged as immoral and sinful by several religions. Although it is no longer perceived as a negative behavior, masturbation is often omitted in the diagnostic inquiry of patients with sexual problems. The aims of this study are to increase the awareness of clinicians to the importance of including questions regarding masturbatory habits in the process of sexual history taking, to analyze cases of male sexual dysfunction (SD) associated with unusual masturbatory practices, and to propose a practical tool for clinicians to diagnose and manage such problems. A clinical study of four cases that include a range of unusual masturbatory practices by young males who applied for sex therapy is described. An intervention plan involving specific questions in case history taking was devised. It was based on detailed understanding of each patient's masturbatory practice and its manifestation in his SD. Effects of identifying and altering masturbatory practices on sexual function. The four men described unusual and awkward masturbatory practices, each of which was associated with different kinds of SD. The unlearning of the masturbatory practices contributed notably to improvement of their sexual function. The four cases in this study indicate that the detailed questioning of masturbatory habits is crucial for a thorough assessment and adequate treatment of sexual problems in men. We propose specific questions on masturbatory behavior as well as a diagnostic and therapeutic flowchart for physicians and sex therapists to address those problems. © 2014 International Society for Sexual Medicine.

Transient cocaine-associated behavioral symptoms rated with a new instrument, the scale for assessment of positive symptoms for cocaine-induced psychosis (SAPS-CIP).

PubMed

Tang, Yi-lang; Kranzler, Henry R; Gelernter, Joel; Farrer, Lindsay A; Pearson, Deborah; Cubells, Joseph F

2009-01-01

Chronic use of cocaine is associated with a variety of behavioral symptoms. The current report describes the assessment of cocaine-related behavioral symptoms (CRB) using the Scale for Assessment of Positive Symptoms of Cocaine-Induced Psychosis (SAPS-CIP). The CRB section, one of the three domains in the SAPS-CIP, consists of sub-domains, including Aggressive/Agitated Behavior, Repetitive/Stereotyped Behavior, and Unusual Social or Sexual Behavior. Severity scores are assigned according to operational criteria, and range from 0 (not present) to 5 (severe). We interviewed 261 unrelated cocaine-abusing adults using the SAPS-CIP, and 243 of them met criteria for inclusion in the study. The proportion of subjects endorsing different classes of CRBs varied across categories, with 109 of 243 (44.9%) subjects reporting aggressive and agitated behaviors, 180 subjects (74.1%) repetitive/stereotyped behaviors, and 192 (79.0%) unusual social/sexual behaviors. A substantial minority of the subjects (10.3-25.1%) reported that they experienced marked-to-severe behavioral symptoms associated with cocaine use. The proportions of subjects endorsing CRB did not differ by ethnic/racial group or by sex. Correlations among the different domains of CRB were strong, but behaviors rated in the CRB section were less well correlated with psychotic symptoms, which were rated in the hallucination and delusion sections of the instrument. A variety of CRBs are common in cocaine-dependent subjects, and many of these are highly intercorrelated. CRBs also correlate with hallucinations and delusions induced by cocaine, but to a lesser degree. Our findings suggest that there may be some common vulnerability factors that contribute to both cocaine-induced psychosis and CRBs.

Arctic Ozone Depletion from UARS MLS Measurements

NASA Technical Reports Server (NTRS)

Manney, G. L.

1995-01-01

Microwave Limb Sounder (MLS) measurements of ozone during four Arctic winters are compared. The evolution of ozone in the lower stratosphere is related to temperature, chlorine monoxide (also measured by MLS), and the evolution of the polar vortex. Lagrangian transport calculations using winds from the United Kingdom Meteorological Office's Stratosphere-Troposphere Data Assimilation system are used to estimate to what extent the evolution of lower stratospheric ozone is controlled by dynamics. Observations, along with calculations of the expected dynamical behavior, show evidence for chemical ozone depletion throughout most of the Arctic lower stratospheric vortex during the 1992-93 middle and late winter, and during all of the 1994-95 winter that was observed by MLS. Both of these winters were unusually cold and had unusually cold and had unusually strong Arctic polar vortices compared to meteorological data over the past 17 years.

An embodied view of octopus neurobiology.

PubMed

Hochner, Binyamin

2012-10-23

Octopuses have a unique flexible body and unusual morphology, but nevertheless they are undoubtedly a great evolutionary success. They compete successfully with vertebrates in their ecological niche using a rich behavioral repertoire more typical of an intelligent predator which includes extremely effective defensive behavior--fast escape swimming and an astonishing ability to adapt their shape and color to their environment. The most obvious characteristic feature of an octopus is its eight long and flexible arms, but these pose a great challenge for achieving the level of motor and sensory information processing necessary for their behaviors. First, coordinating motion is a formidable task because of the infinite degrees of freedom that have to be controlled; and second, it is hard to use body coordinates in this flexible animal to represent sensory information in a central control system. Here I will review experimental results suggesting that these difficulties, arising from the animal's morphology, have imposed the evolution of unique brain/body/behavior relationships best explained as intelligent behavior which emerges from the octopus's embodied organization. The term 'intelligent embodiment' comes from robotics and refers to an approach to designing autonomous robots in which the behavior emerges from the dynamic physical and sensory interactions of the agent's materials, morphology and environment. Consideration of the unusual neurobiology of the octopus in the light of its unique morphology suggests that similar embodied principles are instrumental for understanding the emergence of intelligent behavior in all biological systems. Copyright © 2012 Elsevier Ltd. All rights reserved.

A Newtonian approach to extraordinarily strong negative refraction.

PubMed

Yoon, Hosang; Yeung, Kitty Y M; Umansky, Vladimir; Ham, Donhee

2012-08-02

Metamaterials with negative refractive indices can manipulate electromagnetic waves in unusual ways, and can be used to achieve, for example, sub-diffraction-limit focusing, the bending of light in the 'wrong' direction, and reversed Doppler and Cerenkov effects. These counterintuitive and technologically useful behaviours have spurred considerable efforts to synthesize a broad array of negative-index metamaterials with engineered electric, magnetic or optical properties. Here we demonstrate another route to negative refraction by exploiting the inertia of electrons in semiconductor two-dimensional electron gases, collectively accelerated by electromagnetic waves according to Newton's second law of motion, where this acceleration effect manifests as kinetic inductance. Using kinetic inductance to attain negative refraction was theoretically proposed for three-dimensional metallic nanoparticles and seen experimentally with surface plasmons on the surface of a three-dimensional metal. The two-dimensional electron gas that we use at cryogenic temperatures has a larger kinetic inductance than three-dimensional metals, leading to extraordinarily strong negative refraction at gigahertz frequencies, with an index as large as -700. This pronounced negative refractive index and the corresponding reduction in the effective wavelength opens a path to miniaturization in the science and technology of negative refraction.

High Field Remagnetization of Hematite Concretions from Utah, USA and Czech Republic

NASA Astrophysics Data System (ADS)

Adachi, T.; Kletetschka, G.; Chan, M.; Mikula, V.; Adamovic, J.; Pruner, P.; Schnabl, P.; Wasilewski, P.

2007-03-01

Terrestrial hematite concretions of the Navajo Sandstone have been discussed as analogues to the blueberries on Mars. Magnetic investigation of terrestrial concretions showed unusual behavior of antiferromagnetic hematite-goethite composition that may mem

Steady-state kinetic modeling constrains cellular resting states and dynamic behavior.

PubMed

Purvis, Jeremy E; Radhakrishnan, Ravi; Diamond, Scott L

2009-03-01

A defining characteristic of living cells is the ability to respond dynamically to external stimuli while maintaining homeostasis under resting conditions. Capturing both of these features in a single kinetic model is difficult because the model must be able to reproduce both behaviors using the same set of molecular components. Here, we show how combining small, well-defined steady-state networks provides an efficient means of constructing large-scale kinetic models that exhibit realistic resting and dynamic behaviors. By requiring each kinetic module to be homeostatic (at steady state under resting conditions), the method proceeds by (i) computing steady-state solutions to a system of ordinary differential equations for each module, (ii) applying principal component analysis to each set of solutions to capture the steady-state solution space of each module network, and (iii) combining optimal search directions from all modules to form a global steady-state space that is searched for accurate simulation of the time-dependent behavior of the whole system upon perturbation. Importantly, this stepwise approach retains the nonlinear rate expressions that govern each reaction in the system and enforces constraints on the range of allowable concentration states for the full-scale model. These constraints not only reduce the computational cost of fitting experimental time-series data but can also provide insight into limitations on system concentrations and architecture. To demonstrate application of the method, we show how small kinetic perturbations in a modular model of platelet P2Y(1) signaling can cause widespread compensatory effects on cellular resting states.

EXPLOITATION AND OPTIMIZATION OF RESERVOIR PERFORMANCE IN HUNTON FORMATION, OKLAHOMA

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

Mohan Kelkar

2002-03-31

The West Carney Field in Lincoln County, Oklahoma is one of few newly discovered oil fields in Oklahoma. Although profitable, the field exhibits several unusual characteristics. These include decreasing water-oil ratios, decreasing gas-oil ratios, decreasing bottomhole pressures during shut-ins in some wells, and transient behavior for water production in many wells. This report explains the unusual characteristics of West Carney Field based on detailed geological and engineering analyses. We propose a geological history that explains the presence of mobile water and oil in the reservoir. The combination of matrix and fractures in the reservoir explains the reservoir's flow behavior. Wemore » confirm our hypothesis by matching observed performance with a simulated model and develop procedures for correlating core data to log data so that the analysis can be extended to other, similar fields where the core coverage may be limited.« less

Increased Prevalence of Unusual Sensory Behaviors in Infants at Risk for, and Teens with, Autism Spectrum Disorder.

PubMed

Van Etten, Hannah M; Kaur, Maninderjit; Srinivasan, Sudha M; Cohen, Shereen J; Bhat, Anjana; Dobkins, Karen R

2017-11-01

The current study investigated the prevalence and pattern of unusual sensory behaviors (USBs) in teens with Autism Spectrum Disorder (ASD) and infants (3-36 months) at risk for ASD. From two different sites (UCSD and UConn), caregivers of infants at high (n = 32) and low risk (n = 33) for ASD, and teenagers with (n = 12) and without ASD (n = 11), completed age-appropriate Sensory Profile questionnaires (Infant/Toddler Sensory Profile; Dunn 2002; Adolescent/Adult Sensory Profile; Brown and Dunn 2002). The results show that high-risk infants and teenagers with ASD exhibit higher-than-typical prevalence of USBs. Results of our distribution analyses investigating the direction of sensory atypicalities (greater-than-typical vs. less-than-typical) revealed a fair degree of consistency amongst teens, however, USB patterns were more varied in high-risk infants.

Reduction behavior and kinetics of vanadium-titanium sinters under high potential oxygen enriched pulverized coal injection

NASA Astrophysics Data System (ADS)

Ma, Jin-fang; Wang, Guang-wei; Zhang, Jian-liang; Li, Xin-yu; Liu, Zheng-jian; Jiao, Ke-xin; Guo, Jian

2017-05-01

In this work, the reduction behavior of vanadium-titanium sinters was studied under five different sets of conditions of pulverized coal injection with oxygen enrichment. The modified random pore model was established to analyze the reduction kinetics. The results show that the reduction rate of sinters was accelerated by an increase of CO and H2 contents. Meanwhile, with the increase in CO and H2 contents, the increasing range of the medium reduction index (MRE) of sinters decreased. The increasing oxygen enrichment ratio played a diminishing role in improving the reduction behavior of the sinters. The reducing process kinetic parameters were solved using the modified random role model. The results indicated that, with increasing oxygen enrichment, the contents of CO and H2 in the reducing gas increased. The reduction activation energy of the sinters decreased to between 20.4 and 23.2 kJ/mol.

Exotic s-wave superconductivity in alkali-doped fullerides.

PubMed

Nomura, Yusuke; Sakai, Shiro; Capone, Massimo; Arita, Ryotaro

2016-04-20

Alkali-doped fullerides (A3C60 with A = K, Rb, Cs) show a surprising phase diagram, in which a high transition-temperature (Tc) s-wave superconducting state emerges next to a Mott insulating phase as a function of the lattice spacing. This is in contrast with the common belief that Mott physics and phonon-driven s-wave superconductivity are incompatible, raising a fundamental question on the mechanism of the high-Tc superconductivity. This article reviews recent ab initio calculations, which have succeeded in reproducing comprehensively the experimental phase diagram with high accuracy and elucidated an unusual cooperation between the electron-phonon coupling and the electron-electron interactions leading to Mott localization to realize an unconventional s-wave superconductivity in the alkali-doped fullerides. A driving force behind the exotic physics is unusual intramolecular interactions, characterized by the coexistence of a strongly repulsive Coulomb interaction and a small effectively negative exchange interaction. This is realized by a subtle energy balance between the coupling with the Jahn-Teller phonons and Hund's coupling within the C60 molecule. The unusual form of the interaction leads to a formation of pairs of up- and down-spin electrons on the molecules, which enables the s-wave pairing. The emergent superconductivity crucially relies on the presence of the Jahn-Teller phonons, but surprisingly benefits from the strong correlations because the correlations suppress the kinetic energy of the electrons and help the formation of the electron pairs, in agreement with previous model calculations. This confirms that the alkali-doped fullerides are a new type of unconventional superconductors, where the unusual synergy between the phonons and Coulomb interactions drives the high-Tc superconductivity.

Unusual Crystallization Behavior Close to the Glass Transition

NASA Astrophysics Data System (ADS)

Desgranges, Caroline; Delhommelle, Jerome

2018-03-01

Using molecular simulations, we shed light on the mechanism underlying crystal nucleation in metal alloys and unravel the interplay between crystal nucleation and glass transition, as the conditions of crystallization lie close to this transition. While decreasing the temperature of crystallization usually results in a lower free energy barrier, we find an unexpected reversal of behavior for glass-forming alloys as the temperature of crystallization approaches the glass transition. For this purpose, we simulate the crystallization process in two glass-forming Copper alloys, Ag6 Cu4 , which has a positive heat of mixing, and CuZr, characterized by a large negative heat of mixing. Our results allow us to identify this unusual behavior as directly correlated with a nonmonotonic temperature dependence for the formation energy of connected icosahedral structures, which are incompatible with crystalline order and impede the development of the crystal nucleus, leading to an unexpectedly larger free energy barrier at low temperature. This, in turn, promotes the formation of a predominantly closed-packed critical nucleus, with fewer defects, thereby suggesting a new way to control the structure of the crystal nucleus, which is of key importance in catalysis.

Critical behavior in the system cyclopentanone + water + secondary butyl alcohol

NASA Astrophysics Data System (ADS)

Krishna, U. Santhi; Unni, P. K. Madhavan

2018-05-01

We report detailed measurements of coexistence surface in the ternary system cylcopentanone + water + secondary butyl alcohol. The coexistence surface is seen to have an unusual tunnel like feature and is a potential system in which special critical points such as the Quadruple Critical Point (QCP) could be studied. Analysis of coexistence curves indicates that the system shows 3D-Ising like critical behavior.

Disorders of Behavioral and Emotional Regulation in the First Years of Life: Early Risks and Intervention in the Developing Parent-Infant Relationship

ERIC Educational Resources Information Center

Papousek, Mechthild, Ed.; Schieche, Michael, Ed.; Wurmser, Harald, Ed.

2007-01-01

For every five healthy babies and infants, there is at least one who brings unusual stresses for its parents with behaviors such as inconsolable crying, sleep disorders, refusal to eat, chronic moodiness, incessant demands for attention, fearful clinging, or tantrums. Available for the first time in English, this influential German collection…

Base Rates of Social Skills Acquisition/Performance Deficits, Strengths, and Problem Behaviors: An Analysis of the Social Skills Improvement System-Rating Scales

ERIC Educational Resources Information Center

Gresham, Frank M.; Elliott, Stephen N.; Kettler, Ryan J.

2010-01-01

Base rate information is important in clinical assessment because one cannot know how unusual or typical a phenomenon is without first knowing its base rate in the population. This study empirically determined the base rates of social skills acquisition and performance deficits, social skills strengths, and problem behaviors using a nationally…

Cavitation in flowing superfluid helium

NASA Technical Reports Server (NTRS)

Daney, D. E.

1988-01-01

Flowing superfluid helium cavitates much more readily than normal liquid helium, and there is a marked difference in the cavitation behavior of the two fluids as the lambda point is traversed. Examples of cavitation in a turbine meter and centrifugal pump are given, together with measurements of the cavitation strength of flowing superfluid helium. The unusual cavitation behavior of superfluid helium is attributed to its immense thermal conductivity .

Classics in Chemical Neuroscience: Aripiprazole.

PubMed

Casey, Austen B; Canal, Clinton E

2017-06-21

Aripiprazole was the first antipsychotic developed to possess agonist properties at dopamine D 2 autoreceptors, a groundbreaking strategy that presented a new vista for schizophrenia drug discovery. The dopamine D 2 receptor is the crucial target of all extant antipsychotics, and all developed prior to aripiprazole were D 2 receptor antagonists. Extensive blockade of these receptors, however, typically produces extrapyramidal (movement) side effects, which plagued first-generation antipsychotics, such as haloperidol. Second-generation antipsychotics, such as clozapine, with unique polypharmacology and D 2 receptor binding kinetics, have significantly lower risk of movement side effects but can cause myriad additional ones, such as severe weight gain and metabolic dysfunction. Aripiprazole's polypharmacology, characterized by its unique agonist activity at dopamine D 2 and D 3 and serotonin 5-HT 1A receptors, as well as antagonist activity at serotonin 5-HT 2A receptors, translates to successful reduction of positive, negative, and cognitive symptoms of schizophrenia, while also mitigating risk of weight gain and movement side effects. New observations, however, link aripiprazole to compulsive behaviors in a small group of patients, an unusual side effect for antipsychotics. In this review, we discuss the chemical synthesis, pharmacology, pharmacogenomics, drug metabolism, and adverse events of aripiprazole, and we present a current understanding of aripiprazole's neurotherapeutic mechanisms, as well as the history and importance of aripiprazole to neuroscience.

Antioxidants and Autism: Teachers' Perceptions of Behavioral Changes.

PubMed

Sadek, Amy; Berk, Lee S; Mainess, Karen; Daher, Noha S

2018-06-05

BACKGROUND- Children with Autism Spectrum Disorder (ASD) demonstrate a physiological imbalance between free radicals, resultant from oxidative stress, and antioxidants. Oxidative stress is linked to the pathogenesis of this neurocognitive disorder. The aim of this pilot feasibility study was to examine the effect of consumption of high concentration antioxidant cacao on behavior of children with ASD. METHODS- This was a 4-week pre-test post-test experimental pilot study of high antioxidant cacao and children with ASD. Participants consumed 8 squares (or 16 grams) per day of the dark chocolate which had a concentration of 70% cacao and 30% organic cane sugar (total antioxidant concentration was 8,320). The two main behavioral measures were the Aberrant Behavior Checklist- 2nd Edition and the Autism Spectrum Rating Scale which were completed by the child's teacher at baseline and end of week four. RESULTS- Sixteen participants were recruited for this study. Follow up data was available on 12 participants (9 males, 3 females, mean age of 10.9 ±3.9 years). Significant improvements on the Autism Spectrum Rating Scale were noted in Social/Communication (p=0.03, η2=0.79), Unusual Behaviors (p=0.02, η2=0.70), and Self-Regulation (p=0.04, η2=0.59). No significant changes were noted on any of the Aberrant Behavior Checklist-2 subscales (p>.05). CONCLUSION- Results from this study support the potential therapeutic benefit of antioxidants in improving social communication, unusual behaviors, and self-regulation behaviors of children with ASD. Further robust randomized controlled trials are now necessary to elaborate the validity of these findings.

Understanding the Broad Substrate Repertoire of Nitroreductase Based on Its Kinetic Mechanism*

PubMed Central

Pitsawong, Warintra; Hoben, John P.; Miller, Anne-Frances

2014-01-01

The oxygen-insensitive nitroreductase from Enterobacter cloacae (NR) catalyzes two-electron reduction of nitroaromatics to the corresponding nitroso compounds and, subsequently, to hydroxylamine products. NR has an unusually broad substrate repertoire, which may be related to protein dynamics (flexibility) and/or a simple non-selective kinetic mechanism. To investigate the possible role of mechanism in the broad substrate repertoire of NR, the kinetics of oxidation of NR by para-nitrobenzoic acid (p-NBA) were investigated using stopped-flow techniques at 4 °C. The results revealed a hyperbolic dependence on the p-NBA concentration with a limiting rate of 1.90 ± 0.09 s−1, indicating one-step binding before the flavin oxidation step. There is no evidence for a distinct binding step in which specificity might be enforced. The reduction of p-NBA is rate-limiting in steady-state turnover (1.7 ± 0.3 s−1). The pre-steady-state reduction kinetics of NR by NADH indicate that NADH reduces the enzyme with a rate constant of 700 ± 20 s−1 and a dissociation constant of 0.51 ± 0.04 mm. Thus, we demonstrate simple transient kinetics in both the reductive and oxidative half-reactions that help to explain the broad substrate repertoire of NR. Finally, we tested the ability of NR to reduce para-hydroxylaminobenzoic acid, demonstrating that the corresponding amine does not accumulate to significant levels even under anaerobic conditions. Thus E. cloacae NR is not a good candidate for enzymatic production of aromatic amines. PMID:24706760

Unusual negative magnetoresistance in Bi2Se3-ySy topological insulator under perpendicular magnetic field

NASA Astrophysics Data System (ADS)

Singh, Rahul; Gangwar, Vinod K.; Daga, D. D.; Singh, Abhishek; Ghosh, A. K.; Kumar, Manoranjan; Lakhani, A.; Singh, Rajeev; Chatterjee, Sandip

2018-03-01

The magneto-transport properties of Bi2Se3-ySy were investigated. Magnetoresistance (MR) decreases with an increase in the S content, and finally, for 7% (i.e., y = 0.21) S doping, the magnetoresistance becomes negative. This negative MR is unusual as it is observed when a magnetic field is applied in the perpendicular direction to the plane of the sample. The magneto-transport behavior shows the Shubnikov-de Haas (SdH) oscillation, indicating the coexistence of surface and bulk states. The negative MR has been attributed to the non-trivial bulk conduction.

Numerical Study of a Long-Lived, Isolated Wake Vortex in Ground Effect

NASA Technical Reports Server (NTRS)

Proctor, Fred H.

2014-01-01

This paper examines a case observed during the 1990 Idaho Falls Test program, in which a wake vortex having an unusually long lifetime was observed while in ground effect. A numerical simulation is performed with a Large Eddy Simulation model to understand the response of the environment in affecting this event. In the simulation, it was found that one of the vortices decayed quickly, with the remaining vortex persisting beyond the time-bound of typical vortex lifetimes. This unusual behavior was found to be related to the first and second vertical derivatives of the ambient crosswind.

Effect of the Addition of a Labile Gelatin Component on the Degradation and Solute Release Kinetics of a Stable PEG Hydrogel

PubMed Central

Waldeck, H.; Kao, W. J.

2013-01-01

Characterization of the degradation mechanisms and resulting products of biodegradable materials is critical in understanding the behavior of the material including solute transport and biological response. Previous mathematical analyses of a semi-interpenetrating network (sIPN) containing both labile gelatin and a stable cross-linked poly(ethylene glycol) (PEG) network found that diffusion-based models alone were unable to explain the release kinetics of solutes from the system. In this study, degradation of the sIPN and its effect on solute release and swelling kinetics were investigated. The kinetics of the primary mode of degradation, gelatin dissolution, was dependent on temperature, preparation methods, PEGdA and gelatin concentration, and the weight ratio between the gelatin and PEG. The gelatin dissolution rate positively correlated with both matrix swelling and the release kinetics of high-molecular-weight model compound, FITC-dextran. Coupled with previous in vitro studies, the kinetics of sIPN degradation provided insights into the time-dependent changes in cellular response including adhesion and protein expression. These results provide a facile guide in material formulation to control the delivery of high-molecular-weight compounds with concomitant modulation of cellular behavior. PMID:21801489

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al. Part 1; Oxidation Kinetics

NASA Technical Reports Server (NTRS)

Raj. Sai V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 +/- 9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al. Part 1; Oxidation Kinetics

NASA Technical Reports Server (NTRS)

Raj. Sai V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 9.5 kJ mol-1. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17 Percent Cr and Cu-17 Percent Cr-5 Percent Al. Part 1; Oxidation Kinetics

NASA Technical Reports Server (NTRS)

Raj, S. V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu-17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9+/-9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr-5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR-5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene.

PubMed

Driver, Tom G; Woerpel, K A

2004-08-18

Kinetic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph3P)2AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic behavior in catalyst concentration was observed. A reactive intermediate, a silylsilver complex, was observed using low temperature 29Si NMR spectroscopy. Competition experiments between substituted styrenes and a deficient amount of 1 correlated well with the Hammett equation and provided a rho value of -0.62 +/- 0.02 using sigmap constants. These data support a mechanism involving reversible silver-promoted di-tert-butylsilylene extrusion from 1 followed by irreversible concerted electrophilic attack of the silylsilver intermediate on the alkene.

The onset of fluid-dynamical behavior in relativistic kinetic theory

NASA Astrophysics Data System (ADS)

Noronha, Jorge; Denicol, Gabriel S.

2017-11-01

In this proceedings we discuss recent findings regarding the large order behavior of the Chapman-Enskog expansion in relativistic kinetic theory. It is shown that this series in powers of the Knudsen number has zero radius of convergence in the case of a Bjorken expanding fluid described by the Boltzmann equation in the relaxation time approximation. This divergence stems from the presence of non-hydrodynamic modes, which give non-perturbative contributions to the Knudsen series.

Pair and triple correlations in the A+B-->B diffusion-controlled reaction

NASA Astrophysics Data System (ADS)

Kuzovkov, Vladimir; Kotomin, Eugene

1994-03-01

An exact solution for the one-dimensional kinetics of the diffusion-controlled reaction A+B-->B is obtained by means of the three-particle correlation functions. Because of a lattice discreteness each site could be occupied by a single particle only which leads to the so-called ``bus effect'': Recombination of any particle A is defined by a spatial configuration of two nearest particles B only surrounding A from its left and right. This results in the unusual algebraic decay law, n(t)~t-1, which asymptotically (as t-->∞) does not depend on the trap B concentration.

Water vapor sorption properties of cellulose nanocrystals and nanofibers using dynamic vapor sorption apparatus.

PubMed

Guo, Xin; Wu, Yiqiang; Xie, Xinfeng

2017-10-27

Hygroscopic behavior is an inherent characteristic of nanocellulose which strongly affects its applications. In this study, the water vapor sorption behavior of four nanocellulose samples, such as cellulose nanocrystals and nanofibers with cellulose I and II structures (cellulose nanocrystals (CNC) I, CNC II, cellulose nanofibers (CNF) I, and CNF II) were studied by dynamic vapor sorption. The highly reproducible data including the running time, real-time sample mass, target relative humidity (RH), actual RH, and isotherm temperature were recorded during the sorption process. In analyzing these data, significant differences in the total running time, equilibrium moisture content, sorption hysteresis and sorption kinetics between these four nanocellulose samples were confirmed. It was important to note that CNC I, CNC II, CNF I, and CNF II had equilibrium moisture contents of 21.4, 28.6, 33.2, and 38.9%, respectively, at a RH of 95%. Then, the sorption kinetics behavior was accurately described by using the parallel exponential kinetics (PEK) model. Furthermore, the Kelvin-Voigt model was introduced to interpret the PEK behavior and calculate the modulus of these four nanocellulose samples.

Mechanical Behavior of AZ31B Mg Alloy Sheets under Monotonic and Cyclic Loadings at Room and Moderately Elevated Temperatures

PubMed Central

Nguyen, Ngoc-Trung; Seo, Oh Suk; Lee, Chung An; Lee, Myoung-Gyu; Kim, Ji-hoon; Kim, Heon Young

2014-01-01

Large-strain monotonic and cyclic loading tests of AZ31B magnesium alloy sheets were performed with a newly developed testing system, at different temperatures, ranging from room temperature to 250 °C. Behaviors showing significant twinning during initial in-plane compression and untwinning in subsequent tension at and slightly above room temperature were recorded. Strong yielding asymmetry and nonlinear hardening behavior were also revealed. Considerable Bauschinger effects, transient behavior, and variable permanent softening responses were observed near room temperature, but these were reduced and almost disappeared as the temperature increased. Different stress–strain responses were inherent to the activation of twinning at lower temperatures and non-basal slip systems at elevated temperatures. A critical temperature was identified to account for the transition between the twinning-dominant and slip-dominant deformation mechanisms. Accordingly, below the transition point, stress–strain curves of cyclic loading tests exhibited concave-up shapes for compression or compression following tension, and an unusual S-shape for tension following compression. This unusual shape disappeared when the temperature was above the transition point. Shrinkage of the elastic range and variation in Young’s modulus due to plastic strain deformation during stress reversals were also observed. The texture-induced anisotropy of both the elastic and plastic behaviors was characterized experimentally. PMID:28788514

Attitude-behavior congruity, mindfulness, and self-focused attention: A behavior-analytic reconstruction

PubMed Central

Street, Warren R.

1994-01-01

Social psychologists have responded to research reporting low agreement between attitude measures and related behavior with attempts to explain the incongruities and enhance agreement. This article examines attitude-behavior incongruity from a behavior-analytic point of view. Traditional and behavior-analytic views of attitudes and behaviors are compared. In the behavior-analytic view, answering an attitude scale should be considered as behavior displayed by a person under rather unusual social conditions, not as a reflection of an enduring personal disposition. Reasons why questionnaire-answering behavior will not resemble behavior in other functionally different social conditions are reviewed. Special attention is extended to two representative lines of attitude-behavior research: mindfulness and self-focused attention. Discriminative stimuli in both areas of study have produced more predictable agreement between questionnaire-answering behavior and behavior in other settings. PMID:22478180

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.

The Newell Test Should Commit to Diagnosing Dysfunctions

NASA Technical Reports Server (NTRS)

Clancey, William J.

2003-01-01

"Conceptual coordination" analysis bridges connectionism and symbolic approaches by posting a "process memory" by which categories are physically coordinated (as neural networks) in time. Focusing on dysfunctions and odd behaviors like slips reveals the function of consciousness, especially taken-for-granted constructive processes, different from conventional programming constructs. Newell strongly endorsed identifying architectural limits; the heuristic of "diagnose unusual behaviors" will provide targets of opportunity that greatly strengthens the Newell Test.

Usual and Unusual Care: Existing Practice Control Groups In Randomized Controlled Trials of Behavioral Interventions

PubMed Central

Freedland, Kenneth E.; Mohr, David C.; Davidson, Karina W.; Schwartz, Joseph E.

2011-01-01

Objective To examine the use of existing practice control groups in randomized controlled trials of behavioral interventions, and the role of extrinsic healthcare services in the design and conduct of behavioral trials. Method Selective qualitative review. Results Extrinsic healthcare services, also known as nonstudy care, have important but under-recognized effects on the design and conduct of behavioral trials. Usual care, treatment as usual, standard of care, and other existing practice control groups pose a variety of methodological and ethical challenges, but they play a vital role in behavioral intervention research. Conclusion This review highlights the need for a scientific consensus statement on control groups in behavioral trials. PMID:21536837

Usual and unusual care: existing practice control groups in randomized controlled trials of behavioral interventions.

PubMed

Freedland, Kenneth E; Mohr, David C; Davidson, Karina W; Schwartz, Joseph E

2011-05-01

To evaluate the use of existing practice control groups in randomized controlled trials of behavioral interventions and the role of extrinsic health care services in the design and conduct of behavioral trials. Selective qualitative review. Extrinsic health care services, also known as nonstudy care, have important but under-recognized effects on the design and conduct of behavioral trials. Usual care, treatment-as-usual, standard of care, and other existing practice control groups pose a variety of methodological and ethical challenges, but they play a vital role in behavioral intervention research. This review highlights the need for a scientific consensus statement on control groups in behavioral trials.

Cell shape characterization and classification with discrete Fourier transforms and self-organizing maps.

PubMed

Kriegel, Fabian L; Köhler, Ralf; Bayat-Sarmadi, Jannike; Bayerl, Simon; Hauser, Anja E; Niesner, Raluca; Luch, Andreas; Cseresnyes, Zoltan

2018-03-01

Cells in their natural environment often exhibit complex kinetic behavior and radical adjustments of their shapes. This enables them to accommodate to short- and long-term changes in their surroundings under physiological and pathological conditions. Intravital multi-photon microscopy is a powerful tool to record this complex behavior. Traditionally, cell behavior is characterized by tracking the cells' movements, which yields numerous parameters describing the spatiotemporal characteristics of cells. Cells can be classified according to their tracking behavior using all or a subset of these kinetic parameters. This categorization can be supported by the a priori knowledge of experts. While such an approach provides an excellent starting point for analyzing complex intravital imaging data, faster methods are required for automated and unbiased characterization. In addition to their kinetic behavior, the 3D shape of these cells also provide essential clues about the cells' status and functionality. New approaches that include the study of cell shapes as well may also allow the discovery of correlations amongst the track- and shape-describing parameters. In the current study, we examine the applicability of a set of Fourier components produced by Discrete Fourier Transform (DFT) as a tool for more efficient and less biased classification of complex cell shapes. By carrying out a number of 3D-to-2D projections of surface-rendered cells, the applied method reduces the more complex 3D shape characterization to a series of 2D DFTs. The resulting shape factors are used to train a Self-Organizing Map (SOM), which provides an unbiased estimate for the best clustering of the data, thereby characterizing groups of cells according to their shape. We propose and demonstrate that such shape characterization is a powerful addition to, or a replacement for kinetic analysis. This would make it especially useful in situations where live kinetic imaging is less practical or not possible at all. © 2017 International Society for Advancement of Cytometry. © 2017 International Society for Advancement of Cytometry.

Variability of Practice and the Transfer of Training of Motor Skills

DTIC Science & Technology

1983-11-01

Christina (Eds.), Psychology of motor be- havior and sport (Vol. 2). Champaign, IL: Human Kinetics Publishers, 1977. 36 Kerr, R., & Booth, B. Specific...motor behavior and sport (Vol. 1). Champaign, IL: Human Kinetics Publishers, 1977. 38 061384

KINETIC MODEL OF BIOSURFACTANT ENHANCED HEXADECANE BIODEGRADATION BY PSEUDOMONAS AERUGINOSA. (R827132)

EPA Science Inventory

Many sites of environmental concern contain groundwater contaminated with nonaqueous phase liquids (NAPL). In such sites interfacial processes may affect both the equilibrium and kinetic behavior of the system. In particular, insoluble hydrocarbon partitioning and microbial biode...

Transient atomic behavior and surface kinetics of GaN

NASA Astrophysics Data System (ADS)

Moseley, Michael; Billingsley, Daniel; Henderson, Walter; Trybus, Elaissa; Doolittle, W. Alan

2009-07-01

An in-depth model for the transient behavior of metal atoms adsorbed on the surface of GaN is developed. This model is developed by qualitatively analyzing transient reflection high energy electron diffraction (RHEED) signals, which were recorded for a variety of growth conditions of GaN grown by molecular-beam epitaxy (MBE) using metal-modulated epitaxy (MME). Details such as the initial desorption of a nitrogen adlayer and the formation of the Ga monolayer, bilayer, and droplets are monitored using RHEED and related to Ga flux and shutter cycles. The suggested model increases the understanding of the surface kinetics of GaN, provides an indirect method of monitoring the kinetic evolution of these surfaces, and introduces a novel method of in situ growth rate determination.

Single-exponential activation behavior behind the super-Arrhenius relaxations in glass-forming liquids.

PubMed

Wang, Lianwen; Li, Jiangong; Fecht, Hans-Jörg

2010-11-17

The reported relaxation time for several typical glass-forming liquids was analyzed by using a kinetic model for liquids which invoked a new kind of atomic cooperativity--thermodynamic cooperativity. The broadly studied 'cooperative length' was recognized as the kinetic cooperativity. Both cooperativities were conveniently quantified from the measured relaxation data. A single-exponential activation behavior was uncovered behind the super-Arrhenius relaxations for the liquids investigated. Hence the mesostructure of these liquids and the atomic mechanism of the glass transition became clearer.

Thermodynamic and Kinetic Behavior of the Polystyrene/Poly(vinyl methyl ether) Blend as Studied by Excimer Fluorescence.

DTIC Science & Technology

1986-01-02

AD-A±63 895 THERMODYNAMIC AND KINETIC BEHAVIOR OF THE / POLYSTYRENE/POLY(YINYL METHYL E..(U) STANFORD UNIY CALIFDEPT OF CHEMICAL ENGINEERING C N...Polystyrene/Poly(vinyl methyl ether) Blend 7. DEcFRMN 81 toOR 30USptE8 00~ as Studied by Excimer Fluorescence 6 EFRIGOG EOTNME *AUTHOR() a. CONTRACT OR GRANT...werea fondoare ihemoriisof * ~ Ex e sp fluodecositionsdu to deud Gen e and hoog Pinus Florsneis shownhase migrationprocSECURITY CLASIFICTIO OFd

The D1 and D2 proteins of dinoflagellates: unusually accumulated mutations which influence on PSII photoreaction.

PubMed

Iida, Satoko; Kobiyama, Atsushi; Ogata, Takehiko; Murakami, Akio

2008-01-01

Plastid encoded genes of the dinoflagellates are rapidly evolving and most divergent. The importance of unusually accumulated mutations on structure of PSII core protein and photosynthetic function was examined in the dinoflagellates, Symbiodinium sp. and Alexandrium tamarense. Full-length cDNA sequences of psbA (D1 protein) and psbD (D2 protein) were obtained and compared with the other oxygen-evolving photoautotrophs. Twenty-three amino acid positions (7%) for the D1 protein and 34 positions (10%) for the D2 were mutated in the dinoflagellates, although amino acid residues at these positions were conserved in cyanobacteria, the other algae, and plant. Many mutations were likely to distribute in the N-terminus and the D-E interhelical loop of the D1 protein and helix B of D2 protein, while the remaining regions were well conserved. The different structural properties in these mutated regions were supported by hydropathy profiles. The chlorophyll fluorescence kinetics of the dinoflagellates was compared with Synechocystis sp. PCC6803 in relation to the altered protein structure.

Hexakis(3,6-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)cyclohexane: Closed-shell [6]Radialene or Open-shell Hexa-radicaloid?

PubMed

Wu, Jishan; Feng, Jiaqi; Gopalakrishna, Tullimilli Y; Phan, Hoa

2018-04-19

We report a star-shaped hexaquinocyclohexane molecule 4c, which turns out to be a closed-shell extended [6]radialene with a twisted-boat conformation according to X-ray crystallographic analysis. It was formed by an unusually slow decay of its in situ generated open-shell valence isomer, the hexa-radicaloid 4o, with a half-life time of about 156 min at room temperature. Reaction progress kinetic analysis revealed a large energy barrier of about 95.5 ± 4.3 kJ/mol at room temperature from the hexa-radical form 4o to the contorted [6]radialene form 4c, because the transformation need overcome large steric repulsion between the neighbouring phenoxyl units. Compound 4c can be chemically reduced to radical anion and dianion, and the dianion is actually a diradical dianion, with a calculated diradical character of 71.9%. This study demonstrated the unique chemical bonding nature of contorted quinoidal π-conjugated molecules and a very unusual valence isomerization process. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metastable Superconductivity in Two-Dimensional IrTe2 Crystals.

PubMed

Yoshida, Masaro; Kudo, Kazutaka; Nohara, Minoru; Iwasa, Yoshihiro

2018-05-09

Two-dimensional (2D) materials exhibit unusual physical and chemical properties that are attributed to the thinning-induced modification of their electronic band structure. Recently, reduced thickness was found to dramatically impact not only the static electronic structure, but also the dynamic ordering kinetics. The ordering kinetics of first-order phase transitions becomes significantly slowed with decreasing thickness, and metastable supercooled states can be realized by thinning alone. We therefore focus on layered iridium ditelluride (IrTe 2 ), a charge-ordering system that is transformed into a superconductor by suppressing its first-order transition. Here, we discovered a persistent superconducting zero-resistance state in mechanically exfoliated IrTe 2 thin flakes. The maximum superconducting critical temperature ( T c ) was identical to that which is chemically optimized, and the emergent superconductivity was revealed to have a metastable nature. The discovered robust metastable superconductivity suggests that 2D material is a new platform to induce, control, and functionalize metastable electronic states that are inaccessible in bulk crystals.

A Unified Model of Phantom Energy and Dark Matter

NASA Astrophysics Data System (ADS)

Chaves, Max; Singleton, Douglas

2008-01-01

To explain the acceleration of the cosmological expansion researchers have considered an unusual form of mass-energy generically called dark energy. Dark energy has a ratio of pressure over mass density which obeys w = p/ρ < -1/3. This form of mass-energy leads to accelerated expansion. An extreme form of dark energy, called phantom energy, has been proposed which has w = p/ρ < -1. This possibility is favored by the observational data. The simplest model for phantom energy involves the introduction of a scalar field with a negative kinetic energy term. Here we show that theories based on graded Lie algebras naturally have such a negative kinetic energy and thus give a model for phantom energy in a less ad hoc manner. We find that the model also contains ordinary scalar fields and anti-commuting (Grassmann) vector fields which act as a form of two component dark matter. Thus from a gauge theory based o! n a graded algebra we naturally obtained both phantom energy and dark matter.

Unusual kinetics of poly(ethylene glycol) oxidation with cerium(IV) ions in sulfuric acid medium and implications for copolymer synthesis.

PubMed

Szymański, Jan K; Temprano-Coleto, Fernando; Pérez-Mercader, Juan

2015-03-14

The cerium(IV)-alcohol couple in an acidic medium is an example of a redox system capable of initiating free radical polymerization. When the alcohol has a polymeric nature, the outcome of such a process is a block copolymer, a member of a class of compounds possessing many useful properties. The most common polymer with a terminal -OH group is poly(ethylene glycol) (PEG); however, the detailed mechanism of its reaction with cerium(IV) remains underexplored. In this paper, we report our findings for this reaction based on spectrophotometric measurements and kinetic modeling. We find that both the reaction order and the net rate constant for the oxidation process depend strongly on the nature of the acidic medium used. In order to account for the experimental observations, we postulate that protonation of PEG decreases its affinity for some of the cerium(IV)-sulfate complexes formed in the system.

Wave-particle interactions in rotating mirrorsa)

NASA Astrophysics Data System (ADS)

Fetterman, Abraham J.; Fisch, Nathaniel J.

2011-05-01

Wave-particle interactions in E ×B rotating plasmas feature an unusual effect: particles are diffused by waves in both potential energy and kinetic energy. This wave-particle interaction generalizes the alpha channeling effect, in which radio frequency waves are used to remove alpha particles collisionlessly at low energy. In rotating plasmas, the alpha particles may be removed at low energy through the loss cone, and the energy lost may be transferred to the radial electric field. This eliminates the need for electrodes in the mirror throat, which have presented serious technical issues in past rotating plasma devices. A particularly simple way to achieve this effect is to use a high azimuthal mode number perturbation on the magnetic field. Rotation can also be sustained by waves in plasmas without a kinetic energy source. This type of wave has been considered for plasma centrifuges used for isotope separation. Energy may also be transferred from the electric field to particles or waves, which may be useful for ion heating and energy generation.

Testing BR photocycle kinetics.

PubMed Central

Nagle, J F; Zimanyi, L; Lanyi, J K

1995-01-01

An improved K absorption spectrum in the visible is obtained from previous photocycle data for the D96N mutant of bacteriorhodopsin, and the previously obtained M absorption spectrum in the visible and the fraction cycling are confirmed at 25 degrees C. Data at lower temperatures are consistent with negligible temperature dependence in the spectra from 5 degrees C to 25 degrees C. Detailed analysis strongly indicates that there are two intermediates in addition to the first intermediate K and the last intermediate M. Assuming two of the intermediates have the same spectrum and using the L spectrum obtained previously, the best kinetic model with four intermediates that fits the time course of the intermediates is rather unusual, with two L's on a cul-de-sac. However, a previously proposed, more conventional model with five intermediates, including two L's with the same spectra and two M's with the same spectra, also fits the time course of the intermediates nearly as well. A new criterion that tests an individual proposed spectrum against data is also proposed. PMID:7787034

Kinetic analysis of superparamagnetic iron oxide nanoparticles in the liver of body-temperature-controlled mice using dynamic susceptibility contrast magnetic resonance imaging and an empirical mathematical model.

PubMed

Murase, Kenya; Assanai, Purapan; Takata, Hiroshige; Matsumoto, Nozomi; Saito, Shigeyoshi; Nishiura, Motoko

2015-06-01

The purpose of this study was to develop a method for analyzing the kinetic behavior of superparamagnetic iron oxide nanoparticles (SPIONs) in the murine liver under control of body temperature using dynamic susceptibility contrast magnetic resonance imaging (DSC-MRI) and an empirical mathematical model (EMM). First, we investigated the influence of body temperature on the kinetic behavior of SPIONs in the liver by controlling body temperature using our temperature-control system. Second, we investigated the kinetic behavior of SPIONs in the liver when mice were injected with various doses of GdCl3, while keeping the body temperature at 36°C. Finally, we investigated it when mice were injected with various doses of zymosan, while keeping the body temperature at 36°C. We also investigated the effect of these substances on the number of Kupffer cells by immunohistochemical analysis using the specific surface antigen of Kupffer cells (CD68). To quantify the kinetic behavior of SPIONs in the liver, we calculated the upper limit of the relative enhancement (A), the rates of early contrast uptake (α) and washout or late contrast uptake (β), the parameter related to the slope of early uptake (q), the area under the curve (AUC), the maximum change of transverse relaxation rate (ΔR2) (ΔR2(max)), the time to ΔR2(max) (Tmax), and ΔR2 at the last time point (ΔR2(last)) from the time courses of ΔR2 using the EMM. The β and Tmax values significantly decreased and increased, respectively, with decreasing body temperature, suggesting that the phagocytic activity of Kupffer cells is significantly affected by body temperature. The AUC, ΔR2(max), and ΔR2(last) values decreased significantly with increasing dose of GdCl3, which was consistent with the change in the number of CD68-positive cells. They increased with increasing dose of zymosan, which was also consistent with the change in the number of CD68-positive cells. These results suggest that AUC, ΔR2(max), and ΔR2(last) reflect the number of Kupffer cells. In conclusion, we presented a method for analyzing the kinetic behavior of SPIONs in the liver using DSC-MRI and EMM, and investigated the influence of body temperature, GdCl3, and zymosan using body-temperature-controlled mice. The present study suggests that control of body temperature is essential for investigating the kinetic behavior of SPIONs in the liver and that our method will be applicable and useful for quantifying the responses of Kupffer cells to various drugs under control of body temperature. Copyright © 2015 Elsevier Inc. All rights reserved.

Stepwise Elastic Behavior in a Model Elastomer

NASA Astrophysics Data System (ADS)

Bhawe, Dhananjay M.; Cohen, Claude; Escobedo, Fernando A.

2004-12-01

MonteCarlo simulations of an entanglement-free cross-linked polymer network of semiflexible chains reveal a peculiar stepwise elastic response. For increasing stress, step jumps in strain are observed that do not correlate with changes in the number of aligned chains. We show that this unusual behavior stems from the ability of the system to form multiple ordered chain domains that exclude the cross-linking species. This novel elastomer shows a toughening behavior similar to that observed in biological structural materials, such as muscle proteins and abalone shell adhesive.

Zolpidem-induced amnesia and somnambulism: rare occurrences?

PubMed

Tsai, Jui-Hsiu; Yang, Pinchen; Chen, Cheng-Chung; Chung, Weilum; Tang, Tze-Chun; Wang, Shing-Yaw; Liu, Jong-Kang

2009-01-01

Zolpidem, a non-benzodiazepine hypnotic of the imidazopyridine class, is very effective in treating insomnia with previous claims of little adverse effects. However, zolpidem-induced somnambulism and amnesic sleep-related behavioral problems were begun to be reported in literature but no systemic investigation has been undertaken in non-Western cultures. In our current retrospective survey, 5.1% (13 out of 255) of Taiwanese patients reported change in sleep-related behavior as adverse effects. This serves as a reminder for clinicians to inquire regarding any unusual behavior of parasomniac activities when prescribing zolpidem.

Video cameras on wild birds.

PubMed

Rutz, Christian; Bluff, Lucas A; Weir, Alex A S; Kacelnik, Alex

2007-11-02

New Caledonian crows (Corvus moneduloides) are renowned for using tools for extractive foraging, but the ecological context of this unusual behavior is largely unknown. We developed miniaturized, animal-borne video cameras to record the undisturbed behavior and foraging ecology of wild, free-ranging crows. Our video recordings enabled an estimate of the species' natural foraging efficiency and revealed that tool use, and choice of tool materials, are more diverse than previously thought. Video tracking has potential for studying the behavior and ecology of many other bird species that are shy or live in inaccessible habitats.

Kinetic mechanism and quaternary structure of Aminobacter aminovorans NADH:flavin oxidoreductase: an unusual flavin reductase with bound flavin.

PubMed

Russell, Thomas R; Demeler, Borries; Tu, Shiao-Chun

2004-02-17

The homodimeric NADH:flavin oxidoreductase from Aminobacter aminovorans is an NADH-specific flavin reductase herein designated FRD(Aa). FRD(Aa) was characterized with respect to purification yields, thermal stability, isoelectric point, molar absorption coefficient, and effects of phosphate buffer strength and pH on activity. Evidence from this work favors the classification of FRD(Aa) as a flavin cofactor-utilizing class I flavin reductase. The isolated native FRD(Aa) contained about 0.5 bound riboflavin-5'-phosphate (FMN) per enzyme monomer, but one bound flavin cofactor per monomer was obtainable in the presence of excess FMN or riboflavin. In addition, FRD(Aa) holoenzyme also utilized FMN, riboflavin, or FAD as a substrate. Steady-state kinetic results of substrate titrations, dead-end inhibition by AMP and lumichrome, and product inhibition by NAD(+) indicated an ordered sequential mechanism with NADH as the first binding substrate and reduced FMN as the first leaving product. This is contrary to the ping-pong mechanism shown by other class I flavin reductases. The FMN bound to the native FRD(Aa) can be fully reduced by NADH and subsequently reoxidized by oxygen. No NADH binding was detected using 90 microM FRD(Aa) apoenzyme and 300 microM NADH. All results favor the interpretation that the bound FMN was a cofactor rather than a substrate. It is highly unusual that a flavin reductase using a sequential mechanism would require a flavin cofactor to facilitate redox exchange between NADH and a flavin substrate. FRD(Aa) exhibited a monomer-dimer equilibrium with a K(d) of 2.7 microM. Similarities and differences between FRD(Aa) and certain flavin reductases are discussed.

KINETIC AND DYNAMIC ASPECTS OF ARSENIC TOXICITY

EPA Science Inventory

This project integrates research on aspects of the kinetic and dynamic behavior of arsenic. A PBPK model for arsenic will be developed using metabolism and disposition data from studies in mice. Retention of arsenic in the tissues following exposure to arsenic will be investigate...

Optimizing Feedback Utilization in Motor Skill Training

DTIC Science & Technology

1988-02-01

Abehiorlemphasis. Champaign, IL: Human Kinetics Press. Schmidt, R.A., & White, J.L. (1972). Evidence for an error-detection mechanism in motor skills...motor program. In D.M. Landers & R.W. Christina (Eds.), Psyc g 2 moto behavior d S (Vol 1). Champaign, IL: Human Kinetics Press. Shapiro, D.C. (1978...and sport research. Champaign, IL: Human Kinetics Press. Schmidt, R.A. (in press). Toward a better understanding of motor learning. Theoretical and

Metadynamic and static recrystallization softening behavior of a bainite steel

NASA Astrophysics Data System (ADS)

Li, Lixin; Zheng, Liangyu; Ye, Ben; Tong, Zeqiong

2018-01-01

The metadynamic recrystallization (MDRX) and static recrystallization (SRX) softening behavior of a bainite steel was investigated by two-pass isothermal compression experiments at temperatures of 1173, 1273, 1373, and 1473 K and strain rates of 0.01, 0.1, 1, and 10 s-1 with inter-pass times of 1, 5, 10, and 30 s on a Gleeble-1500 thermo-mechanical simulator. Kinetic equations were developed to evaluate the softening fractions caused by MDRX and SRX. A comparison between the experimental and predicted softening fractions showed that the proposed kinetic equations can provide a precise estimation of the MDRX and SRX behavior of the studied steel. The results based on the kinetic equations indicated that the MDRX and SRX softening fraction increases with the increase in strain rate, deformation temperature, inter-pass time, and pre-strain; the activation energy of MDRX is much smaller than that of SRX; and the no-recrystallization temperature of the investigated steel is 1179.4 K.

Variations in protein/flavin hydrogen bonding in a LOV domain produce non-Arrhenius kinetics of adduct decay†

PubMed Central

Zoltowski, Brian D.; Nash, Abigail I.; Gardner, Kevin H.

2011-01-01

Light Oxygen Voltage (LOV) domains utilize a conserved blue light-dependent mechanism to control a diverse array of effector domains in biological and engineered proteins. Variations in the kinetics and efficiency of LOV photochemistry fine tune various aspects of the photic response. Characterization of the kinetics of a key aspect of this photochemical mechanism in EL222, a blue-light responsive DNA binding protein from Erythrobacter litoralis HTCC2594, reveals unique non-Arrhenius behavior in the rate of dark state cleavage of the photochemically-generated adduct. Sequence analysis and mutagenesis studies establish that this effect stems from a Gln to Ala mutation unique to EL222 and homologous proteins from marine bacteria. Kinetic and spectroscopic analyses reveal that hydrogen bonding interactions between the FMN N1, O2 and ribityl hydroxyls with the surrounding protein regulate photocycle kinetics and stabilize the LOV active site from temperature-induced alteration in local structure. Substitution of residues interacting with the N1-O2 locus modulates adduct stability, structural flexibility and sequestration of the active site from bulk solvent without perturbation of light-activated DNA binding. Together, these variants link non-Arrhenius behavior to specific alteration of an H-bonding network, while affording tunability of photocycle kinetics. PMID:21923139

Variations in protein-flavin hydrogen bonding in a light, oxygen, voltage domain produce non-Arrhenius kinetics of adduct decay.

PubMed

Zoltowski, Brian D; Nash, Abigail I; Gardner, Kevin H

2011-10-18

Light, oxygen, voltage (LOV) domains utilize a conserved blue light-dependent mechanism to control a diverse array of effector domains in biological and engineered proteins. Variations in the kinetics and efficiency of LOV photochemistry fine-tune various aspects of the photic response. Characterization of the kinetics of a key aspect of this photochemical mechanism in EL222, a blue light responsive DNA binding protein from Erythrobacter litoralis HTCC2594, reveals unique non-Arrhenius behavior in the rate of dark-state cleavage of the photochemically generated adduct. Sequence analysis and mutagenesis studies establish that this effect stems from a Gln to Ala mutation unique to EL222 and homologous proteins from marine bacteria. Kinetic and spectroscopic analyses reveal that hydrogen bonding interactions between the FMN N1, O2, and ribityl hydroxyls and the surrounding protein regulate photocycle kinetics and stabilize the LOV active site from temperature-induced alteration in local structure. Substitution of residues interacting with the N1-O2 locus modulates adduct stability, structural flexibility, and sequestration of the active site from bulk solvent without perturbation of light-activated DNA binding. Together, these variants link non-Arrhenius behavior to specific alteration of an H-bonding network, while affording tunability of photocycle kinetics. © 2011 American Chemical Society

Interaction and Correlation Effects in Quasi Two-dimensional Materials

NASA Astrophysics Data System (ADS)

Louie, Steven G.

2015-03-01

Experimental and theoretical studies of atomically thin quasi two-dimensional materials (typically related to some parent van der Waals layered crystals) and their nanostructures have revealed that these systems can exhibit highly unusual behaviors. In this talk, we discuss some theoretical studies of the electronic, transport and optical properties of such systems. We present results on graphene and graphene nanostructures as well as other quasi-2D systems such as monolayer and few-layer transition metal dichalcogenides (e.g., MoS2, MoSe2, WS2, and WSe2) and metal monochalcogenides (such as GaSe and FeSe). Owing to their reduced dimensionality, these systems present opportunities for unusual manifestation of concepts and phenomena that may not be so prominent or have not been seen in bulk materials. Symmetry and many-body interaction effects often play a critical role in shaping qualitatively and quantitatively their properties. Several quantum phenomena are discussed, including novel and dominant exciton effects, tunable magnetism, electron supercollimation by disorder, unusual plasmon behaviors, and possible enhanced superconductivity in some of these systems. We investigate their physical origins and compare theoretical predictions with experimental data. This work was supported by DOE under Contract No. DE-AC02-05CH11231 and by NSF under Grant No. DMR10-1006184. I would like to acknowledge collaborations with members of the Louie group and the experimental groups of Crommie, Heinz, Wang, and Zhang.

The S4–S5 Linker Acts as a Signal Integrator for hERG K+ Channel Activation and Deactivation Gating

PubMed Central

Ng, Chai Ann; Perry, Matthew D.; Tan, Peter S.; Hill, Adam P.; Kuchel, Philip W.; Vandenberg, Jamie I.

2012-01-01

Human ether-à-go-go-related gene (hERG) K+ channels have unusual gating kinetics. Characterised by slow activation/deactivation but rapid inactivation/recovery from inactivation, the unique gating kinetics underlie the central role hERG channels play in cardiac repolarisation. The slow activation and deactivation kinetics are regulated in part by the S4–S5 linker, which couples movement of the voltage sensor domain to opening of the activation gate at the distal end of the inner helix of the pore domain. It has also been suggested that cytosolic domains may interact with the S4–S5 linker to regulate activation and deactivation kinetics. Here, we show that the solution structure of a peptide corresponding to the S4–S5 linker of hERG contains an amphipathic helix. The effects of mutations at the majority of residues in the S4–S5 linker of hERG were consistent with the previously identified role in coupling voltage sensor movement to the activation gate. However, mutations to Ser543, Tyr545, Gly546 and Ala548 had more complex phenotypes indicating that these residues are involved in additional interactions. We propose a model in which the S4–S5 linker, in addition to coupling VSD movement to the activation gate, also contributes to interactions that stabilise the closed state and a separate set of interactions that stabilise the open state. The S4–S5 linker therefore acts as a signal integrator and plays a crucial role in the slow deactivation kinetics of the channel. PMID:22359612

A surprisingly complex aqueous chemistry of the simplest amino acid. A pulse radiolysis and theoretical study on H/D kinetic isotope effects in the reaction of glycine anions with hydroxyl radicals.

PubMed

Stefanić, I; Ljubić, I; Bonifacić, M; Sabljić, A; Asmus, K-D; Armstrong, D A

2009-04-07

A pulse radiolysis study was carried out of the reaction rate constants and kinetic isotope effects of hydroxyl-radical-induced H/D abstraction from the most-simple alpha-amino acid glycine in its anionic form in water. The rate constants and yields of three predominantly formed radical products, glycyl (NH2-*CH-CO2-), aminomethyl (NH2-*CH2), and aminyl (*NH-CH2-CO2-) radicals, as well as of their partially or fully deuterated analogs, were found to be of comparable magnitude. The primary, secondary, and primary/secondary H/D kinetic isotope effects on the rate constants were determined with respect to each of the three radicals. The unusual variety of products for such an elementary reaction between two small and simple species indicates a complex mechanism with several reactions taking place simultaneously. Thus, a theoretical modeling of the reaction mechanism and kinetics in the gas- and aqueous phase was performed by using the unrestricted density functional theory with the BB1K functional (employing the polarizable continuum model for the aqueous phase), unrestricted coupled cluster UCCSD(T) method, and improved canonical variational theory. Several hydrogen-bonded prereaction complexes and transition states were detected. In particular, the calculations pointed to a significant mechanistic role of the three-electron two-orbital (sigma/sigma* N therefore O) hemibonded prereaction complexes in the aqueous phase. A good agreement with the experimental rate constants and kinetic isotope effects was achieved by downshifting the calculated reaction barriers by 3 kcal mol(-1) and damping the NH(D) stretching frequency by a factor of 0.86.

An unusual metallic behavior in a Ag4SSe single crystal

NASA Astrophysics Data System (ADS)

Matteppanavar, Shidaling; Bui, Nguyen Hai An; van Smaalen, Sander; Thamizhavel, A.; Ramakrishnan, S.

2018-04-01

We report the magnetic susceptibility, resistivity and heat capacity measurements on high quality single crystalline tetra silver sulphoselenide (Ag4SSe). The magnetic susceptibility and resistivity measurements show anomalies around 260 K. The large diamagnetic drop with hysteresis at the transition implies a first order transition. Such a diamagnetic drop cannot be ascribed to the formation of charge density wave (CDW) since the temperature dependence of the resistivity shows no upturn at this transition. Infact the resistivity is decreasing with decreasing temperature, indicating a metallic behavior. However, unlike normal metals, the resistivity is almost temperature independent in the temperature range from 4-180 K. Usually, when one observes a diamagnetic transition, it is assumed to be due to a drop in the density of states at the Fermi level which leads to the decrease in the Pauli paramagnetic susceptibility. Such a decrease in the density of states often results in an increase in resistivity unless mobility of the charge carriers changes significantly. Hence, we believe that in Ag4SSe, the structural transition causes an unusual Fermi surface reconstruction which in turn leads to a strange metallic behavior at low temperatures.

Particle size effect on strength, failure, and shock behavior in polytetrafluoroethylene-Al-W granular composite materials

NASA Astrophysics Data System (ADS)

Herbold, E. B.; Nesterenko, V. F.; Benson, D. J.; Cai, J.; Vecchio, K. S.; Jiang, F.; Addiss, J. W.; Walley, S. M.; Proud, W. G.

2008-11-01

The variation of metallic particle size and sample porosity significantly alters the dynamic mechanical properties of high density granular composite materials processed using a cold isostatically pressed mixture of polytetrafluoroethylene (PTFE), aluminum (Al), and tungsten (W) powders. Quasistatic and dynamic experiments are performed with identical constituent mass fractions with variations in the size of the W particles and pressing conditions. The relatively weak polymer matrix allows the strength and fracture modes of this material to be governed by the granular type behavior of agglomerated metal particles. A higher ultimate compressive strength was observed in relatively high porosity samples with small W particles compared to those with coarse W particles in all experiments. Mesoscale granular force chains of the metallic particles explain this unusual phenomenon as observed in hydrocode simulations of a drop-weight test. Macrocracks forming below the critical failure strain for the matrix and unusual behavior due to a competition between densification and fracture in dynamic tests of porous samples were also observed. Numerical modeling of shock loading of this granular composite material demonstrated that the internal energy, specifically thermal energy, of the soft PTFE matrix can be tailored by the W particle size distribution.

Epistatic interactions influence terrestrial–marine functional shifts in cetacean rhodopsin

PubMed Central

2017-01-01

Like many aquatic vertebrates, whales have blue-shifting spectral tuning substitutions in the dim-light visual pigment, rhodopsin, that are thought to increase photosensitivity in underwater environments. We have discovered that known spectral tuning substitutions also have surprising epistatic effects on another function of rhodopsin, the kinetic rates associated with light-activated intermediates. By using absorbance spectroscopy and fluorescence-based retinal release assays on heterologously expressed rhodopsin, we assessed both spectral and kinetic differences between cetaceans (killer whale) and terrestrial outgroups (hippo, bovine). Mutation experiments revealed that killer whale rhodopsin is unusually resilient to pleiotropic effects on retinal release from key blue-shifting substitutions (D83N and A292S), largely due to a surprisingly specific epistatic interaction between D83N and the background residue, S299. Ancestral sequence reconstruction indicated that S299 is an ancestral residue that predates the evolution of blue-shifting substitutions at the origins of Cetacea. Based on these results, we hypothesize that intramolecular epistasis helped to conserve rhodopsin's kinetic properties while enabling blue-shifting spectral tuning substitutions as cetaceans adapted to aquatic environments. Trade-offs between different aspects of molecular function are rarely considered in protein evolution, but in cetacean and other vertebrate rhodopsins, may underlie multiple evolutionary scenarios for the selection of specific amino acid substitutions. PMID:28250185

Kinetic behavior of Candida guilliermondii yeast during xylitol production from Brewer's spent grain hemicellulosic hydrolysate.

PubMed

Mussatto, Solange I; Dragone, Giuliano; Roberto, Inês C

2005-01-01

Brewer's spent grain, the main byproduct of breweries, was hydrolyzed with dilute sulfuric acid to produce a hemicellulosic hydrolysate (containing xylose as the main sugar). The obtained hydrolysate was used as cultivation medium by Candidaguilliermondii yeast in the raw form (containing 20 g/L xylose) and after concentration (85 g/L xylose), and the kinetic behavior of the yeast during xylitol production was evaluated in both media. Assays in semisynthetic media were also performed to compare the yeast performance in media without toxic compounds. According to the results, the kinetic behavior of the yeast cultivated in raw hydrolysate was as effective as in semisynthetic medium containing 20 g/L xylose. However, in concentrated hydrolysate medium, the xylitol production efficiency was 30.6% and 42.6% lower than in raw hydrolysate and semisynthetic medium containing 85 g/L xylose, respectively. In other words, the xylose-to-xylitol bioconversion from hydrolysate medium was strongly affected when the initial xylose concentration was increased; however, similar behavior did not occur from semisynthetic media. The lowest efficiency of xylitol production from concentrated hydrolysate can be attributed to the high concentration of toxic compounds present in this medium, resulting from the hydrolysate concentration process.

Conditions for critical effects in the mass action kinetics equations for water radiolysis

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

Wittman, Richard S.; Buck, Edgar C.; Mausolf, Edward J.

We report on a subtle global feature of the mass action kinetics equations for water radiolysis that results in predictions of a critical behavior in H2O2 and associated radical concentrations. While radiolysis kinetics has been studied extensively in the past, it is only in recent years that high speed computing has allowed the rapid exploration of the solution over widely varying dose and compositional conditions. We explore the radiolytic production of H2O2 under various externally fixed conditions of molecular H2 and O2 that have been regarded as problematic in the literature – specifically, “jumps” in predicted concentrations, and inconsistencies betweenmore » predictions and experiments have been reported for alpha radiolysis. We computationally map-out a critical concentration behavior for alpha radiolysis kinetics using a comprehensive set of reactions. We then show that all features of interest are accurately reproduced with 15 reactions. An analytical solution for steady-state concentrations of the 15 reactions reveals regions in [H2] and [O2] where the H2O2 concentration is not unique – both stable and unstable concentrations exist. The boundary of this region can be characterized analytically as a function of G-values and rate constants independent of dose rate. Physically, the boundary can be understood as separating a region where a steady-state H2O2 concentration exists, from one where it does not exist without a direct decomposition reaction. We show that this behavior is consistent with reported alpha radiolysis data and that no such behavior should occur for gamma radiolysis. We suggest experiments that could verify or discredit a critical concentration behavior for alpha radiolysis and could place more restrictive ranges on G-values from derived relationships between them.« less

Kinetic Description of the Impedance Probe

NASA Astrophysics Data System (ADS)

Oberrath, Jens; Lapke, Martin; Mussenbrock, Thomas; Brinkmann, Ralf

2011-10-01

Active plasma resonance spectroscopy is a well known diagnostic method. Many concepts of this method are theoretically investigated and realized as a diagnostic tool, one of which is the impedance probe (IP). The application of such a probe in plasmas with pressures of a few Pa raises the question whether kinetic effects have to be taken into account or not. To address this question a kinetic model is necessary. A general kinetic model for an electrostatic concept of active plasma spectroscopy was presented by R.P. Brinkmann and can be used to describe the multipole resonance probe (MRP). In principle the IP is interpretable as a special case of the MRP in lower order. Thus, we are able to describe the IP by the kinetic model of the MRP. Based on this model we derive a solution to investigate the influence of kinetic effects to the resonance behavior of the IP. Active plasma resonance spectroscopy is a well known diagnostic method. Many concepts of this method are theoretically investigated and realized as a diagnostic tool, one of which is the impedance probe (IP). The application of such a probe in plasmas with pressures of a few Pa raises the question whether kinetic effects have to be taken into account or not. To address this question a kinetic model is necessary. A general kinetic model for an electrostatic concept of active plasma spectroscopy was presented by R.P. Brinkmann and can be used to describe the multipole resonance probe (MRP). In principle the IP is interpretable as a special case of the MRP in lower order. Thus, we are able to describe the IP by the kinetic model of the MRP. Based on this model we derive a solution to investigate the influence of kinetic effects to the resonance behavior of the IP. The authors acknowledge the support by the Deutsche Forschungsgemeinschaft (DFG) via the Ruhr University Research School and the Federal Ministry of Education and Research in frame of the PluTO project.

10 CFR 712.13 - Supervisory review.

Code of Federal Regulations, 2012 CFR

2012-01-01

... HRP management official. Types of behavior and conditions that would indicate a concern include, but...) Irresponsibility in performing assigned duties; (10) Inability to deal with stress, or the appearance of being under unusual stress; (11) Failure to comply with work directives, hostility or aggression toward fellow...

10 CFR 712.13 - Supervisory review.

Code of Federal Regulations, 2011 CFR

2011-01-01

... HRP management official. Types of behavior and conditions that would indicate a concern include, but...) Irresponsibility in performing assigned duties; (10) Inability to deal with stress, or the appearance of being under unusual stress; (11) Failure to comply with work directives, hostility or aggression toward fellow...

10 CFR 712.13 - Supervisory review.

Code of Federal Regulations, 2013 CFR

2013-01-01

... HRP management official. Types of behavior and conditions that would indicate a concern include, but...) Irresponsibility in performing assigned duties; (10) Inability to deal with stress, or the appearance of being under unusual stress; (11) Failure to comply with work directives, hostility or aggression toward fellow...

10 CFR 712.13 - Supervisory review.

Code of Federal Regulations, 2014 CFR

2014-01-01

... HRP management official. Types of behavior and conditions that would indicate a concern include, but...) Irresponsibility in performing assigned duties; (10) Inability to deal with stress, or the appearance of being under unusual stress; (11) Failure to comply with work directives, hostility or aggression toward fellow...

Eating Disorders among College Women.

ERIC Educational Resources Information Center

Basow, Susan A.; Schneck, Renae

In the past 10 years, eating disorders among adolescent females have become of increasing concern. To assess the prevalence of eating disorders, unusual eating-related behaviors and attitudes, and psychological states among college women, 677 women, from three private northeastern United States colleges, completed a questionnaire assessing…

Technology-Enhanced Discovery

ERIC Educational Resources Information Center

Harrow, Chris; Chin, Lillian

2014-01-01

Exploration, innovation, proof: For students, teachers, and others who are curious, keeping an open mind and being ready to investigate unusual or unexpected properties will always lead to learning something new. Technology can further this process, allowing various behaviors to be analyzed that were previously memorized or poorly understood. This…

Coarsening of Ni(3)Si precipitates in binary Ni-Si alloys

NASA Astrophysics Data System (ADS)

Cho, Jin-Hoon

The coarsening behavior of coherent gammasp'\\ (Nisb3Si) precipitates with volume fractions, f, ranging from 0.017 to 0.32 in binary Ni-Si alloys was investigated. All of the alloys were aged at 650sp° C for times as long as 2760 h and measurements were made of the kinetics of coarsening, particle size distributions and the evolution of particle morphologies using transmission electron microscopy. The kinetics of solute depletion were investigated using measurements of the ferromagnetic Curie temperature. We successfully overcame the difficulties in obtaining uniform spatial distributions of precipitates at small f by employing an up-quenching treatment; alloys with f less than 0.1 were pre-aged at 530sp° C prior to re-aging at the normal aging temperature of 650sp° C. Almost identical coarsening behavior exhibited by an alloy subjected to both isothermal and up-quenching treatments confirm that the up-quenching treatments do not affect any aspect of the coarsening behavior. Consistent with previous studies, the particles are spherical in shape when small and evolve to a cuboidal shape, with flat faces parallel to {}, as they grow. This shape transition was characterized quantitatively by analyzing the intensity distributions of Fast Fourier Transform spectra generated from the digitized images of TEM micrographs. The precipitates display no tendency towards becoming plate-shaped and they resist coalescence even at the largest sizes, which approach 400 nm in diameter at 2760 h of aging for higher volume fraction alloys. For f < 0.1, the kinetics of coarsening and solute depletion as well as the standard deviation of the particle size distributions decrease as f increases. This anomalous behavior has been documented previously by other investigators, but is contrary to the predictions of theories that incorporate the volume fraction effect in coarsening kinetics. We find no convincing evidence to suggest that f influences any aspect of the coarsening behavior at larger f. It is suggested that the lack of agreement between the volume fraction effects observed experimentally and those predicted theoretically stems from the elastic interactions having a strong influence on the kinetics of coarsening, effectively counteracting the accelerating influence of f on the coarsening kinetics predicted by the theories.

Coherence parameter measurements for neon and hydrogen

NASA Astrophysics Data System (ADS)

Wright, Robert; Hargreaves, Leigh; Khakoo, Murtadha; Zatsarinny, Oleg; Bartschat, Klaus; Stauffer, Al

2015-09-01

We present recent coherence parameter measurements for excitation of neon and hydrogen by 50 eV electrons. The measurements were made using a crossed electron/gas beam spectrometer, featuring a hemispherically selected electron energy analyzer for detecting scattered electrons and double-reflection VUV polarization analyzer to register fluorescence photons. Time-coincidence counting methods on the electron and photon signals were employed to determine Stokes Parameters at each scattering angle, with data measured at angles between 20 - 115 degrees. The data are compared with calculated results using the B-Spline R-Matrix (BSR) and Relativistic Distorted Wave (RDW) approaches. Measurements were made of both the linear (Plin and γ) and circular (Lperp) parameters for the lowest lying excited states in these two targets. We particularly focus on results in the Lperp parameter, which shows unusual behavior in these particular targets, including strong sign changes implying reversal of the angular momentum transfer. In the case of neon, the unusual behavior is well captured by the BSR, but not by other models.

Tuning the Growth Pattern in 2D Confinement Regime of Sm2O3 and the Emerging Room Temperature Unusual Superparamagnetism

PubMed Central

Guria, Amit K.; Dey, Koushik; Sarkar, Suresh; Patra, Biplab K.; Giri, Saurav; Pradhan, Narayan

2014-01-01

Programming the reaction chemistry for superseding the formation of Sm2O3 in a competitive process of formation and dissolution, the crystal growth patterns are varied and two different nanostructures of Sm2O3 in 2D confinement regime are designed. Among these, the regular and self-assembled square platelets nanostructures exhibit paramagnetic behavior analogous to the bulk Sm2O3. But, the other one, 2D flower like shaped nanostructure, formed by irregular crystal growth, shows superparamagnetism at room temperature which is unusual for bulk paramagnet. It has been noted that the variation in the crystal growth pattern is due to the difference in the binding ability of two organic ligands, oleylamine and oleic acid, used for the synthesis and the magnetic behavior of the nanostructures is related to the defects incorporated during the crystal growth. Herein, we inspect the formation chemistry and plausible origin of contrasting magnetism of these nanostructures of Sm2O3. PMID:25269458

The use of marine reserves in evaluating the dive fishery for the warty sea cucumber, Parastichopus parvimensis in California, U.S.A

USGS Publications Warehouse

Schroeder, S.C.; Reed, D.C.; Kushner, D.J.; Estes, J.A.; Ono, D.S.

2001-01-01

In this paper we describe an instance of unusual, agonistic behavior in a flock of migrant Short-billed Dowitchers (Limnodromus griseus) . We compare this behavior to that of other flocks feeding at the same time at other locations in the same estuary and then present evidence suggesting that this behavior resulted from the patchy distribution of the probable foraging resource of this flock, eggs of the horseshoe crab (Limulus polyphemus). We propose that an extremely patchy resource has increased the agonistic behavior within the flock by increasing the variation in foraging success among individuals.

Disentangling prenatal and inherited influences in humans with an experimental design.

PubMed

Rice, Frances; Harold, Gordon T; Boivin, Jacky; Hay, Dale F; van den Bree, Marianne; Thapar, Anita

2009-02-17

Exposure to adversity in utero at a sensitive period of development can bring about physiological, structural, and metabolic changes in the fetus that affect later development and behavior. However, the link between prenatal environment and offspring outcomes could also arise and confound because of the relation between maternal and offspring genomes. As human studies cannot randomly assign offspring to prenatal conditions, it is difficult to test whether in utero events have true causal effects on offspring outcomes. We used an unusual approach to overcome this difficulty whereby pregnant mothers are either biologically unrelated or related to their child as a result of in vitro fertilization (IVF). In this sample, prenatal smoking reduces offspring birth weight in both unrelated and related offspring, consistent with effects arising through prenatal mechanisms independent of the relation between the maternal and offspring genomes. In contrast, the association between prenatal smoking and offspring antisocial behavior depended on inherited factors because association was only present in related mothers and offspring. The results demonstrate that this unusual prenatal cross-fostering design is feasible and informative for disentangling inherited and prenatal effects on human health and behavior. Disentangling these different effects is invaluable for pinpointing markers of prenatal adversity that have a causal effect on offspring outcomes. The origins of behavior and many common complex disorders may begin in early life, therefore this experimental design could pave the way for identifying prenatal factors that affect behavior in future generations.

Fundamental Studies of the Mechanical Behavior of Microelectronic Thin Film Materials

DTIC Science & Technology

1991-01-01

scanning, wafer curvature technique to study the kinetics of crystallization of amorphous silicon. When a thin film of amorphous silicon crystallizes...the film and the kinetics of the crystallization process. We find the tensile stress in the film to increase by about 500 MPa when crystallization...occurs. This is a very large stress that could have significance for device processing and applications. By measuring the kinetics of this stress change

Sorption kinetics of diuron on volcanic ash derived soils.

PubMed

Cáceres-Jensen, Lizethly; Rodríguez-Becerra, Jorge; Parra-Rivero, Joselyn; Escudey, Mauricio; Barrientos, Lorena; Castro-Castillo, Vicente

2013-10-15

Diuron sorption kinetic was studied in Andisols, Inceptisol and Ultisols soils in view of their distinctive physical and chemical properties: acidic pH and variable surface charge. Two types of kinetic models were used to fit the experimental dates: those that allow to establish principal kinetic parameters and modeling of sorption process (pseudo-first-order, pseudo-second-order), and some ones frequently used to describe solute transport mechanisms of organic compounds on different sorbents intended for remediation purposes (Elovich equation, intraparticle diffusion, Boyd, and two-site nonequilibrium models). The best fit was obtained with the pseudo-second-order model. The rate constant and the initial rate constant values obtained through this model demonstrated the behavior of Diuron in each soil, in Andisols were observed the highest values for both parameters. The application of the models to describe solute transport mechanisms allowed establishing that in all soils the mass transfer controls the sorption kinetic across the boundary layer and intraparticle diffusion into macropores and micropores. The slowest sorption rate was observed on Ultisols, behavior which must be taken into account when the leaching potential of Diuron is considered. Copyright © 2013 Elsevier B.V. All rights reserved.

Neutron lifetimes behavior analysis considering the two-region kinetic model in the IPEN/MB-01 reactor

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

Gonnelli, Eduardo; Diniz, Ricardo

2014-11-11

This is a complementary work about the behavior analysis of the neutron lifetimes that was developed in the IPEN/MB-01 nuclear reactor facility. The macroscopic neutron noise technique was experimentally employed using pulse mode detectors for two stages of control rods insertion, where a total of twenty levels of subcriticality have been carried out. It was also considered that the neutron reflector density was treated as an additional group of delayed neutrons, being a sophisticated approach in the two-region kinetic theoretical model.

Chemically stabilized epitaxial wurtzite-BN thin film

NASA Astrophysics Data System (ADS)

Vishal, Badri; Singh, Rajendra; Chaturvedi, Abhishek; Sharma, Ankit; Sreedhara, M. B.; Sahu, Rajib; Bhat, Usha; Ramamurty, Upadrasta; Datta, Ranjan

2018-03-01

We report on the chemically stabilized epitaxial w-BN thin film grown on c-plane sapphire by pulsed laser deposition under slow kinetic condition. Traces of no other allotropes such as cubic (c) or hexagonal (h) BN phases are present. Sapphire substrate plays a significant role in stabilizing the metastable w-BN from h-BN target under unusual PLD growth condition involving low temperature and pressure and is explained based on density functional theory calculation. The hardness and the elastic modulus of the w-BN film are 37 & 339 GPa, respectively measured by indentation along <0001> direction. The results are extremely promising in advancing the microelectronic and mechanical tooling industry.

'Mass allergy': acute scombroid poisoning in a deployed Australian Defence Force health facility.

PubMed

Ward, David Ian

2011-02-01

On the last night of disaster relief operations in Sumatra, Indonesia, a mass casualty event occurred that involved deployed Australian Defence Force personnel. Symptoms of acute urticaria, angioedema, wheeze and gastrointestinal upset were experienced to varying degrees by 16% of the deployed element. The present report describes a presumed scombroid poisoning cluster and demonstrates the difficulties of operating in a deployed environment, the confusion that might be associated with evolving non-kinetic mass casualties, and provides a learning opportunity for an unusual mass casualty incident. © 2011 The Author. EMA © 2011 Australasian College for Emergency Medicine and Australasian Society for Emergency Medicine.

The NO+O3 reaction: a triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly.

PubMed

Savarino, J; Bhattacharya, S K; Morin, S; Baroni, M; Doussin, J-F

2008-05-21

Atmospheric nitrate shows a large oxygen isotope anomaly (Delta 17 O), characterized by an excess enrichment of 17 O over 18 O, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NOx=NO+NO2). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NO(x), greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO+O3. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8+/-5)%(+/-2 sigma) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O3 to NO2, which is described by the linear relationship Delta 17 O(NO2)=A x Delta 17 O(O3)+B, with A=1.18+/-0.07(+/-1 sigma) and B=(6.6+/-1.5)[per thousand](+/-1 sigma). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.

Oxidation of atomic gold ions: thermochemistry for the activation of O(2) and N(2)O BY Au(+) ((1)S(0) and (3)D).

PubMed

Li, Feng-Xia; Gorham, Katrine; Armentrout, P B

2010-10-28

Reaction of Au(+) ((1)S(0) and (3)D) with O(2) and N(2)O is studied as a function of kinetic energy using guided ion beam tandem mass spectrometry. A flow tube ion source produces Au(+) primarily in its (1)S(0) (5d(10)) electronic ground state level but with some (3)D and perhaps higher lying excited states. The distribution of states can be altered by adding N(2)O, which completely quenches the excited states, or CH(4) to the flow gases. Cross sections as a function of kinetic energy are measured for both neutral reagents and both ground and excited states of Au(+). Formation of AuO(+) is common to both systems with the N(2)O system also exhibiting AuN(2)(+) and AuNO(+) formation. All reactions of Au(+) ((1)S(0)) are observed to be endothermic, whereas the excitation energy available to the (3)D state allows some reactions to be exothermic. Because of the closed shell character of ground state Au(+) ((1)S(0), 5d(10)), the reactivity of these systems is low and has cross sections with onsets and peaks at higher energies than expected from the known thermochemistry but lower than energies expected from impulsive processes. Analyses of the endothermic reaction cross sections yield the 0 K bond dissociation energy (BDE) in eV of D(0)(Au(+)-O) = 1.12 ± 0.08, D(0)(Au(+)-N(2)) ≥ 0.30 ± 0.04, and D(0)(Au(+)-NO) = 0.89 ± 0.17, values that are all speculative because of the unusual experimental behavior. Combining the AuO(+) BDE measured here with literature data also yields the ionization energy of AuO as 10.38 ± 0.23 eV. Quantum chemical calculations show reasonable agreement with the experimental bond energies and provide the electronic structures of these species.

Liquid-phase hydrogenation of citral over Pt/SiO{sub 2} catalysts. 1. Temperature effects on activity and selectivity

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

Singh, U.K.; Vannice, M.A.

2000-04-01

Liquid-phase hydrogenation of citral (3,7-dimethyl-2,6-octadienal) over Pt/SiO{sub 2} catalysts was studied in the temperature and pressure ranges 298--423 K and 7--21 atm, respectively. The reaction kinetics were shown to be free of artifacts arising from transport limitations and poisoning effects. The reaction rate in hexane at the solvent exhibited an activity minimum at 373 K. The initial turnover frequency for citral disappearance over 1.44% Pt/SiO{sub 2} catalyst at 20 atm H{sub 2} pressure decreased from 0.19 s{sup {minus}1} at 298 K to 0.02 s{sup {minus}1} at 373 K, but exhibited normal Arrhenius behavior between 373 and 423 K with anmore » activation energy of 7 kcal/mol. Reaction at 298 K produced substantial deactivation, with the rate decreasing by more than an order of magnitude during the first 4 h of reaction; however, reaction at temperatures greater than 373 K exhibited negligible deactivation and a constant rate up to citral conversions greater than 70%. These unusual temperature effects were modeled using Langmuir-Hinshelwood kinetics invoking dissociative adsorption of hydrogen, competitive adsorption between hydrogen and the organic compounds, and addition of the second hydrogen atom to each reactant as the rate-determining step. Decomposition of the unsaturated alcohol (either geraniol or nerol) was proposed to occur concurrently with the hydrogenation steps to yield adsorbed CO and carbonaceous species which cause the deactivation, but at higher temperatures these species could be removed from the Pt surface by desorption or rapid hydrogenation, respectively. The activity minimum observed in the present study is attributed to the relative rates of the alcohol decomposition reaction and CO desorption, with the decomposition reaction having an activation barrier lower than that for CO desorption.« less

76 FR 21073 - Notice of Intent To Seek Approval To Continue an Information Collection

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-14

... Excellence in Science, Mathematics and Engineering Mentoring (PAESMEM) program. In 2003, to comply with E... would ``receive recommendations made by any other nationally representative scientific or engineering..., biological, mathematical, engineering or social and behavioral sciences. 2. Achievements of an unusually...

Music Therapy for the Visually Impaired.

ERIC Educational Resources Information Center

Steele, Anita Louise; Crawford, Celeste

1982-01-01

The development and implementation of a music therapy program to achieve behavioral change in visually impaired children and adolescents are described. Goals targeted by the music therapist at the Cleveland Society for the Blind include altering unusual body movements, poor posture, and other mannerisms often associated with blindness. (SEW)

76 FR 12761 - Notice of Intent To Seek Approval To Continue an Information Collection

Federal Register 2010, 2011, 2012, 2013, 2014

2011-03-08

... social and behavioral sciences. 2. Achievements of an unusually significant nature in relation to the... NATIONAL SCIENCE FOUNDATION Notice of Intent To Seek Approval To Continue an Information Collection AGENCY: National Science Foundation. ACTION: Notice and Request for Comments. SUMMARY: The...

Aggregation and foraging behavior of imported cabbageworm (Lepidoptera: pieridae) adults on blue vervain flowers

USDA-ARS?s Scientific Manuscript database

The imported cabbageworm [Pieris rapae (L.) (Lepidoptera: Pieridae)], also known as the cabbage white butterfly, is an important specialized pest on cruciferous plants (Brassicales: Brassicaceae) worldwide. an unusual aggregation of the cabbage white butterflies was observed on a patch of flowering...

Who Can You Trust? Protecting Your Organization from Internal Fraud.

ERIC Educational Resources Information Center

Lukaszewski, Thomas E.

1997-01-01

Discusses how to protect a child care organization from employee fraud. Differentiates employee and management fraud and examines reasons fraud is committed. Suggests procedures for protecting an organization from fraud, including establishing an effective internal control system, paying attention to unusual employee behavior, reviewing expense…

Enantioseparation of angiotensin II receptor type 1 blockers: evaluation of 6-substituted carbamoyl benzimidazoles on immobilized polysaccharide-based chiral stationary phases. Unusual temperature behavior.

PubMed

Su, Ran; Hou, Zhun; Sang, Lihong; Zhou, Zhi-Ming; Fang, Hao; Yang, Xinying

2017-09-15

Enantioseparation of thirteen 6-substituted carbamoyl benzimidazoles by high-performance liquid chromatography (HPLC) was investigated using two immobilized polysaccharide-based chiral stationary phases (CSPs), Chiralpak IC and Chiralpak IA, in normal-phase mode. Most of the examined compounds were completely resolved. The effects of a polar alcohol modifier, analyte structure, and column temperature on the chiral recognition were investigated. Furthermore, the structure-retention relationship was evaluated, and thermodynamic parameters were calculated from plots of ln k' or ln α versus 1/T. The thermodynamic parameters indicated that the separations were enthalpy-driven. Moreover, nonlinear van't Hoff plots were obtained on Chiralpak IA. However, two unusual phenomena were observed: (1) an unusual increase in retention with increasing temperature with linear van't Hoff plots on Chiralpak IC and (2) an extremely high T iso value (i.e., several thousand degrees centigrade). Copyright © 2017 Elsevier B.V. All rights reserved.

Innovation in Aerodynamic Design Features of Soviet Missiles

NASA Technical Reports Server (NTRS)

Spearman, M. Leroy

2006-01-01

Wind tunnel investigations of some tactical and strategic missile systems developed by the former Soviet Union have been included in the basic missile research programs of the NACA/NASA. Studies of the Soviet missiles sometimes revealed innovative design features that resulted in unusual or unexpected aerodynamic characteristics. In some cases these characteristics have been such that the measured performance of the missile exceeds what might have been predicted. In other cases some unusual design features have been found that would alleviate what might otherwise have been a serious aerodynamic problem. In some designs, what has appeared to be a lack of refinement has proven to be a matter of expediency. It is a purpose of this paper to describe some examples of unusual design features of some Soviet missiles and to illustrate the effectiveness of the design features on the aerodynamic behavior of the missile. The paper draws on the experience of the author who for over 60 years was involved in the aerodynamic wind tunnel testing of aircraft and missiles with the NACA/NASA.

Unusual magnetoelectric memory and polarization reversal in the kagome staircase compound N i3V2O8

NASA Astrophysics Data System (ADS)

Liu, Y. J.; Wang, J. F.; He, Z. Z.; Lu, C. L.; Xia, Z. C.; Ouyang, Z. W.; Liu, C. B.; Chen, R.; Matsuo, A.; Kohama, Y.; Kindo, K.; Tokunaga, M.

2018-05-01

We study the electric polarization of the kagome staircase N i3V2O8 in magnetic fields up to 30 T and report a magnetoelectric memory effect controlled by bias electric fields. The explored ferroelectric phase in 19 -24 T is electrically controlled, whereas the ferroelectric phase in 2 -11 T exhibits unusual memory effects. We determine a characteristic critical magnetic field H3=11 T , below which strong memory exists and the polarization is frozen even in opposite bias fields. But when magnetic fields exceed H3, the frozen polarization is released and polarization reversal appears by tuning bias electric fields. We ascribe these phenomena to the pinning-depinning mechanism: nucleation and the accompanying pinning of chiral domain walls cooperatively induce the frozen behavior; the polarization reversal results from the depinning through the ferroelectrtic-to-paraelectric phase transition in high magnetic fields. Our experimental results reveal that the first-order phase transition plays an important role in these unusual memory effects.

Thermosensory perception regulates speed of movement in response to temperature changes in Drosophila melanogaster.

PubMed

Soto-Padilla, Andrea; Ruijsink, Rick; Sibon, Ody C M; van Rijn, Hedderik; Billeter, Jean-Christophe

2018-04-12

Temperature influences physiology and behavior of all organisms. For ectotherms, which lack central temperature regulation, temperature adaptation requires sheltering from or moving to a heat source. As temperature constrains the rate of metabolic reactions, it can directly affect ectotherm physiology and thus behavioral performance. This direct effect is particularly relevant for insects whose small body readily equilibrates with ambient temperature. In fact, models of enzyme kinetics applied to insect behavior predict performance at different temperatures, suggesting that thermal physiology governs behavior. However, insects also possess thermosensory neurons critical for locating preferred temperatures, showing cognitive control. This suggests that temperature-related behavior can emerge directly from a physiological effect, indirectly as consequence of thermosensory processing, or through both. To separate the roles of thermal physiology and cognitive control, we developed an arena that allows fast temperature changes in time and space, and in which animals' movements are automatically quantified. We exposed wild-type and thermosensory receptor mutants Drosophila melanogaster to a dynamic temperature environment and tracked their movements. The locomotor speed of wild-type flies closely matched models of enzyme kinetics, but the behavior of thermosensory mutants did not. Mutations in thermosensory receptor dTrpA1 ( Transient receptor potential ) expressed in the brain resulted in a complete lack of response to temperature changes, while mutation in peripheral thermosensory receptor Gr28b(D) resulted in diminished response. We conclude that flies react to temperature through cognitive control, informed by interactions between various thermosensory neurons, whose behavioral output resembles that of enzyme kinetics. © 2018. Published by The Company of Biologists Ltd.

Effects of High Altitude Hypoxia on Lung and Chest Wall Function during Exercise

DTIC Science & Technology

1990-01-27

to Muscular Exercise. Epidemiology. Behavior change. and Intervention in Chronic Lung Disease. (L. Hall and G. Meyer, editors), Human Kinetics Publ...Aaron. Feedback and Feed-Forward Mechanisms. Future Directions in Exercise and Sport Science Research. (J.S. Skinner, et al., eds). Human Kinetics Books

The Influences of Exposure Pattern and Duration on Elimination Kinetics and Exposure Assessment of Tetrachloroethylene in Humans. Yeh-Chung Chien

EPA Pesticide Factsheets

The current investigation was designed and conducted to examine the body kinetic behaviors by means of breath analysis under various exposure conditions to test the validity of using exhaled breath as a biological marker of exposure.

Kinetic-Family-Drawing Styles and Emotionally Disturbed Childhood Behavior

ERIC Educational Resources Information Center

McPhee, John P.; Wegner, Kenneth W.

1976-01-01

Purpose of the study was to achieve empirical verification that Kinetic-Family-Drawing (KFD) styles were reflected by children with moderate/severe emotionally disturbed interpersonal relationships as opposed to the nonstylized drawings of adjusted children. The results confirmed the general existence of KFD style; however, style was not…

Oxidation kinetics of some Ni-Cr alloys.

PubMed

Baran, G

1983-01-01

Oxidation kinetics of four Ni-Cr alloys and a high-purity nickel standard was determined under isothermal conditions in an air atmosphere. In addition, weight gains of the alloys were measured during a simulated pre-oxidation treatment. The alloys' behavior suggests that mechanisms of oxidation vary with temperature and alloy composition.

Cellular level models as tools for cytokine design.

PubMed

Radhakrishnan, Mala L; Tidor, Bruce

2010-01-01

Cytokines and growth factors are critical regulators that connect intracellular and extracellular environments through binding to specific cell-surface receptors. They regulate a wide variety of immunological, growth, and inflammatory response processes. The overall signal initiated by a population of cytokine molecules over long time periods is controlled by the subtle interplay of binding, signaling, and trafficking kinetics. Building on the work of others, we abstract a simple kinetic model that captures relevant features from cytokine systems as well as related growth factor systems. We explore a large range of potential biochemical behaviors, through systematic examination of the model's parameter space. Different rates for the same reaction topology lead to a dramatic range of biochemical network properties and outcomes. Evolution might productively explore varied and different portions of parameter space to create beneficial behaviors, and effective human therapeutic intervention might be achieved through altering network kinetic properties. Quantitative analysis of the results reveals the basis for tensions among a number of different network characteristics. For example, strong binding of cytokine to receptor can increase short-term receptor activation and signal initiation but decrease long-term signaling due to internalization and degradation. Further analysis reveals the role of specific biochemical processes in modulating such tensions. For instance, the kinetics of cytokine binding and receptor activation modulate whether ligand-receptor dissociation can generally occur before signal initiation or receptor internalization. Beyond analysis, the same models and model behaviors provide an important basis for the design of more potent cytokine therapeutics by providing insight into how binding kinetics affect ligand potency. (c) 2010 American Institute of Chemical Engineers

Relationships between molecular structure and kinetic and thermodynamic controls in lipid systems. Part III. Crystallization and phase behavior of 1-palmitoyl-2,3-stearoyl-sn-glycerol (PSS) and tristearoylglycerol (SSS) binary system.

PubMed

Bouzidi, Laziz; Narine, Suresh S

2012-01-01

The phase behavior of 1-palmitoyl-2,3-distearoyl-sn-glycerol (PSS)/tristearoylglycerol (SSS) binary system was investigated in terms of polymorphism, crystallization and melting behavior, microstructure and solid fat content (SFC) using widely different constant cooling rates. Kinetic phase diagrams were experimentally determined from the DSC heating thermograms and analyzed using a thermodynamic model to account for non-ideality of mixing. The kinetic phase diagram presented a typical eutectic behavior with a eutectic point at the 0.5(PSS) mixture with a probable precipitation line from 0.5(PSS) to 1.0(PSS), regardless of the rate at which the sample was cooled. The eutectic temperature decreased only slightly with increasing cooling rate. PSS has a strong effect on the physical properties of the PSS-SSS mixtures. In fact, the overall phase behavior of the PSS-SSS binary system was determined, for a very large part, by the asymmetrical TAG. Moreover, PSS is a key driver of the high stability observed in crystal growth, polymorphism and phase development. Levels as low as 10% PSS, when cooled slowly, and 30% when cooled rapidly, were found to be sufficient to suppress the effect of thermal processing. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Successful lithium treatment of transvestism associated with manic-depression.

PubMed

Ward, N G

1975-09-01

A case of transvestism in a 24-year-old manic-depressive man is described. The behavior had been maintained for 2 years and disappeared soon after lithium treatment was begun. It has not returned during the first year on lithium. Dynamic and behavioral explanations for this unusual therapeutic response are considered. The dynamic explanation involves the assumption that the transvestism was perpetuated by mood-dependent motives that were eliminated by lithium. The behavioral explanation involves the assumption that the manic state itself became an intermittent reinforcer for the transvestism, and the lithium, by eliminating the mania, created a relatively permanent extinction period.

Translational animal models of autism and neurodevelopmental disorders.

PubMed

Crawley, Jacqueline N

2012-09-01

Autism is a neurodevelopmental disorder whose diagnosis is based on three behavioral criteria: unusual reciprocal social interactions, deficits in communication, and stereotyped repetitive behaviors with restricted interests. A large number of de novo single gene mutations and chromosomal deletions are associated with autism spectrum disorders. Based on the strong genetic evidence, mice with targeted mutations in homologous genes have been generated as translational research tools. Mouse models of autism have revealed behavioral and biological outcomes of mutations in risk genes. The field is now poised to employ the most robust phenotypes in the most replicable mouse models for preclinical screening of novel therapeutics.

Unusual behavior by Bison, Bison bison, toward Elk, Cervus elaphus, and wolves, Canis lupus

USGS Publications Warehouse

Mech, L.D.; McIntyre, R.T.; Smith, D.W.

2004-01-01

Incidents are described of Bison (Bison bison) in Yellowstone National Park mauling and possibly killing a young Elk (Cervus elaphus) calf, chasing wolves (Canis lupus) off Elk they had just killed or were killing, and keeping the wolves away for extended periods. During one of the latter cases, the Bison knocked a wolf-wounded Elk down. Bison were also seen approaching wolves that were resting and sleeping, rousting them, following them to new resting places and repeating this behavior. These behaviors might represent some type of generalized hyper-defensiveness that functions as an anti-predator strategy.

Unusual behavior by bison, Bison bison, toward elk, Cervus elaphus, and wolves, Canis lupus

USGS Publications Warehouse

Mech, L.D.; McIntyre, R.T.; Smith, D.W.

2004-01-01

Incidents are described of bison (Bison bison) in Yellowstone National Park mauling and possibly killing a young elk (Cervus elaphus) calf, chasing wolves (Canis lupus) off elk they had just killed or were killing, and keeping the wolves away for extended periods. During one of the latter cases, the bison knocked a wolf-wounded elk down. Bison were also seen approaching wolves that were resting and sleeping, rousting them, following them to new resting places and repeating this behavior. These behaviors might represent some type of generalized hyper-defensiveness that functions as an anti-predator strategy.

Subunit Dissociation and Metal Binding by Escherichia coli apo-Manganese Superoxide Dismutase

PubMed Central

Whittaker, Mei M.; Lerch, Thomas F.; Kirillova, Olga; Chapman, Michael S.; Whittaker, James W.

2010-01-01

Metal binding by apo-manganese superoxide dismutase (apo-MnSOD) is essential for functional maturation of the enzyme. Previous studies have demonstrated that metal binding by apo-MnSOD is conformationally gated, requiring protein reorganization for the metal to bind. We have now solved the X-ray crystal structure of apo-MnSOD at 1.9 Å resolution. The organization of active site residues is independent of the presence of the metal cofactor, demonstrating that protein itself templates the unusual metal coordination geometry. Electrophoretic analysis of mixtures of apo- and (Mn2)-MnSOD, dye-conjugated protein, or C-terminal Strep-tag II fusion protein reveals a dynamic subunit exchange process associated with cooperative metal binding by the two subunits of the dimeric protein. In contrast, (S126C) (SS) apo-MnSOD, which contains an inter-subunit covalent disulfide crosslink, exhibits anticooperative metal binding. The protein concentration dependence of metal uptake kinetics implies that protein dissociation is involved in metal binding by the wild type apo-protein, although other processes may also contribute to gating metal uptake. Protein concentration dependent small-zone size exclusion chromatography is consistent with apo-MnSOD dimer dissociation at low protein concentration (KD = 1×10−6 M). Studies on metal uptake by apo-MnSOD in Escherichia coli cells show that the protein exhibits similar behavior in vivo and in vitro. PMID:21044611

High-pressure X-ray diffraction, Raman, and computational studies of MgCl2 up to 1 Mbar: Extensive pressure stability of the β-MgCl2 layered structure.

PubMed

Stavrou, Elissaios; Yao, Yansun; Zaug, Joseph M; Bastea, Sorin; Kalkan, Bora; Konôpková, Zuzana; Kunz, Martin

2016-08-12

Magnesium chloride (MgCl2) with the rhombohedral layered CdCl2-type structure (α-MgCl2) has been studied experimentally using synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy using a diamond-anvil cell up to 100 GPa at room temperature and theoretically using first-principles density functional calculations. The results reveal a pressure-induced second-order structural phase transition to a hexagonal layered CdI2-type structure (β-MgCl2) at 0.7 GPa: the stacking sequence of the Cl anions are altered resulting in a reduction of the c-axis length. Theoretical calculations confirm this phase transition sequence and the calculated transition pressure is in excellent agreement with the experiment. Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phase. According to our experimental results MgCl2 remains in a 2D layered phase up to 100 GPa and further, the 6-fold coordination of Mg cations is retained. Theoretical calculations of relative enthalpy suggest that this extensive pressure stability is due to a low enthalpy of the layered structure ruling out kinetic barrier effects. This observation is unusual, as it contradicts with the general structural behavior of highly compressed AB2 compounds.

High-pressure X-ray diffraction, Raman, and computational studies of MgCl 2 up to 1 Mbar: Extensive pressure stability of the β-MgCl 2 layered structure

DOE PAGES

Stavrou, Elissaios; Yao, Yansun; Zaug, Joseph M.; ...

2016-08-12

We studied magnesium chloride (MgCl 2) with the rhombohedral layered CdCl 2-type structure (α-MgCl 2), experimentally, using synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy using a diamond-anvil cell up to 100 GPa at room temperature and theoretically using first-principles density functional calculations. Our results reveal a pressure-induced second-order structural phase transition to a hexagonal layered CdI 2-type structure (β-MgCl 2) at 0.7 GPa: the stacking sequence of the Cl anions are altered resulting in a reduction of the c-axis length. Theoretical calculations confirm this phase transition sequence and the calculated transition pressure is in excellent agreement with the experiment.more » Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phase. According to our experimental results MgCl 2 remains in a 2D layered phase up to 100 GPa and further, the 6-fold coordination of Mg cations is retained. Theoretical calculations of relative enthalpy suggest that this extensive pressure stability is due to a low enthalpy of the layered structure ruling out kinetic barrier effects. Our observation is unusual, as it contradicts with the general structural behavior of highly compressed AB 2 compounds.« less

Structure, reactivity and electronic properties of Mn doped Ni13 clusters

NASA Astrophysics Data System (ADS)

Banerjee, Radhashyam; Datta, Soumendu; Mookerjee, Abhijit

2013-06-01

In this work we have studied the structural and magnetic properties of Ni13 cluster mono- and bi-doped with Mn atoms. We have noted their tendency of being reactive toward the H2 molecule. We have found unusually enhanced stability in the mono-doped cluster (i.e. of the Ni12Mn) and the diminished stability of the corresponding chemisorbed cluster, Ni12MnH2. Our analysis of the stability and HOMO-LUMO gap explains this unusual behavior. Interestingly, we have also seen the quenching in the net magnetic moment upon H2 absorption in the doped NiMnm alloy clusters. This has been reported earlier for smaller Nin clusters [1].

Biphasic Kinetic Behavior of E. coli WrbA, an FMN-Dependent NAD(P)H:Quinone Oxidoreductase

PubMed Central

Kishko, Iryna; Harish, Balasubramanian; Zayats, Vasilina; Reha, David; Tenner, Brian; Beri, Dhananjay; Gustavsson, Tobias; Ettrich, Rüdiger; Carey, Jannette

2012-01-01

The E. coli protein WrbA is an FMN-dependent NAD(P)H:quinone oxidoreductase that has been implicated in oxidative defense. Three subunits of the tetrameric enzyme contribute to each of four identical, cavernous active sites that appear to accommodate NAD(P)H or various quinones, but not simultaneously, suggesting an obligate tetramer with a ping-pong mechanism in which NAD departs before oxidized quinone binds. The present work was undertaken to evaluate these suggestions and to characterize the kinetic behavior of WrbA. Steady-state kinetics results reveal that WrbA conforms to a ping-pong mechanism with respect to the constancy of the apparent Vmax to Km ratio with substrate concentration. However, the competitive/non-competitive patterns of product inhibition, though consistent with the general class of bi-substrate reactions, do not exclude a minor contribution from additional forms of the enzyme. NMR results support the presence of additional enzyme forms. Docking and energy calculations find that electron-transfer-competent binding sites for NADH and benzoquinone present severe steric overlap, consistent with the ping-pong mechanism. Unexpectedly, plots of initial velocity as a function of either NADH or benzoquinone concentration present one or two Michaelis-Menten phases depending on the temperature at which the enzyme is held prior to assay. The effect of temperature is reversible, suggesting an intramolecular conformational process. WrbA shares these and other details of its kinetic behavior with mammalian DT-diaphorase, an FAD-dependent NAD(P)H:quinone oxidoreductase. An extensive literature review reveals several other enzymes with two-plateau kinetic plots, but in no case has a molecular explanation been elucidated. Preliminary sedimentation velocity analysis of WrbA indicates a large shift in size of the multimer with temperature, suggesting that subunit assembly coupled to substrate binding may underlie the two-plateau behavior. An additional aim of this report is to bring under wider attention the apparently widespread phenomenon of two-plateau Michaelis-Menten plots. PMID:22952804

Broad Ligament Perivascular Epithelioid Cell Tumor (PEComa) of Uncertain Malignant Potential.

PubMed

Mathew, Mary; Nayal, Bhavna; Rao, Lakshmi; Nagel, Bhawna

2016-01-01

PEComas are uncommon mesenchymal tumors often involving the pelvic organs. They have an unpredictable behavior. Accurate diagnosis and long-term follow-up is therefore essential in these patients. We report this case of PEComa of uncertain malignant potential in an unusual location with excellent prognosis.

The Unusual Suspects: Myths and Misconceptions Associated with PECS

ERIC Educational Resources Information Center

Bondy, Andy

2012-01-01

The Picture Exchange Communication System (PECS) is an alternative/augmentative communication protocol designed to help children and adults with autism and related disabilities to engage in functional communication. The protocol was developed over a number of years and was based on Skinner's analysis of verbal behavior. Publications about the…

A Short Stay, a Long-Lasting Lesson.

ERIC Educational Resources Information Center

Benham, Dianne C.

1991-01-01

Presents an integrated schoolwide program in which students learn about pet care and the behaviors of 14 unusual animals. Each participating teacher sets up one animal center describing the animal and the animal's habitat. Centers change at the end of each month. Discusses costs and learning benefits of the program. (MDH)

Ion kinetic scale in the solar wind observed.

PubMed

Śafránková, Jana; Němeček, Zdeněk; Přech, Lubomír; Zastenker, Georgy N

2013-01-11

This Letter shows the first results from the solar wind monitor onboard the Spektr-R spacecraft which measures plasma moments with a time resolution of 31 ms. This high-time resolution allows us to make direct observations of solar wind turbulence below ion kinetic length scales. We present examples of the frequency spectra of the density, velocity, and thermal velocity. Our study reveals that although these parameters exhibit the same behavior at the magnetohydrodynamic scale, their spectra are remarkably different at the kinetic scale.

Investigations of the Controlling Factors for Air Emissions Associated With the Dredging of Indiana Harbor and Canal (IHC) and CDF Operations

DTIC Science & Technology

2008-04-01

concepts of a transient toxic constituent loss and transport model for both solids and chemical incorporating a kinetic approach rather than equilibrium...to air. A transient kinetic mass-transfer model was applied to the data and it was found that the TSS level was the most critical parameter for...measured (Thibodeaux et al. 2004). The transient behavior followed the expected theory of the mass-transfer kinetic, but the conventional LEA model

Phase-field modeling of diffusional phase behaviors of solid surfaces: A case study of phase-separating Li XFePO 4 electrode particles

DOE PAGES

Heo, Tae Wook; Chen, Long-Qing; Wood, Brandon C.

2015-04-08

In this paper, we present a comprehensive phase-field model for simulating diffusion-mediated kinetic phase behaviors near the surface of a solid particle. The model incorporates elastic inhomogeneity and anisotropy, diffusion mobility anisotropy, interfacial energy anisotropy, and Cahn–Hilliard diffusion kinetics. The free energy density function is formulated based on the regular solution model taking into account the possible solute-surface interaction near the surface. The coherency strain energy is computed using the Fourier-spectral iterative-perturbation method due to the strong elastic inhomogeneity with a zero surface traction boundary condition. Employing a phase-separating Li XFePO 4 electrode particle for Li-ion batteries as a modelmore » system, we perform parametric three-dimensional computer simulations. The model permits the observation of surface phase behaviors that are different from the bulk counterpart. For instance, it reproduces the theoretically well-established surface modes of spinodal decomposition of an unstable solid solution: the surface mode of coherent spinodal decomposition and the surface-directed spinodal decomposition mode. We systematically investigate the influences of major factors on the kinetic surface phase behaviors during the diffusional process. Finally, our simulation study provides insights for tailoring the internal phase microstructure of a particle by controlling the surface phase morphology.« less

Kinetic analysis on precursors for iturin A production from Bacillus amyloliquefaciens BPD1.

PubMed

Wu, Jiun-Yan; Liao, Jen-Hung; Shieh, Chwen-Jen; Hsieh, Feng-Chia; Liu, Yung-Chuan

2018-06-12

In this study, the precursor effect for iturin A production was quantitatively analyzed. A strain identified as Bacillus amyloliquefaciens BPD1 (Ba-BPD1) was selected due to its ability to produce iturin A. The enhancement of iturin A production in a submerged culture was tested using various additives, including palmitic acid, oils, and complex amino acids. Among these, complex amino acids triggered the highest yield at 559 mg/L. The respective amino acids that contribute to the structure of iturin A were used as precursors. In fact, it was found that the addition of l-proline, l-glutamine, l-asparagine and l-serine could improve iturin A yield in the defined medium. However, during the kinetic analysis, all the amino acids exhibited a lower saturation level than l-serine, which exhibited a high saturation level at 1.2% resulting in an iturin A yield of 914 mg/L. In contrast, a negative effect was observed following the addition of l-tyrosine. To analyze the kinetic behavior of l-serine, three kinetic models were adopted: the kinetic order equation, the Langmuir kinetic equation, and a modified logistic equation. The regression results showed that the modified logistic model was the best fit for the kinetic behavior of l-serine as the major precursor, which could be further referred to the biosynthesis pathway of iturin A. Among the proposed processes for iturin A production, this study achieved the highest iturin A levels as a result of the addition of precursors. Copyright © 2018 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Coupling of TRAC-PF1/MOD2, Version 5.4.25, with NESTLE

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

Knepper, P.L.; Hochreiter, L.E.; Ivanov, K.N.

1999-09-01

A three-dimensional (3-D) spatial kinetics capability within a thermal-hydraulics system code provides a more correct description of the core physics during reactor transients that involve significant variations in the neutron flux distribution. Coupled codes provide the ability to forecast safety margins in a best-estimate manner. The behavior of a reactor core and the feedback to the plant dynamics can be accurately simulated. For each time step, coupled codes are capable of resolving system interaction effects on neutronics feedback and are capable of describing local neutronics effects caused by the thermal hydraulics and neutronics coupling. With the improvements in computational technology,more » modeling complex reactor behaviors with coupled thermal hydraulics and spatial kinetics is feasible. Previously, reactor analysis codes were limited to either a detailed thermal-hydraulics model with simplified kinetics or multidimensional neutron kinetics with a simplified thermal-hydraulics model. The authors discuss the coupling of the Transient Reactor Analysis Code (TRAC)-PF1/MOD2, Version 5.4.25, with the NESTLE code.« less

Application of the distributed activation energy model to the kinetic study of pyrolysis of the fresh water algae Chlorococcum humicola.

PubMed

Kirtania, Kawnish; Bhattacharya, Sankar

2012-03-01

Apart from capturing carbon dioxide, fresh water algae can be used to produce biofuel. To assess the energy potential of Chlorococcum humicola, the alga's pyrolytic behavior was studied at heating rates of 5-20K/min in a thermobalance. To model the weight loss characteristics, an algorithm was developed based on the distributed activation energy model and applied to experimental data to extract the kinetics of the decomposition process. When the kinetic parameters estimated by this method were applied to another set of experimental data which were not used to estimate the parameters, the model was capable of predicting the pyrolysis behavior, in the new set of data with a R(2) value of 0.999479. The slow weight loss, that took place at the end of the pyrolysis process, was also accounted for by the proposed algorithm which is capable of predicting the pyrolysis kinetics of C. humicola at different heating rates. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

Kinetic Energy and Angular Distributions of He and Ar Atoms Evaporating from Liquid Dodecane.

PubMed

Patel, Enamul-Hasan; Williams, Mark A; Koehler, Sven P K

2017-01-12

We report both kinetic energy and angular distributions for He and Ar atoms evaporating from C 12 H 26 . All results were obtained by performing molecular dynamics simulations of liquid C 12 H 26 with around 10-20 noble gas atoms dissolved in the liquid and by subsequently following the trajectories of the noble gas atoms after evaporation from the liquid. Whereas He evaporates with a kinetic energy distribution of (1.05 ± 0.03) × 2RT (corrected for the geometry used in experiments: (1.08 ± 0.03) × 2RT, experimentally obtained value: (1.14 ± 0.01) × 2RT), Ar displays a kinetic energy distribution that better matches a Maxwell-Boltzmann distribution at the temperature of the liquid ((0.99 ± 0.04) × 2RT). This behavior is also reflected in the angular distributions, which are close to a cosine distribution for Ar but slightly narrower, especially for faster atoms, in the case of He. This behavior of He is most likely due to the weak interaction potential between He and the liquid hydrocarbon.

Relaxation processes in a low-order three-dimensional magnetohydrodynamics model

NASA Technical Reports Server (NTRS)

Stribling, Troy; Matthaeus, William H.

1991-01-01

The time asymptotic behavior of a Galerkin model of 3D magnetohydrodynamics (MHD) has been interpreted using the selective decay and dynamic alignment relaxation theories. A large number of simulations has been performed that scan a parameter space defined by the rugged ideal invariants, including energy, cross helicity, and magnetic helicity. It is concluded that time asymptotic state can be interpreted as a relaxation to minimum energy. A simple decay model, based on absolute equilibrium theory, is found to predict a mapping of initial onto time asymptotic states, and to accurately describe the long time behavior of the runs when magnetic helicity is present. Attention is also given to two processes, operating on time scales shorter than selective decay and dynamic alignment, in which the ratio of kinetic to magnetic energy relaxes to values 0(1). The faster of the two processes takes states initially dominant in magnetic energy to a state of near-equipartition between kinetic and magnetic energy through power law growth of kinetic energy. The other process takes states initially dominant in kinetic energy to the near-equipartitioned state through exponential growth of magnetic energy.

Potential and kinetic energetic analysis of phonon modes in varied molecular solids

NASA Astrophysics Data System (ADS)

Kraczek, Brent

2015-03-01

We calculate partitioned kinetic and potential energies of the phonon modes in molecular solids to illuminate the dynamical behavior of the constituent molecules. This enables analysis of the relationship between the characteristics of sets of phonon modes, molecular structure and chemical reactivity by partitioning the kinetic energy into the translational, rotational and vibrational motions of groups of atoms (including molecules), and the potential energy into the energy contained within interatomic interactions. We consider three solids of differing size and rigidity: naphthalene (C1 0 H6), nitromethane (CH3NO2)andα-HMX(C4H8N8O8). Naphthalene and nitromethane mostly act in the semi-rigid manner often expected in molecular solids. HMX exhibits behavior that is significantly less-rigid. While there are definite correlations between the kinetic and potential energetic analyses, there are also differences, particularly in the excitation of chemical bonds by low-frequency lattice modes. This suggests that in many cases computational and experimental methods dependent on atomic displacements may not identify phonon modes active in chemical reactivity.

Curing kinetics of visible light curing dental resin composites investigated by dielectric analysis (DEA).

PubMed

Steinhaus, Johannes; Hausnerova, Berenika; Haenel, Thomas; Großgarten, Mandy; Möginger, Bernhard

2014-03-01

During the curing process of light curing dental composites the mobility of molecules and molecule segments is reduced leading to a significant increase of the viscosity as well as the ion viscosity. Thus, the kinetics of the curing behavior of 6 different composites was derived from dielectric analysis (DEA) using especially redesigned flat sensors with interdigit comb electrodes allowing for irradiation at the top side and measuring the ion viscosity at the bottom side. As the ion viscosities of dental composites change 1-3 orders of magnitude during the curing process, DEA provides a sensitive approach to evaluate their curing behavior, especially in the phase of undisturbed chain growth. In order to determine quantitative kinetic parameters a kinetic model is presented and examined for the evaluation of the ion viscosity curves. From the obtained results it is seen that DEA might be employed in the investigation of the primary curing process, the quality assurance of ingredients as well as the control of processing stability of the light curing dental composites. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Unified Bohm criterion

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

Kos, L.; Tskhakaya, D. D.; Jelić, N.

2015-09-15

Recent decades have seen research into the conditions necessary for the formation of the monotonic potential shape in the sheath, appearing at the plasma boundaries like walls, in fluid, and kinetic approximations separately. Although either of these approaches yields a formulation commonly known as the much-acclaimed Bohm criterion (BC), the respective results involve essentially different physical quantities that describe the ion gas behavior. In the fluid approach, such a quantity is clearly identified as the ion directional velocity. In the kinetic approach, the ion behavior is formulated via a quantity (the squared inverse velocity averaged by the ion distribution function)more » without any clear physical significance, which is, moreover, impractical. In the present paper, we try to explain this difference by deriving a condition called here the Unified Bohm Criterion, which combines an advanced fluid model with an upgraded explicit kinetic formula in a new form of the BC. By introducing a generalized polytropic coefficient function, the unified BC can be interpreted in a form that holds, irrespective of whether the ions are described kinetically or in the fluid approximation.« less

Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics.

PubMed

Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Wu, Joan; Chen, Shulin

2016-11-01

The present study aims to investigate the thermal decomposition behaviors and kinetics of biomass (cellulose/Douglas fir sawdust) and plastics (LDPE) in a non-catalytic and catalytic co-pyrolysis over ZSM-5 catalyst by using a thermogravimetric analyzer (TGA). It was found that there was a positive synergistic interaction between biomass and plastics according to the difference of weight loss (ΔW), which could decrease the formation of solid residue at the end of the experiment. The first order reaction model well fitted for both non-catalytic and catalytic co-pyrolysis of biomass with plastics. The activation energy (E) of Cellulose-LDPE-Catalyst and DF-LDPE-Catalyst are only 89.51 and 54.51kJ/mol, respectively. The kinetics analysis showed that adding catalyst doesn't change the decomposition mechanism. As a result, the kinetic study on catalytic co-pyrolysis of biomass with plastics was suggested that the catalytic co-pyrolysis is a promising technique that can significantly reduce the energy input. Copyright © 2016 Elsevier Ltd. All rights reserved.

Emergence of kinetic behavior in streaming ultracold neutral plasmas

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

McQuillen, P.; Castro, J.; Bradshaw, S. J.

2015-04-15

We create streaming ultracold neutral plasmas by tailoring the photoionizing laser beam that creates the plasma. By varying the electron temperature, we control the relative velocity of the streaming populations, and, in conjunction with variation of the plasma density, this controls the ion collisionality of the colliding streams. Laser-induced fluorescence is used to map the spatially resolved density and velocity distribution function for the ions. We identify the lack of local thermal equilibrium and distinct populations of interpenetrating, counter-streaming ions as signatures of kinetic behavior. Experimental data are compared with results from a one-dimensional, two-fluid numerical simulation.

Modeling of near-wall turbulence

NASA Technical Reports Server (NTRS)

Shih, T. H.; Mansour, N. N.

1990-01-01

An improved k-epsilon model and a second order closure model is presented for low Reynolds number turbulence near a wall. For the k-epsilon model, a modified form of the eddy viscosity having correct asymptotic near wall behavior is suggested, and a model for the pressure diffusion term in the turbulent kinetic energy equation is proposed. For the second order closure model, the existing models are modified for the Reynolds stress equations to have proper near wall behavior. A dissipation rate equation for the turbulent kinetic energy is also reformulated. The proposed models satisfy realizability and will not produce unphysical behavior. Fully developed channel flows are used for model testing. The calculations are compared with direct numerical simulations. It is shown that the present models, both the k-epsilon model and the second order closure model, perform well in predicting the behavior of the near wall turbulence. Significant improvements over previous models are obtained.

Unusual Voltage-Gated Sodium Currents as Targets for Pain.

PubMed

Barbosa, C; Cummins, T R

2016-01-01

Pain is a serious health problem that impacts the lives of many individuals. Hyperexcitability of peripheral sensory neurons contributes to both acute and chronic pain syndromes. Because voltage-gated sodium currents are crucial to the transmission of electrical signals in peripheral sensory neurons, the channels that underlie these currents are attractive targets for pain therapeutics. Sodium currents and channels in peripheral sensory neurons are complex. Multiple-channel isoforms contribute to the macroscopic currents in nociceptive sensory neurons. These different isoforms exhibit substantial variations in their kinetics and pharmacology. Furthermore, sodium current complexity is enhanced by an array of interacting proteins that can substantially modify the properties of voltage-gated sodium channels. Resurgent sodium currents, atypical currents that can enhance recovery from inactivation and neuronal firing, are increasingly being recognized as playing potentially important roles in sensory neuron hyperexcitability and pain sensations. Here we discuss unusual sodium channels and currents that have been identified in nociceptive sensory neurons, describe what is known about the molecular determinants of the complex sodium currents in these neurons. Finally, we provide an overview of therapeutic strategies to target voltage-gated sodium currents in nociceptive neurons. Copyright © 2016 Elsevier Inc. All rights reserved.

Distinct Protein Sorting and Localization to Premelanosomes, Melanosomes, and Lysosomes in Pigmented Melanocytic Cells✪

PubMed Central

Raposo, Graça; Tenza, Danielle; Murphy, Diane M.; Berson, Joanne F.; Marks, Michael S.

2001-01-01

Melanosomes and premelanosomes are lysosome-related organelles with a unique structure and cohort of resident proteins. We have positioned these organelles relative to endosomes and lysosomes in pigmented melanoma cells and melanocytes. Melanosome resident proteins Pmel17 and TRP1 localized to separate vesicular structures that were distinct from those enriched in lysosomal proteins. In immunogold-labeled ultrathin cryosections, Pmel17 was most enriched along the intralumenal striations of premelanosomes. Increased pigmentation was accompanied by a decrease in Pmel17 and by an increase in TRP1 in the limiting membrane. Both proteins were largely excluded from lysosomal compartments enriched in LAMP1 and cathepsin D. By kinetic analysis of fluid phase uptake and immunogold labeling, premelanosomal proteins segregated from endocytic markers within an unusual endosomal compartment. This compartment contained Pmel17, was accessed by BSA–gold after 15 min, was acidic, and displayed a cytoplasmic planar coat that contained clathrin. Our results indicate that premelanosomes and melanosomes represent a distinct lineage of organelles, separable from conventional endosomes and lysosomes within pigmented cells. Furthermore, they implicate an unusual clathrin-coated endosomal compartment as a site from which proteins destined for premelanosomes and lysosomes are sorted. PMID:11266471

Alfven resonance mode conversion in the Phaedrus-T current drive experiments: Modelling and density fluctuations measurements

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

Vukovic, M.; Harper, M.; Breun, R.

1995-12-31

Current drive experiments on the Phaedrus-T tokamak performed with a low field side two-strap fast wave antenna at frequencies below {omega}{sub cH} show loop volt drops of up to 30% with strap phasing (0, {pi}/2). RF induced density fluctuations in the plasma core have also been observed with a microwave reflectometer. It is believed that they are caused by kinetic Alfven waves generated by mode conversion of fast waves at the Alfven resonance. Correlation of the observed density fluctuations with the magnitude of the {Delta}V{sub loop} suggest that the {Delta}V{sub loop} is attributable to current drive/heating due to mode convertedmore » kinetic Alfven waves. The toroidal cold plasma wave code LION is used to model the Alfven resonance mode conversion surfaces in the experiments while the cylindrical hot plasma kinetic wave code ISMENE is used to model the behavior of kinetic Alfven waves at the Alfven resonance location. Initial results obtained from limited density, magnetic field, antenna phase, and impurity scans show good agreement between the RF induced density fluctuations and the predicted behavior of the kinetic Alfven waves. Detailed comparisons between the density fluctuations and the code predictions are presented.« less

Highly resolved fluid flows: "liquid plasmas" at the kinetic level.

PubMed

Morfill, Gregor E; Rubin-Zuzic, Milenko; Rothermel, Hermann; Ivlev, Alexei V; Klumov, Boris A; Thomas, Hubertus M; Konopka, Uwe; Steinberg, Victor

2004-04-30

Fluid flow around an obstacle was observed at the kinetic (individual particle) level using "complex (dusty) plasmas" in their liquid state. These "liquid plasmas" have bulk properties similar to water (e.g., viscosity), and a comparison in terms of similarity parameters suggests that they can provide a unique tool to model classical fluids. This allows us to study "nanofluidics" at the most elementary-the particle-level, including the transition from fluid behavior to purely kinetic transport. In this (first) experimental investigation we describe the kinetic flow topology, discuss our observations in terms of fluid theories, and follow this up with numerical simulations.

[Asperger Syndrome and/or Clinical High Risk of Psychosis? A Differential Diagnostic Challenge].

PubMed

Schmidt, Stefanie J; Behar, Ayla; Schultze-Lutter, Frauke

2018-03-01

Asperger Syndrome and/or Clinical High Risk of Psychosis? A Differential Diagnostic Challenge This case-study deals with the often difficult differential diagnosis of Asperger syndrome and a clinical high risk state of psychosis, in particular as indicated by attenuated psychotic symptoms, as well as with its therapeutic implications. The presented case is a 10-year old girl, who has not been diagnosed with an autism spectrum disorder before being referred to a specialized center for early detection of psychosis due to possible hallucinatory experiences and delusional ideas. We demonstrate how to perform a context-sensitive differential diagnosis to distinguish between specific interests as well as related behaviors and unusual thought content as well as perceptive abnormalities, between paranoid ideas and biased interpretations of the behaviors of others typical for autism, and between disorganized symptoms and autistic unusual communication and social behavior. The resulting dual diagnoses in our case-study formed the basis for a complex differential indication, which considered both the increased stress vulnerability associated with an increased risk for the development of psychosis as well as the rigid thinking style associated with autism. Our case-report shows that such a precise differential indication can lead to stabilization over the long-term, even in patients with dual diagnoses.

Emoticon-Based Ambivalent Expression: A Hidden Indicator for Unusual Behaviors in Weibo.

PubMed

Hu, Yue; Zhao, Jichang; Wu, Junjie

2016-01-01

Recent decades have witnessed online social media being a big-data window for testifying conventional social theories quantitatively and exploring much detailed human behavioral patterns. In this paper, by tracing the emoticon use in Weibo, a group of hidden "ambivalent users" are disclosed for frequently posting ambivalent tweets containing both positive and negative emotions. Further investigation reveals that this ambivalent expression could be a novel indicator of many unusual social behaviors. For instance, ambivalent users with the female as the majority like to make a sound in midnights and at weekends. They mention their close friends frequently in ambivalent tweets, which attract more replies and serve as a more private communication way. Ambivalent users also respond differently to public affairs from others and demonstrate more interests in entertainment and sports events. Moreover, the sentiment shift in ambivalent tweets is more evident than usual and exhibits a clear "negative to positive" pattern. The above observations, though being promiscuous seemingly, actually point to the self-regulation of negative mood in Weibo, which could find its basis from the traditional emotion management theories in sociology but makes an important extension to the online environment in this study. Finally, as an interesting corollary, ambivalent users are found connected with compulsive buyers and turn out to be perfect targets for online marketing.

An Unusual Salt Effect in an Interfacial Nucleophilic Substitution Reaction.

PubMed

Li, Shuheng; Mrksich, Milan

2018-06-12

This paper reports a kinetic characterization of the interfacial reaction of N-methylpyrrolidine with a self-assembled monolayer presenting an iodoalkyl group. SAMDI (self-assembled monolayers for matrix-assisted laser desorption/ionization) mass spectrometry was used to determine the extent of reaction for monolayers that were treated with a range of concentrations of the nucleophile for a range of times. These data revealed a second-order rate constant for the reaction that was approximately 100-fold greater than that for the analogous solution-phase reaction. However, addition of sodium iodide to the reaction mixture resulted in a 7-fold decrease in the reaction rate. Addition of bromide and chloride salts also gave slower rate constants for the reaction, but only at 100- and 1000-fold higher concentrations than was observed with iodide, respectively. The corresponding solution-phase reactions, by contrast, had rate constants that were unaffected by the concentration of halide salts. This work provides a well-characterized example illustrating the extent to which the kinetics and properties of an interfacial reaction can depart substantially from their better-understood solution-phase counterparts.

Catalytic strategy for carbon−carbon bond scission by the cytochrome P450 OleT

PubMed Central

Grant, Job L.; Mitchell, Megan E.; Makris, Thomas Michael

2016-01-01

OleT is a cytochrome P450 that catalyzes the hydrogen peroxide-dependent metabolism of Cn chain-length fatty acids to synthesize Cn-1 1-alkenes. The decarboxylation reaction provides a route for the production of drop-in hydrocarbon fuels from a renewable and abundant natural resource. This transformation is highly unusual for a P450, which typically uses an Fe4+−oxo intermediate known as compound I for the insertion of oxygen into organic substrates. OleT, previously shown to form compound I, catalyzes a different reaction. A large substrate kinetic isotope effect (≥8) for OleT compound I decay confirms that, like monooxygenation, alkene formation is initiated by substrate C−H bond abstraction. Rather than finalizing the reaction through rapid oxygen rebound, alkene synthesis proceeds through the formation of a reaction cycle intermediate with kinetics, optical properties, and reactivity indicative of an Fe4+−OH species, compound II. The direct observation of this intermediate, normally fleeting in hydroxylases, provides a rationale for the carbon−carbon scission reaction catalyzed by OleT. PMID:27555591

Trajectory Calculations for Bergman Cyclization Predict H/D Kinetic Isotope Effects Due to Nonstatistical Dynamics in the Product.

PubMed

Doubleday, Charles; Boguslav, Mayla; Howell, Caronae; Korotkin, Scott D; Shaked, David

2016-06-22

An unusual H/D kinetic isotope effect (KIE) is described, in which isotopic selectivity arises primarily from nonstatistical dynamics in the product. In DFT-based quasiclassical trajectories of Bergman cyclization of (Z)-3-hexen-1,5-diyne (1) at 470 K, the new CC bond retains its energy, and 28% of nascent p-benzyne recrosses back to the enediyne on a vibrational time scale. The competing process of intramolecular vibrational redistribution (IVR) in p-benzyne is too slow to prevent this. Deuteration increases the rate of IVR, which decreases the fraction of recrossing and increases the yield of statistical (trapable) p-benzyne, 2. Trapable yields for three isotopomers of 2 range from 72% to 86%. The resulting KIEs for Bergman cyclization differ substantially from KIEs predicted by transition state theory, which suggests that IVR in this reaction can be studied by conventional KIEs. Leakage of vibrational zero point energy (ZPE) into the reaction coordinate was probed by trajectories in which initial ZPE in the CH/CD stretching modes was reduced by 25%. This did not change the predicted KIEs.

Surface Interaction Kinetics of GaAs (100) Surfaces Under Electron Cyclotron Resonance Nitrogen Plasma Exposure

NASA Astrophysics Data System (ADS)

O'Steen, M. L.; Hauenstein, R. J.; Bandić, Z. Z.; Feenstra, R. M.; Hwang, S. J.; McGill, T. C.

1996-03-01

GaN is a robust semiconducting material offering a large, direct bandgap appropriate for use in blue-green to UV light emitting diodes and laser diodes. Attainment of device quality GaN has been difficult due to the lack of substrate materials that are suitably matched to the unusually small lattice parameter of GaN. To better control heteroepitaxial growth quality, a fundamental study of the initial stages of GaN growth by Electron Cyclotron Resonance Nitrogen Plasma-Assisted Molecular Beam Epitaxy (ECR-MBE) has been performed. The effect of an ECR Nitrogen plasma on a GaAs (100) surface is examined through time resolved reflection high energy electron diffraction, high resolution x-ray diffraction, and cross-sectional scanning tunneling microscopy. Fully commensurate GaN_yAs_1-y/GaAs heterostructures involving ultrathin GaN_yAs_1-y layers are obtained, and thermally activated microscopic growth processes are identified and quantitatively characterized through the aid of a specially developed kinetic model. The implications for ECR-MBE growth of GaN/GaAs mutilayers is discussed.

Writing in the Air: Contributions of Finger Movement to Cognitive Processing

PubMed Central

Itaguchi, Yoshihiro; Yamada, Chiharu; Fukuzawa, Kazuyoshi

2015-01-01

The present study investigated the interactions between motor action and cognitive processing with particular reference to kanji-culture individuals. Kanji-culture individuals often move their finger as if they are writing when they are solving cognitive tasks, for example, when they try to recall the spelling of English words. This behavior is called kusho, meaning air-writing in Japanese. However, its functional role is still unknown. To reveal the role of kusho behavior in cognitive processing, we conducted a series of experiments, employing two different cognitive tasks, a construction task and a stroke count task. To distinguish the effects of the kinetic aspects of kusho behavior, we set three hand conditions in the tasks; participants were instructed to use either kusho, unrelated finger movements or do nothing during the response time. To isolate possible visual effects, two visual conditions in which participants saw their hand and the other in which they did not, were introduced. We used the number of correct responses and response time as measures of the task performance. The results showed that kusho behavior has different functional roles in the two types of cognitive tasks. In the construction task, the visual feedback from finger movement facilitated identifying a character, whereas the kinetic feedback or motor commands for the behavior did not help to solve the task. In the stroke count task, by contrast, the kinetic aspects of the finger movements influenced counting performance depending on the type of the finger movement. Regardless of the visual condition, kusho behavior improved task performance and unrelated finger movements degraded it. These results indicated that motor behavior contributes to cognitive processes. We discussed possible mechanisms of the modality dependent contribution. These findings might lead to better understanding of the complex interaction between action and cognition in daily life. PMID:26061273

Writing in the Air: Contributions of Finger Movement to Cognitive Processing.

PubMed

Itaguchi, Yoshihiro; Yamada, Chiharu; Fukuzawa, Kazuyoshi

2015-01-01

The present study investigated the interactions between motor action and cognitive processing with particular reference to kanji-culture individuals. Kanji-culture individuals often move their finger as if they are writing when they are solving cognitive tasks, for example, when they try to recall the spelling of English words. This behavior is called kusho, meaning air-writing in Japanese. However, its functional role is still unknown. To reveal the role of kusho behavior in cognitive processing, we conducted a series of experiments, employing two different cognitive tasks, a construction task and a stroke count task. To distinguish the effects of the kinetic aspects of kusho behavior, we set three hand conditions in the tasks; participants were instructed to use either kusho, unrelated finger movements or do nothing during the response time. To isolate possible visual effects, two visual conditions in which participants saw their hand and the other in which they did not, were introduced. We used the number of correct responses and response time as measures of the task performance. The results showed that kusho behavior has different functional roles in the two types of cognitive tasks. In the construction task, the visual feedback from finger movement facilitated identifying a character, whereas the kinetic feedback or motor commands for the behavior did not help to solve the task. In the stroke count task, by contrast, the kinetic aspects of the finger movements influenced counting performance depending on the type of the finger movement. Regardless of the visual condition, kusho behavior improved task performance and unrelated finger movements degraded it. These results indicated that motor behavior contributes to cognitive processes. We discussed possible mechanisms of the modality dependent contribution. These findings might lead to better understanding of the complex interaction between action and cognition in daily life.

Unusual dewetting of thin polymer films in liquid media containing a poor solvent and a nonsolvent.

PubMed

Xu, Lin; Sharma, Ashutosh; Joo, Sang Woo; Liu, Hui; Shi, Tongfei

2014-12-16

We investigate the control of pattern size and kinetics in spontaneous dewetting of thin polymer films (polystyrene) that are stable to thermal annealing by annealing in a poor solvent (acetone)/nonsolvent (ethanol or n-hexane) liquid mixture. Dewetting occurs by the formation and growth of circular holes that coalesce to form droplets. The influence of the nature and the volume fraction of the nonsolvents on the contact angle of polymer droplets, number density of holes, and the kinetics of holes formation and growth is studied. Addition of ethanol greatly increases the hole density and slows down the kinetics substantially, while affecting only a small change in wettability. n-Hexane addition shows an interesting nonmonotonic response in decreasing the hole density and contact angle in the volume fraction range of 0-0.3 but an opposite effect beyond that. Although the two nonsolvents chosen cannot by themselves induce dewetting, their relative affinity for the solid substrate vis-à-vis acetone can strongly influence the observed dewetting scenarios that are not understood by the existing theoretical considerations. n-Hexane, for example, has great affinity for silicon substrate. In addition to the changes in wettability, viscosity, and film interfacial tension engendered by the nonsolvents, the possibility of the formation of adsorbed liquid layers at the substrate-polymer interface, which can modify the interfacial friction and slippage, needs to be considered.

Energy barriers and rates of tautomeric transitions in DNA bases: ab initio quantum chemical study.

PubMed

Basu, Soumalee; Majumdar, Rabi; Das, Gourab K; Bhattacharyya, Dhananjay

2005-12-01

Tautomeric transitions of DNA bases are proton transfer reactions, which are important in biology. These reactions are involved in spontaneous point mutations of the genetic material. In the present study, intrinsic reaction coordinates (IRC) analyses through ab initio quantum chemical calculations have been carried out for the individual DNA bases A, T, G, C and also A:T and G:C base pairs to estimate the kinetic and thermodynamic barriers using MP2/6-31G** method for tautomeric transitions. Relatively higher values of kinetic barriers (about 50-60 kcal/mol) have been observed for the single bases, indicating that tautomeric alterations of isolated single bases are quite unlikely. On the other hand, relatively lower values of the kinetic barriers (about 20-25 kcal/mol) for the DNA base pairs A:T and G:C clearly suggest that the tautomeric shifts are much more favorable in DNA base pairs than in isolated single bases. The unusual base pairing A':C, T':G, C':A or G':T in the daughter DNA molecule, resulting from a parent DNA molecule with tautomeric shifts, is found to be stable enough to result in a mutation. The transition rate constants for the single DNA bases in addition to the base pairs are also calculated by computing the free energy differences between the transition states and the reactants.

Wave kinetics of drift-wave turbulence and zonal flows beyond the ray approximation

NASA Astrophysics Data System (ADS)

Zhu, Hongxuan; Zhou, Yao; Ruiz, D. E.; Dodin, I. Y.

2018-05-01

Inhomogeneous drift-wave turbulence can be modeled as an effective plasma where drift waves act as quantumlike particles and the zonal-flow velocity serves as a collective field through which they interact. This effective plasma can be described by a Wigner-Moyal equation (WME), which generalizes the quasilinear wave-kinetic equation (WKE) to the full-wave regime, i.e., resolves the wavelength scale. Unlike waves governed by manifestly quantumlike equations, whose WMEs can be borrowed from quantum mechanics and are commonly known, drift waves have Hamiltonians very different from those of conventional quantum particles. This causes unusual phase-space dynamics that is typically not captured by the WKE. We demonstrate how to correctly model this dynamics with the WME instead. Specifically, we report full-wave phase-space simulations of the zonal-flow formation (zonostrophic instability), deterioration (tertiary instability), and the so-called predator-prey oscillations. We also show how the WME facilitates analysis of these phenomena, namely, (i) we show that full-wave effects critically affect the zonostrophic instability, particularly its nonlinear stage and saturation; (ii) we derive the tertiary-instability growth rate; and (iii) we demonstrate that, with full-wave effects retained, the predator-prey oscillations do not require zonal-flow collisional damping, contrary to previous studies. We also show how the famous Rayleigh-Kuo criterion, which has been missing in wave-kinetic theories of drift-wave turbulence, emerges from the WME.

Convergent evolution of plant and animal embryo defences by hyperstable non-digestible storage proteins.

PubMed

Pasquevich, María Yanina; Dreon, Marcos Sebastián; Qiu, Jian-Wen; Mu, Huawei; Heras, Horacio

2017-11-20

Plants have evolved sophisticated embryo defences by kinetically-stable non-digestible storage proteins that lower the nutritional value of seeds, a strategy that have not been reported in animals. To further understand antinutritive defences in animals, we analysed PmPV1, massively accumulated in the eggs of the gastropod Pomacea maculata, focusing on how its structure and structural stability features affected its capacity to withstand passage through predator guts. The native protein withstands >50 min boiling and resists the denaturing detergent sodium dodecyl sulphate (SDS), indicating an unusually high structural stability (i.e., kinetic stability). PmPV1 is highly resistant to in vitro proteinase digestion and displays structural stability between pH 2.0-12.0 and 25-85 °C. Furthermore, PmPV1 withstands in vitro and mice digestion and is recovered unchanged in faeces, supporting an antinutritive defensive function. Subunit sequence similarities suggest a common origin and tolerance to mutations. This is the first known animal genus that, like plant seeds, lowers the nutritional value of eggs by kinetically-stable non-digestible storage proteins that survive the gut of predators unaffected. The selective pressure of the harsh gastrointestinal environment would have favoured their appearance, extending by convergent evolution the presence of plant-like hyperstable antinutritive proteins to unattended reproductive stages in animals.

The influence of sequence context and length on the kinetics of DNA duplex formation from complementary hairpins possessing (CNG) repeats.

PubMed

Paiva, Anthony M; Sheardy, Richard D

2005-04-20

The formation of unusual structures during DNA replication has been invoked for gene expansion in genomes possessing triplet repeat sequences, CNG, where N = A, C, G, or T. In particular, it has been suggested that the daughter strand of the leading strand partially dissociates from the parent strand and forms a hairpin. The equilibrium between the fully duplexed parent:daugter species and the parent:hairpin species is dependent upon their relative stabilities and the rates of reannealing of the daughter strand back to the parent. These stabilities and rates are ultimately influenced by the sequence context of the DNA and its length. Previous work has demonstrated that longer strands are more stable than shorter strands and that the identity of N also influences the thermal stability [Paiva, A. M.; Sheardy, R. D. Biochemistry 2004, 43, 14218-14227]. Here, we show that the rate of duplex formation from complementary hairpins is also sequence context and length dependent. In particular, longer duplexes have higher activation energies than shorter duplexes of the same sequence context. Further, [(CCG):(GGC)] duplexes have lower activation energies than corresponding [(CAG):(GTC)] duplexes of the same length. Hence, hairpins formed from long CNG sequences are more thermodynamically stable and have slower kinetics for reannealing to their complement than shorter analogues. Gene expansion can now be explained in terms of thermodynamics and kinetics.

Interface Reactions and Synthetic Reaction of Composite Systems

PubMed Central

Park, Joon Sik; Kim, Jeong Min

2010-01-01

Interface reactions in composite systems often determine their overall properties, since product phases usually formed at interfaces during composite fabrication processing make up a large portion of the composites. Since most composite materials represent a ternary or higher order materials system, many studies have focused on analyses of diffusion phenomena and kinetics in multicomponent systems. However, the understanding of the kinetic behavior increases the complexity, since the kinetics of each component during interdiffusion reactions need to be defined for interpreting composite behaviors. From this standpoint, it is important to clarify the interface reactions for producing compatible interfaces with desired product phases. A thermodynamic evaluation such as a chemical potential of involving components can provide an understanding of the diffusion reactions, which govern diffusion pathways and product phase formation. A strategic approach for designing compatible interfaces is discussed in terms of chemical potential diagrams and interface morphology, with some material examples.

Reactions of chlorine nitrate with HCl and H2O. [ozone controlling chemistry in stratosphere

NASA Technical Reports Server (NTRS)

Hatakeyama, Shiro; Leu, Ming-Taun

1986-01-01

The kinetics of the reactions of chlorine nitrate with HCl and H2O are characterized using a static photolysis/Fourier transform infrared spectrophotometer apparatus. For the homogeneous gas-phase reaction with HCl, an upper limit for the rate constant of less than 8.4 x 10 to the -21st, and for the reaction with H2O, a limit of less than 3.4 x 10 to the -21st cu cm/molecule per s, were obtained at 296 + or - 2 K. The yield of HNO3 is almost unity in both cases, and no synergistic effect is noted between HCl and H2O. The kinetic behavior of the reaction with H2O is well described by simple first-order kinetics, while the behavior of the reaction with HCl is described in terms of the Langmuir adsorption isotherm.

Nonequilibrium phase coexistence and criticality near the second explosion limit of hydrogen combustion

NASA Astrophysics Data System (ADS)

Newcomb, Lucas B.; Alaghemandi, Mohammad; Green, Jason R.

2017-07-01

While hydrogen is a promising source of clean energy, the safety and optimization of hydrogen technologies rely on controlling ignition through explosion limits: pressure-temperature boundaries separating explosive behavior from comparatively slow burning. Here, we show that the emergent nonequilibrium chemistry of combustible mixtures can exhibit the quantitative features of a phase transition. With stochastic simulations of the chemical kinetics for a model mechanism of hydrogen combustion, we show that the boundaries marking explosive domains of kinetic behavior are nonequilibrium critical points. Near the pressure of the second explosion limit, these critical points terminate the transient coexistence of dynamical phases—one that autoignites and another that progresses slowly. Below the critical point temperature, the chemistry of these phases is indistinguishable. In the large system limit, the pseudo-critical temperature converges to the temperature of the second explosion limit derived from mass-action kinetics.

Chemical kinetic reaction mechanism for the combustion of propane

NASA Technical Reports Server (NTRS)

Jachimowski, C. J.

1984-01-01

A detailed chemical kinetic reaction mechanism for the combustion of propane is presented and discussed. The mechanism consists of 27 chemical species and 83 elementary chemical reactions. Ignition and combustion data as determined in shock tube studies were used to evaluate the mechanism. Numerical simulation of the shock tube experiments showed that the kinetic behavior predicted by the mechanism for stoichiometric mixtures is in good agrement with the experimental results over the entire temperature range examined (1150-2600K). Sensitivity and theoretical studies carried out using the mechanism revealed that hydrocarbon reactions which are involved in the formation of the HO2 radical and the H2O2 molecule are very important in the mechanism and that the observed nonlinear behavior of ignition delay time with decreasing temperature can be interpreted in terms of the increased importance of the HO2 and H2O2 reactions at the lower temperatures.

Coding gestural behavior with the NEUROGES--ELAN system.

PubMed

Lausberg, Hedda; Sloetjes, Han

2009-08-01

We present a coding system combined with an annotation tool for the analysis of gestural behavior. The NEUROGES coding system consists of three modules that progress from gesture kinetics to gesture function. Grounded on empirical neuropsychological and psychological studies, the theoretical assumption behind NEUROGES is that its main kinetic and functional movement categories are differentially associated with specific cognitive, emotional, and interactive functions. ELAN is a free, multimodal annotation tool for digital audio and video media. It supports multileveled transcription and complies with such standards as XML and Unicode. ELAN allows gesture categories to be stored with associated vocabularies that are reusable by means of template files. The combination of the NEUROGES coding system and the annotation tool ELAN creates an effective tool for empirical research on gestural behavior.

Uncovering Oscillations, Complexity, and Chaos in Chemical Kinetics Using Mathematica

NASA Astrophysics Data System (ADS)

Ferreira, M. M. C.; Ferreira, W. C., Jr.; Lino, A. C. S.; Porto, M. E. G.

1999-06-01

Unlike reactions with no peculiar temporal behavior, in oscillatory reactions concentrations can rise and fall spontaneously in a cyclic or disorganized fashion. In this article, the software Mathematica is used for a theoretical study of kinetic mechanisms of oscillating and chaotic reactions. A first simple example is introduced through a three-step reaction, called the Lotka model, which exhibits a temporal behavior characterized by damped oscillations. The phase plane method of dynamic systems theory is introduced for a geometric interpretation of the reaction kinetics without solving the differential rate equations. The equations are later numerically solved using the built-in routine NDSolve and the results are plotted. The next example, still with a very simple mechanism, is the Lotka-Volterra model reaction, which oscillates indefinitely. The kinetic process and rate equations are also represented by a three-step reaction mechanism. The most important difference between this and the former reaction is that the undamped oscillation has two autocatalytic steps instead of one. The periods of oscillations are obtained by using the discrete Fourier transform (DFT)-a well-known tool in spectroscopy, although not so common in this context. In the last section, it is shown how a simple model of biochemical interactions can be useful to understand the complex behavior of important biological systems. The model consists of two allosteric enzymes coupled in series and activated by its own products. This reaction scheme is important for explaining many metabolic mechanisms, such as the glycolytic oscillations in muscles, yeast glycolysis, and the periodic synthesis of cyclic AMP. A few of many possible dynamic behaviors are exemplified through a prototype glycolytic enzymatic reaction proposed by Decroly and Goldbeter. By simply modifying the initial concentrations, limit cycles, chaos, and birhythmicity are computationally obtained and visualized.

Fostering Academic Creativity in Gifted Students. ERIC Digest #E484.

ERIC Educational Resources Information Center

Torrance, E. Paul; Goff, Kathy

This digest describes academic creativity and offers suggestions for its development in gifted students. Creative learning and learning by authority are contrasted and examples of each are given. The naturally creative behavior of young children is noted. Among suggestions offered to teachers are: respect the unusual questions of children; show…

Taking Charge: A Handbook for Parents Whose Children Have Emotional Handicaps.

ERIC Educational Resources Information Center

Kelker, Katharin A.

The manual is designed to provide information and support to parents of emotionally disturbed children. The first chapter, "Feelings Come First," deals with such topics as identifying unusual behavior, impact on parents and other family members, coming to terms with feelings, and advice from other parents. Chapter 2, "Finding Some Help," defines…

Multidisciplinary Developmental Evaluation Improves Early Diagnosis of Infantile Autism.

ERIC Educational Resources Information Center

Siegel, B.; And Others

A life-course perspective of the diagnostic histories of 75 autistic individuals (ages 4-25) was obtained through the use of parent surveys and a review of their charts. The study was made to understand better how children who presented with uneven or unusual behavioral development are identified as developmentally multihandicapped. Areas examined…

The Effect of Microgravity on the Growth of Silica Nanostructures

NASA Technical Reports Server (NTRS)

Smith, D. D.; Sibille, L.; Cronise, R.; Oldenburg, S. J.; Wolfe, D.; Halas, N. J.

2001-01-01

The process of the formation of structures from coagulating ensembles is fundamentally important since the collective behavior of the constituents often results in dramatically improved or unusual mechanical, thermal, chemical, and optical properties. In this study we examine the effect of microgravity on the formation of silica structures, specifically particles and gels.

Unusual behavior of quiet-time zonal and vertical plasma drift velocities over Jicamarca during the recent extended solar minimum of 2008

NASA Astrophysics Data System (ADS)

Santos, Ângela M.; Abdu, Mangalathayil A.; Souza, Jonas R.; Batista, Inez S.; Sobral, José H. A.

2017-11-01

The influence of the recent deep and prolonged solar minimum on the daytime zonal and vertical plasma drift velocities during quiet time is investigated in this work. Analyzing the data obtained from incoherent scatter radar from Jicamarca (11.95° S, 76.87° W) we observe an anomalous behavior of the zonal plasma drift during June 2008 characterized by lower than usual daytime westward drift and its early afternoon reversal to eastward. As a case study the zonal drift observed on 24 June 2008 is modeled using a realistic low-latitude ionosphere simulated by the Sheffield University Plasmasphere-Ionosphere Model-INPE (SUPIM-INPE). The results show that an anomalously low zonal wind was mainly responsible for the observed anomalous behavior in the zonal drift. A comparative study of the vertical plasma drifts obtained from magnetometer data for some periods of maximum (2000-2002) and minimum solar activity (1998, 2008, 2010) phases reveal a considerable decrease on the E-region conductivity and the dynamo electric field during 2008. However, we believe that the contribution of these characteristics to the unusual behavior of the zonal plasma drift is significantly smaller than that arising from the anomalously low zonal wind. The SUPIM-INPE result of the critical frequency of the F layer (foF2) over Jicamarca suggested a lower radiation flux than that predicted by solar irradiance model (SOLAR2000) for June 2008.

Modeling of autocatalytic hydrolysis of adefovir dipivoxil in solid formulations.

PubMed

Dong, Ying; Zhang, Yan; Xiang, Bingren; Deng, Haishan; Wu, Jingfang

2011-04-01

The stability and hydrolysis kinetics of a phosphate prodrug, adefovir dipivoxil, in solid formulations were studied. The stability relationship between five solid formulations was explored. An autocatalytic mechanism for hydrolysis could be proposed according to the kinetic behavior which fits the Prout-Tompkins model well. For the classical kinetic models could hardly describe and predict the hydrolysis kinetics of adefovir dipivoxil in solid formulations accurately when the temperature is high, a feedforward multilayer perceptron (MLP) neural network was constructed to model the hydrolysis kinetics. The build-in approaches in Weka, such as lazy classifiers and rule-based learners (IBk, KStar, DecisionTable and M5Rules), were used to verify the performance of MLP. The predictability of the models was evaluated by 10-fold cross-validation and an external test set. It reveals that MLP should be of general applicability proposing an alternative efficient way to model and predict autocatalytic hydrolysis kinetics for phosphate prodrugs.

AN UNUSUAL PATTERN OF GENE FLOW BETWEEN THE TWO SOCIAL FORMS OF THE FIRE ANT SOLENOPSIS INVICTA.

PubMed

Ross, Kenneth G; Shoemaker, D DeWayne

1993-10-01

Uncertainty over the role of shifts in social behavior in the process of speciation in social insects has stimulated interest in determining the extent of gene flow between conspecific populations differing in colony social organization. Allele and genotype frequencies at 12 neutral polymorphic protein markers, as well as the numbers of alleles at the sex-determining locus (loci), are shown here to be consistent with significant ongoing gene flow between two geographically adjacent populations of Solenopsis invicta that differ in colony queen number. Data from a thirteenth protein marker that is under strong differential selection in the two social forms confirm that such gene flow occurs. Data from this selected locus, combined with knowledge of the reproductive biology of the two social forms, further suggest that interform gene flow is largely unidirectional and mediated through males only. This unusual pattern of gene flow results from the influence of the unique social enviroments of the two forms on the behavior of workers and on the reproductive physiology of sexuals. © 1993 The Society for the Study of Evolution.

Diblock copolymers of polystyrene- b-poly(1,3-cyclohexadiene) exhibiting unique three-phase microdomain morphologies

DOE PAGES

Misichronis, Konstantinos; Chen, Jihua; Kahk, Jong K.; ...

2016-03-29

Here, the synthesis and molecular characterization of a series of conformationally asymmetric polystyrene-block-poly(1,3-cyclohexadiene) (PS- b-PCHD) diblock copolymers (PCHD: ~90% 1,4 and ~10% 1,2), by sequential anionic copolymerization high vacuum techniques, is reported. A wide range of volume fractions (0.27 ≤ Φ PS ≤ 0.91) was studied by transmission electron microscopy and small-angle X-ray scattering in order to explore in detail the microphase separation behavior of these flexible/semiflexible diblock copolymers. Unusual morphologies, consisting of PCHD core(PCHD-1,4)–shell(PCHD-1,2) cylinders in PS matrix and three-phase (PS, PCHD-1,4, PCHD-1,2) four-layer lamellae, were observed suggesting that the chain stiffness of the PCHD block and the strongmore » dependence of the interaction parameter χ on the PCHD microstructures are important factors for the formation of this unusual microphase separation behavior in PS- b-PCHD diblock copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1564–1572« less

Translational animal models of autism and neurodevelopmental disorders

PubMed Central

Crawley, Jacqueline N.

2012-01-01

Autism is a neurodevelopmental disorder whose diagnosis is based on three behavioral criteria: unusual reciprocal social interactions, deficits in communication, and stereotyped repetitive behaviors with restricted interests. A large number of de novo single gene mutations and chromosomal deletions are associated with autism spectrum disorders. Based on the strong genetic evidence, mice with targeted mutations in homologous genes have been generated as translational research tools. Mouse models of autism have revealed behavioral and biological outcomes of mutations in risk genes. The field is now poised to employ the most robust phenotypes in the most replicable mouse models for preclinical screening of novel therapeutics. PMID:23226954

Late Neandertals and the intentional removal of feathers as evidenced from bird bone taphonomy at Fumane Cave 44 ky B.P., Italy.

PubMed

Peresani, Marco; Fiore, Ivana; Gala, Monica; Romandini, Matteo; Tagliacozzo, Antonio

2011-03-08

A large and varied avifaunal bone assemblage from the final Mousterian levels of Grotta di Fumane, northern Italy, reveals unusual human modifications on species that are not clearly relatable to feeding or utilitarian uses (i.e., lammergeier, Eurasian black vulture, golden eagle, red-footed falcon, common wood pigeon, and Alpine chough). Cut, peeling, and scrape marks, as well as diagnostic fractures and a breakthrough, are observed exclusively on wings, indicating the intentional removal of large feathers by Neandertals. The species involved, the anatomical elements affected, and the unusual type and location of the human modifications indicate an activity linked to the symbolic sphere and the behavioral modernity of this European autochthonous population.

Anomalous glassy dynamics in simple models of dense biological tissue

NASA Astrophysics Data System (ADS)

Sussman, Daniel M.; Paoluzzi, M.; Marchetti, M. Cristina; Manning, M. Lisa

2018-02-01

In order to understand the mechanisms for glassy dynamics in biological tissues and shed light on those in non-biological materials, we study the low-temperature disordered phase of 2D vertex-like models. Recently it has been noted that vertex models have quite unusual behavior in the zero-temperature limit, with rigidity transitions that are controlled by residual stresses and therefore exhibit very different scaling and phenomenology compared to particulate systems. Here we investigate the finite-temperature phase of two-dimensional Voronoi and Vertex models, and show that they have highly unusual, sub-Arrhenius scaling of dynamics with temperature. We connect the anomalous glassy dynamics to features of the potential energy landscape associated with zero-temperature inherent states.

Unusually large Stokes shift for a near-infrared emitting DNA-stabilized silver nanocluster

NASA Astrophysics Data System (ADS)

Ammitzbøll Bogh, Sidsel; Carro-Temboury, Miguel R.; Cerretani, Cecilia; Swasey, Steven M.; Copp, Stacy M.; Gwinn, Elisabeth G.; Vosch, Tom

2018-04-01

In this paper we present a new near-IR emitting silver nanocluster (NIR-DNA-AgNC) with an unusually large Stokes shift between absorption and emission maximum (211 nm or 5600 cm-1). We studied the effect of viscosity and temperature on the steady state and time-resolved emission. The time-resolved results on NIR-DNA-AgNC show that the relaxation dynamics slow down significantly with increasing viscosity of the solvent. In high viscosity solution, the spectral relaxation stretches well into the nanosecond scale. As a result of this slow spectral relaxation in high viscosity solutions, a multi-exponential fluorescence decay time behavior is observed, in contrast to the more mono-exponential decay in low viscosity solution.

Rapid Speech Transmission Index predictions and auralizations of unusual instructional spaces at MIT's new Stata Center

NASA Astrophysics Data System (ADS)

Conant, David A.

2005-04-01

The Stata Center for Computer, Information and Intelligence Sciences, recently opened at the Massachusetts Institute of Technology, includes a variety of oddly-shaped seminar rooms in addition to lecture spaces of somewhat more conventional form. The architects design approach prohibited following conventional, well understood room-acoustical behavior yet MIT and the design team were keenly interested in ensuring that these spaces functioned exceptionally well, acoustically. CATT-Acoustic room modeling was employed to assess RASTI through multiple design iterations for all these spaces. Presented here are computational and descriptive results achieved for these rooms which are highly-regarded by faculty. They all sound peculiarly good, given their unusual form. In addition, binaural auralizations for selected spaces are provided.

Tuning of superconductivity by Ni substitution into noncentrosymmetric ThC o1 -xN ixC2

NASA Astrophysics Data System (ADS)

Grant, T. W.; Cigarroa, O. V.; Rosa, P. F. S.; Machado, A. J. S.; Fisk, Z.

2017-07-01

The recently discovered noncentrosymmetric superconductor ThCoC2 was observed to show unusual superconducting behavior with a critical temperature of Tc=2.65 K . Here we investigate the effect of nickel substitution on the superconducting state in ThC o1 -xN ixC2 . Magnetization, resistivity, and heat capacity measurements demonstrate Ni substitution has a dramatic effect with critical temperature increased up to Tc=12.1 K for x =0.4 Ni concentration, which is a rather high transition temperature for a noncentrosymmetric superconductor. In addition, the unusual superconducting characteristics observed in pure ThCoC2 appear to be suppressed or tuned with Ni substitution towards a more conventional fully gapped superconductor.

Reverse Stability Kinetics of Meat Pigment Oxidation in Aqueous Extract from Fresh Beef.

PubMed

Frelka, John C; Phinney, David M; Wick, Macdonald P; Heldman, Dennis R

2017-12-01

The use of kinetic models is an evolving approach to describing quality changes in foods during processes, including storage. Previous studies indicate that the oxidation rate of myoglobin is accelerated under frozen storage conditions, a phenomenon termed reverse stability. The goal of this study was to develop a model for meat pigment oxidation to incorporate the phenomenon of reverse stability. In this investigation, the model system was an aqueous extract from beef which was stored under a range of temperatures, both unfrozen and frozen. The kinetic analysis showed that in unfrozen solutions, the temperature dependence of oxidation rate followed Arrhenius kinetics. However, under in frozen solutions the rate of oxidation increased with decreasing temperature until reaching a local maximum around -20 °C. The addition of NaCl to the model system increased oxidation rates at all temperatures, even above the initial freezing temperature. This observation suggests that this reaction is dependent on the ionic strength of the solution as well as temperature. The mechanism of this deviant kinetic behavior is not fully understood, but this study shows that the interplay of temperature and composition on the rate of oxidation of meat pigments is complicated and may involve multiple mechanisms. A better understanding of the kinetics of quality loss in a meat system allows for a re-examination of the current recommendations for frozen storage. The deviant kinetic behavior observed in this study indicates that the relationship between quality loss and temperature in a frozen food is not as simple as once thought. Product-specific recommendations could be implemented in the future that would allow for a decrease in energy consumption without a significant loss of quality. © 2017 Institute of Food Technologists®.

Kinetics of Methylmercury Production Revisited

DOE PAGES

Olsen, Todd A.; Muller, Katherine A.; Painter, Scott L.; ...

2018-01-27

Laboratory measurements of the biologically mediated methylation of mercury (Hg) to the neurotoxin monomethylmercury (MMHg) often exhibit kinetics that are inconsistent with first-order kinetic models. Using time-resolved measurements of filter passing Hg and MMHg during methylation/demethylation assays, a multisite kinetic sorption model, and reanalyses of previous assays, we show in this paper that competing kinetic sorption reactions can lead to time-varying availability and apparent non-first-order kinetics in Hg methylation and MMHg demethylation. The new model employing a multisite kinetic sorption model for Hg and MMHg can describe the range of behaviors for time-resolved methylation/demethylation data reported in the literature includingmore » those that exhibit non-first-order kinetics. Additionally, we show that neglecting competing sorption processes can confound analyses of methylation/demethylation assays, resulting in rate constant estimates that are systematically biased low. Finally, simulations of MMHg production and transport in a hypothetical periphyton biofilm bed illustrate the implications of our new model and demonstrate that methylmercury production may be significantly different than projected by single-rate first-order models.« less

Response of dorsomedial prefrontal cortex predicts altruistic behavior

PubMed Central

Waytz, Adam; Zaki, Jamil; Mitchell, Jason P.

2012-01-01

Human beings have an unusual proclivity for altruistic behavior, and recent commentators have suggested that these prosocial tendencies arise from our unique capacity to understand the minds of others (i.e., to mentalize). The current studies test this hypothesis by examining the relation between altruistic behavior and the reflexive engagement of a neural system reliably associated with mentalizing. Results indicated that activity in the dorsomedial prefrontal cortex (dorsal MPFC)—a region consistently involved in understanding others’ mental states—predicts both monetary donations to others and time spent helping others. These findings address long-standing questions about the proximate source of human altruism by suggesting that prosocial behavior results, in part, from our broader tendency for social-cognitive thought. PMID:22649243

The unique kinetic behavior of the very large NAD-dependent glutamate dehydrogenase from Janthinobacterium lividum.

PubMed

Kawakami, Ryushi; Oyama, Masaki; Sakuraba, Haruhiko; Ohshima, Toshihisa

2010-01-01

The kinetics of a very large NAD-dependent glutamate dehydrogenase from Janthinobacterium lividum showed positive cooperativity toward alpha-ketoglutarate and NADH, and the Michaelis-Menten type toward ammonium chloride in the absence of the catalytic activator, L-aspartate. An increase in the maximum activity accompanied the decrease in the S(0.5) values for alpha-ketoglutarate and NADH with the addition of L-aspartate, and the kinetic response for alpha-ketoglutarate changed completely to a typical Michaelis-Menten type in the presence of 10 mM L-aspartate.

Impact of nonabsorbing control rod tips on kinetics feedback for BWR turbine trip without bypass RETRAN-03 analyses

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

Feltus, M.A.; Knerr, R.; Shoop, U.

1993-01-01

RETRAN-03 studies were performed for the boiling water reactor (BWR) turbine trip without bypass (TTWOB) event to investigate how the non-neutron-absorbing material on control rod tips affect scram delay timing and reactivity feedback. Scram delay, Doppler temperature, and moderator void (density) feedback were varied to assess their relative impact on kinetics behavior. Although a generic point-kinetics RETRAN-03 TTWOB model 2 was employed, actual plant information was used to develop the basic and parametric cases.

Origin of Unusual Dependencies of LUMO Levels on Conjugation Length in Quinoidal Fused Oligosiloles

NASA Astrophysics Data System (ADS)

Misawa, Nana; Fujii, Mikiya; Shintani, Ryo; Tsuda, Tomohiro; Nozaki, Kyoko; Yamashita, Koichi

Quinoidal fused oligosiloles, a new family of silicon-bridged π-conjugated compounds, have been synthesized and their physical properties showed a unique trend in their LUMO levels, which become higher with longer π-conjugation. Although this trend was reproduced by the DFT calculations, its origin remained to be discussed. In this work we performed quantum chemical calculations and discovered that the unusual LUMO trend is attributable to the π-frameworks. We elucidated its origin by orbital correlation diagrams based on classical Hückel calculations, essentially. However, LUMO trends cannot fully be explained only by Hückel calculations because of the lack of the consideration of geometries. In the case of quinoidal fused oligosiloles, judging from DFT calculation results, the presence of silole fused structure play an important role in fixing the bond angles of the linear polyenes as an interior angle of siloles, leading to the unusual LUMO behavior. The qualitative but essential understanding of these LUMO trend would provide new insight into molecular design of π-conjugated compounds for tuning their LUMO levels.

A pediatric intramedullary spinal cord tumor with unusual solid-cystic and papillary features: a case report.

PubMed

Iwasaki, Takeshi; Kato, Masako; Horie, Yasushi; Kato, Shinsuke; Akatsuka, Keiichi; Watanabe, Takashi; Kuwamoto, Satoshi; Murakami, Ichiro; Hayashi, Kazuhiko

2011-12-01

Spinal cord tumors are rare in children. We report a novel case of pediatric intramedullary spinal cord tumor with unusual solid-cystic and papillary features. Clinically, the patient presented at the age of 3 years with motor deficit and urinary incontinence, and MRI demonstrated multilocular cystic lesions in the thoracic spine. Histologically the tumor consisted of solid, sheet-like components and branching papillary structures, and immunohistochemistry demonstrated positive reactivity for epithelial membrane antigen, cytokeratins (7, AE1/3, CAM5.2), E-cadherin and transthyretin, and negativity for GFAP, S-100 protein, synaptophysin and neurofilament. These histological and immunohistochemical findings appeared to be unique, and were not compatible with the features of classical ependymoma or choroid plexus papilloma. The clinical behavior, characterized by relatively rapid tumor regrowth after surgical resection and a relatively high MIB-1 labeling index, suggest that this tumor might have had moderate malignant potential. This pediatric case appears to be particularly informative with regard to the tumor biology or tumorigenesis of intramedullary spinal cord tumor with unusual solid-cystic and papillary features. © 2011 Japanese Society of Neuropathology.

Phase coherent transport in hybrid superconductor-topological insulator devices

NASA Astrophysics Data System (ADS)

Finck, Aaron

2015-03-01

Heterostructures of superconductors and topological insulators are predicted to host unusual zero energy bound states known as Majorana fermions, which can robustly store and process quantum information. Here, I will discuss our studies of such heterostructures through phase-coherent transport, which can act as a unique probe of Majorana fermions. We have extensively explored topological insulator Josephson junctions through SQUID and single-junction diffraction patterns, whose unusual behavior give evidence for low-energy Andreev bound states. In topological insulator devices with closely spaced normal and superconducting leads, we observe prominent Fabry-Perot oscillations, signifying gate-tunable, quasi-ballistic transport that can elegantly interact with Andreev reflection. Superconducting disks deposited on the surface of a topological insulator generate Aharonov-Bohm-like oscillations, giving evidence for unusual states lying near the interface between the superconductor and topological insulator surface. Our results point the way towards sophisticated interferometers that can detect and read out the state of Majorana fermions in topological systems. This work was done in collaboration with Cihan Kurter, Yew San Hor, and Dale Van Harlingen. We acknowledge funding from Microsoft Project Q.

Modified unified kinetic scheme for all flow regimes.

PubMed

Liu, Sha; Zhong, Chengwen

2012-06-01

A modified unified kinetic scheme for the prediction of fluid flow behaviors in all flow regimes is described. The time evolution of macrovariables at the cell interface is calculated with the idea that both free transport and collision mechanisms should be considered. The time evolution of macrovariables is obtained through the conservation constraints. The time evolution of local Maxwellian distribution is obtained directly through the one-to-one mapping from the evolution of macrovariables. These improvements provide more physical realities in flow behaviors and more accurate numerical results in all flow regimes especially in the complex transition flow regime. In addition, the improvement steps introduce no extra computational complexity.

Transition Behaviors of Configurations of Colloidal Particles at a Curved Oil-Water Interface

PubMed Central

Lee, Mina; Xia, Ming; Park, Bum Jun

2016-01-01

We studied the transition behaviors of colloidal arrangements confined at a centro-symmetrically curved oil-water interface. We found that assemblies composed of several colloidal particles at the curved interface exhibit at least two unique patterns that can be attributed to two factors: heterogeneity of single-colloid self-potential and assembly kinetics. The presence of the two assembly structures indicates that an essential energy barrier between the two structures exists and that one of the structures is kinetically stable. This energy barrier can be overcome via external stimuli (e.g., convection and an optical force), leading to dynamic transitions of the assembly patterns. PMID:28773263

Correlating cytotoxicity to elution behaviors of composite resins in term of curing kinetic.

PubMed

Meng, Junquan; Yang, Huichuan; Cao, Man; Li, Lei; Cai, Qing

2017-09-01

Cytotoxicity of photocurable composite resins is a key issue for their safe use in dental restoration. Curing kinetic and elution behaviors of the composite resin would have decisive effects on its cytotoxicity. In this study, composite resins composed of bisphenol-glycidyl dimethacrylate (Bis-GMA), triethyleneglycol dimethacrylate (TEGDMA), camphorquinone (CQ), N,N-dimethylaminoethyl methacrylate (DMAEMA) and barium glass powders were prepared by setting the photoinitiators CQ/DMAEMA at 0.5wt%, 1wt% or 3wt% of the total weight of Bis-GMA/TEGDMA. The ratio of Bis-GMA/TEGDMA was 6:4, the ratio of CQ/DMAEMA was 1:1, and the incorporated inorganic powder was 75wt%. Then, curing kinetics were studied by using real-time Fourier transform infrared spectroscopy (FTIR) and photo-DSC (differential scanning calorimeter). Elution behaviors in both ethanol solution and deionized water were monitored by using liquid chromatogram/mass spectrometry (LC/MS). Cytotoxicity was evaluated by in vitro culture of L929 fibroblasts. Finally, they were all analyzed and correlated in terms of initiator contents. It was found that the commonly used 0.5wt% of photoinitiators was somewhat insufficient in obtaining composite resin with low cytotoxicity. Copyright © 2017. Published by Elsevier B.V.

Kinetic Behavior of Exchange-Driven Growth with Catalyzed-Birth Processes

NASA Astrophysics Data System (ADS)

Wang, Hai-Feng; Lin, Zhen-Quan; Kong, Xiang-Mu

2006-12-01

Two catalyzed-birth models of n-species (n>=2) aggregates with exchange-driven growth processes are proposed and compared. In the first one, the exchange reaction occurs between any two aggregates Amk and Amj of the same species with the rate kernels Km(k,j) = Kmkj (m = 1,2,...,n, n>=2), and aggregates of An species catalyze a monomer-birth of Al species (l = 1,2,...,n-1) with the catalysis rate kernel Jl(k,j) = Jlkjυ. The kinetic behaviors are investigated by means of the mean-field theory. We find that the evolution behavior of aggregate-size distribution alk(t) of Al species depends crucially on the value of the catalysis rate parameter υ: (i) alk(t) obeys the conventional scaling law in the case of υ<=0, (ii) alk(t) satisfies a modified scaling form in the case of υ>0. In the second model, the mechanism of monomer-birth of An-species catalyzed by Al species is added on the basis of the first model, that is, the aggregates of Al and An species catalyze each other to cause monomer-birth. The kinetic behaviors of Al and An species are found to fall into two categories for the different υ: (i) growth obeying conventional scaling form with υ<=0, (ii) gelling at finite time with υ>0.

Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

USGS Publications Warehouse

Xia, Xinyu; Ellis, Geoffrey S.; Ma, Qisheng; Tang, Yongchun

2014-01-01

The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C2–5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C2–5 hydrocarbons becoming more enriched in 13C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ13C2+ values (>−10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3) and a final, or late-stage, TSR reaction in which hydrocarbon oxidation continues at a slower rate via the non-autocatalytic reduction of sulfate by gaseous hydrocarbons.

Kinetics and mechanism of styrene epoxidation by chlorite: role of chlorine dioxide.

PubMed

Leigh, Jessica K; Rajput, Jonathan; Richardson, David E

2014-07-07

An investigation of the kinetics and mechanism for epoxidation of styrene and para-substituted styrenes by chlorite at 25 °C in the pH range of 5-6 is described. The proposed mechanism in water and water/acetonitrile includes seven oxidation states of chlorine (-I, 0, I, II, III, IV, and V) to account for the observed kinetics and product distributions. The model provides an unusually detailed quantitative mechanism for the complex reactions that occur in mixtures of chlorine species and organic substrates, particularly when the strong oxidant chlorite is employed. Kinetic control of the reaction is achieved by the addition of chlorine dioxide to the reaction mixture, thereby eliminating a substantial induction period observed when chlorite is used alone. The epoxidation agent is identified as chlorine dioxide, which is continually formed by the reaction of chlorite with hypochlorous acid that results from ClO produced by the epoxidation reaction. The overall stoichiometry is the result of two competing chain reactions in which the reactive intermediate ClO reacts with either chlorine dioxide or chlorite ion to produce hypochlorous acid and chlorate or chloride, respectively. At high chlorite ion concentrations, HOCl is rapidly eliminated by reaction with chlorite, minimizing side reactions between HOCl and Cl2 with the starting material. Epoxide selectivity (>90% under optimal conditions) is accurately predicted by the kinetic model. The model rate constant for direct reaction of styrene with ClO2(aq) to produce epoxide is (1.16 ± 0.07) × 10(-2) M(-1) s(-1) for 60:40 water/acetonitrile with 0.20 M acetate buffer. Rate constants for para substituted styrenes (R = -SO3(-), -OMe, -Me, -Cl, -H, and -NO2) with ClO2 were determined. The results support the radical addition/elimination mechanism originally proposed by Kolar and Lindgren to account for the formation of styrene oxide in the reaction of styrene with chlorine dioxide.

Unusual superconducting behavior in HfV2Ga4

NASA Astrophysics Data System (ADS)

Santos, F. B.; Correa, L. E.; de Lima, B. S.; Cigarroa, O. V.; da Luz, M. S.; Grant, T.; Fisk, Z.; Machado, A. J. S.

2018-04-01

Bulk superconductivity in HfV2Ga4 with critical temperature close to 4.1 K was determined via magnetic susceptibility, electrical resistivity and specific heat measurements. Both the upper and lower critical field dependence with reduced temperature (T /Tc) exhibit non-conventional behavior. The electronic component of specific heat shows a double-jump, the first close to Tc and the other close to 0.75Tc. We speculate about the nature of the douple jump observed in specific heat considering two plausable scenarios: bulk inhomogeneities and the existence of a second gap.

HCH, endosulfan, and fluvalinate residue behavior in pigeonpea (Cajanus cajan L. Millsp)

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

Mukherjee, I.; Gopal, M.; Yaduraju, N.T.

Pigeonpea (Cajanus cajan L. Millsp) is one of the major pulse crop of India. The loss of pigeonpea crop due to pod and foliage pests is significant, the major pests being pod fly, hairy caterpillar, aphids, white fly, plume moth borer, leaf caterpillar and jassids. It is imperative to save every grain by chemical control methods but these toxicants should not leave unusually high residues on the edible parts. In this paper the authors report the residue behavior of three different insecticides namely, hexachlorocyclohexane, endosulfan and fluvalinate on this crop.

Critical behavior in graphene with Coulomb interactions.

PubMed

Wang, Jianhui; Fertig, H A; Murthy, Ganpathy

2010-05-07

We demonstrate that, in the presence of Coulomb interactions, electrons in graphene behave like a critical system, supporting power law correlations with interaction-dependent exponents. An asymptotic analysis shows that the origin of this behavior lies in particle-hole scattering, for which the Coulomb interaction induces anomalously close approaches. With increasing interaction strength the relevant power law changes from real to complex, leading to an unusual instability characterized by a complex-valued susceptibility in the thermodynamic limit. Measurable quantities, as well as the connection to classical two-dimensional systems, are discussed.

Complex structural behavior of oligopurine-oligopyrimidine sequence cloned within the supercoiled plasmid.

PubMed Central

Parniewski, P; Galazka, G; Wilk, A; Klysik, J

1989-01-01

Synthetic sequence GATCC(AG)7ATCG(AT)4CG(AG)7 was cloned into plasmid and its structural behavior under the influence of supercoiling was analysed by chemical modification at variety of experimental conditions. It was found that this sequence adopts at least two different non-B conformations depending on -delta and pH values. Moreover, 12 nucleotide long non-pur.pyr spacer region separating two identical (AG)7 blocks does not provide a significant energy barrier protecting against unusual structures formation. Images PMID:2644622

The arbuscular mycorrhizal fungus Glomus intraradices is haploid and has a small genome size in the lower limit of eukaryotes.

PubMed

Hijri, Mohamed; Sanders, Ian R

2004-02-01

The genome size, complexity, and ploidy of the arbuscular mycorrhizal fungus (AMF) Glomus intraradices was determined using flow cytometry, reassociation kinetics, and genomic reconstruction. Nuclei of G. intraradices from in vitro culture, were analyzed by flow cytometry. The estimated average length of DNA per nucleus was 14.07+/-3.52 Mb. Reassociation kinetics on G. intraradices DNA indicated a haploid genome size of approximately 16.54 Mb, comprising 88.36% single copy DNA, 1.59% repetitive DNA, and 10.05% fold-back DNA. To determine ploidy, the DNA content per nucleus measured by flow cytometry was compared with the genome estimate of reassociation kinetics. G. intraradices was found to have a DNA index (DNA per nucleus per haploid genome size) of approximately 0.9, indicating that it is haploid. Genomic DNA of G. intraradices was also analyzed by genomic reconstruction using four genes (Malate synthase, RecA, Rad32, and Hsp88). Because we used flow cytometry and reassociation kinetics to reveal the genome size of G. intraradices and show that it is haploid, then a similar value for genome size should be found when using genomic reconstruction as long as the genes studied are single copy. The average genome size estimate was 15.74+/-1.69 Mb indicating that these four genes are single copy per haploid genome and per nucleus of G. intraradices. Our results show that the genome size of G. intraradices is much smaller than estimates of other AMF and that the unusually high within-spore genetic variation that is seen in this fungus cannot be due to high ploidy.

Wave induced supersonic rotation in mirrors

NASA Astrophysics Data System (ADS)

Fetterman, Abraham

2010-11-01

Wave-particle interactions in ExB supersonically rotating plasmas feature an unusual effect: particles are diffused by waves in both potential energy and kinetic energy [1]. This wave-particle interaction generalizes the alpha channeling effect, in which radio frequency waves are used to remove alpha particles collisionlessly at low energy. In rotating plasmas, the alpha particles may be removed at low energy through the loss cone, and the energy lost may be transferred to the radial electric field. This eliminates the need for electrodes in the mirror throat, which have presented serious technical issues in past rotating plasma devices. A particularly simple way to achieve this effect is to use a high azimuthal mode number perturbation on the magnetic field [2]. In the rotating frame, this perturbation is seen as a wave near the alpha particle cyclotron harmonic, and can break the azimuthal symmetry and magnetic moment conservation without changing the particle's total energy. The particle may exit if it reduces its kinetic energy and becomes more trapped if it gains kinetic energy, leading to a steady state current that maintains the field. Simulations of single particles in rotating mirrors show that a stationary wave can extract enough energy from alpha particles for a reactor to be self-sustaining. Rotation can also be sustained by waves in plasmas without a kinetic energy source. This type of wave has been considered for plasma centrifuges used for isotope separation [3]. [4pt] [1] A. J. Fetterman and N. J. Fisch, Phys Rev Lett 101, 205003 (2008). [0pt] [2] A. J. Fetterman and N. J. Fisch, Phys. Plasmas 17, 042112 (2010). [0pt] [3] A. J. Fetterman and N. J. Fisch, Plasma Sources Sci. Tech. 18, 045003 (2009).

Application of the kinetic and isotherm models for better understanding of the behaviors of silver nanoparticles adsorption onto different adsorbents.

PubMed

Syafiuddin, Achmad; Salmiati, Salmiati; Jonbi, Jonbi; Fulazzaky, Mohamad Ali

2018-07-15

It is the first time to do investigation the reliability and validity of thirty kinetic and isotherm models for describing the behaviors of adsorption of silver nanoparticles (AgNPs) onto different adsorbents. The purpose of this study is therefore to assess the most reliable models for the adsorption of AgNPs onto feasibility of an adsorbent. The fifteen kinetic models and fifteen isotherm models were used to test secondary data of AgNPs adsorption collected from the various data sources. The rankings of arithmetic mean were estimated based on the six statistical analysis methods of using a dedicated software of the MATLAB Optimization Toolbox with a least square curve fitting function. The use of fractal-like mixed 1, 2-order model for describing the adsorption kinetics and that of Fritz-Schlunder and Baudu models for describing the adsorption isotherms can be recommended as the most reliable models for AgNPs adsorption onto the natural and synthetic adsorbent materials. The application of thirty models have been identified for the adsorption of AgNPs to clarify the usefulness of both groups of the kinetic and isotherm equations in the rank order of the levels of accuracy, and this significantly contributes to understandability and usability of the proper models and makes to knowledge beyond the existing literatures. Copyright © 2018 Elsevier Ltd. All rights reserved.

A chimeric LysK-lysostaphin fusion enzyme lysing Staphylococcus aureus cells: a study of both kinetics of inactivation and specifics of interaction with anionic polymers

USDA-ARS?s Scientific Manuscript database

A staphylolytic fusion protein (K-L) was created, harboring three unique lytic activities comprised of the LysK CHAP endopeptidase, and amidase domains, and the lysostaphin glycyl-glycine endopeptidase domain. To assess the potential of possible therapeutic applications, the kinetic behavior of K-L...

Adsorption mechanism of cadmium on juniper bark and wood

Treesearch

Eun Woo Shin; K. G. Karthikeyan; Mandla A. Tshabalala

2007-01-01

In this study the capacity of sorbents prepared from juniper wood (JW) and bark (JB) to adsorb cadmium (Cd) from aqueous solutions at different pH values was compared. Adsorption behavior was characterized through adsorption kinetics, adsorption isotherms, and adsorption edge experiments. Results from kinetics and isotherm experiments showed that JB (76.3–91.6 lmol Cd...

Climatic variability of a fire-weather index based on turbulent kinetic energy and the Haines Index

Treesearch

Warren E. Heilman; Xindi Bian

2010-01-01

Combining the Haines Index (HI) with near-surface turbulent kinetic energy (TKEs) through a product of the two values (HITKEs) has shown promise as an indicator of the atmospheric potential for extreme and erratic fire behavior in the U.S. Numerical simulations of fire-weather evolution during past wildland fire episodes in...

Langevin equation versus kinetic equation: Subdiffusive behavior of charged particles in a stochastic magnetic field

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

Balescu, R.; Wang, H.; Misguich, J.H.

1994-12-01

The running diffusion coefficient [ital D]([ital t]) is evaluated for a system of charged particles undergoing the effect of a fluctuating magnetic field and of their mutual collisions. The latter coefficient can be expressed either in terms of the mean square displacement (MSD) of a test particle, or in terms of a correlation between a fluctuating distribution function and the magnetic field fluctuation. In the first case a stochastic differential equation of Langevin type for the position of a test particle must be solved; the second problem requires the determination of the distribution function from a kinetic equation. Using suitablemore » simplifications, both problems are amenable to exact analytic solution. The conclusion is that the equivalence of the two approaches is by no means automatically guaranteed. A new type of object, the hybrid kinetic equation'' is constructed: it automatically ensures the equivalence with the Langevin results. The same conclusion holds for the generalized Fokker--Planck equation. The (Bhatnagar--Gross--Krook) (BGK) model for the collisions yields a completely wrong result. A linear approximation to the hybrid kinetic equation yields an inexact behavior, but represents an acceptable approximation in the strongly collisional limit.« less

Refined BCF-type boundary conditions for mesoscale surface step dynamics

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

Zhao, Renjie; Ackerman, David M.; Evans, James W.

Deposition on a vicinal surface with alternating rough and smooth steps is described by a solid-on-solid model with anisotropic interactions. Kinetic Monte Carlo (KMC) simulations of the model reveal step pairing in the absence of any additional step attachment barriers. We explore the description of this behavior within an analytic Burton-Cabrera-Frank (BCF)-type step dynamics treatment. Without attachment barriers, conventional kinetic coefficients for the rough and smooth steps are identical, as are the predicted step velocities for a vicinal surface with equal terrace widths. However, we determine refined kinetic coefficients from a two-dimensional discrete deposition-diffusion equation formalism which accounts for stepmore » structure. These coefficients are generally higher for rough steps than for smooth steps, reflecting a higher propensity for capture of diffusing terrace adatoms due to a higher kink density. Such refined coefficients also depend on the local environment of the step and can even become negative (corresponding to net detachment despite an excess adatom density) for a smooth step in close proximity to a rough step. Incorporation of these refined kinetic coefficients into a BCF-type step dynamics treatment recovers quantitatively the mesoscale step-pairing behavior observed in the KMC simulations.« less

Automated analysis of non-mass-enhancing lesions in breast MRI based on morphological, kinetic, and spatio-temporal moments and joint segmentation-motion compensation technique

NASA Astrophysics Data System (ADS)

Hoffmann, Sebastian; Shutler, Jamie D.; Lobbes, Marc; Burgeth, Bernhard; Meyer-Bäse, Anke

2013-12-01

Dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) represents an established method for the detection and diagnosis of breast lesions. While mass-like enhancing lesions can be easily categorized according to the Breast Imaging Reporting and Data System (BI-RADS) MRI lexicon, a majority of diagnostically challenging lesions, the so called non-mass-like enhancing lesions, remain both qualitatively as well as quantitatively difficult to analyze. Thus, the evaluation of kinetic and/or morphological characteristics of non-masses represents a challenging task for an automated analysis and is of crucial importance for advancing current computer-aided diagnosis (CAD) systems. Compared to the well-characterized mass-enhancing lesions, non-masses have no well-defined and blurred tumor borders and a kinetic behavior that is not easily generalizable and thus discriminative for malignant and benign non-masses. To overcome these difficulties and pave the way for novel CAD systems for non-masses, we will evaluate several kinetic and morphological descriptors separately and a novel technique, the Zernike velocity moments, to capture the joint spatio-temporal behavior of these lesions, and additionally consider the impact of non-rigid motion compensation on a correct diagnosis.

Refined BCF-type boundary conditions for mesoscale surface step dynamics

DOE PAGES

Zhao, Renjie; Ackerman, David M.; Evans, James W.

2015-06-24

Deposition on a vicinal surface with alternating rough and smooth steps is described by a solid-on-solid model with anisotropic interactions. Kinetic Monte Carlo (KMC) simulations of the model reveal step pairing in the absence of any additional step attachment barriers. We explore the description of this behavior within an analytic Burton-Cabrera-Frank (BCF)-type step dynamics treatment. Without attachment barriers, conventional kinetic coefficients for the rough and smooth steps are identical, as are the predicted step velocities for a vicinal surface with equal terrace widths. However, we determine refined kinetic coefficients from a two-dimensional discrete deposition-diffusion equation formalism which accounts for stepmore » structure. These coefficients are generally higher for rough steps than for smooth steps, reflecting a higher propensity for capture of diffusing terrace adatoms due to a higher kink density. Such refined coefficients also depend on the local environment of the step and can even become negative (corresponding to net detachment despite an excess adatom density) for a smooth step in close proximity to a rough step. Incorporation of these refined kinetic coefficients into a BCF-type step dynamics treatment recovers quantitatively the mesoscale step-pairing behavior observed in the KMC simulations.« less

Observation and explanation of two-dimensional interconversion of oximes with multiple heart-cutting using comprehensive multidimensional gas chromatography.

PubMed

Kulsing, Chadin; Nolvachai, Yada; Wong, Yong Foo; Glouzman, Melissa I; Marriott, Philip J

2018-04-20

Real-time interconversion processes produce unconventional peak broadening in gas chromatography (GC), and can be used to generate kinetic and thermodynamic data. In this study, an unusual separation situation in comprehensive two dimensional GC where two dimensional interconversion (i.e. a raised plateau in both first and second dimension, 1 D and 2 D) was observed in analysis of oxime isomers. This resulted in a characteristic and unusual rectangular peak shape in the two dimensional result. A related theoretical approach was introduced to explain the peak shape supported by simulation results which can be varied depending on concentration profiles and kinetics of the process. The simulated results were supported by experimental results obtained by a comprehensive heart-cut multidimensional GC (H/C MDGC) approach which was developed to clearly investigate isomerisation of E/Z oxime molecules in both 1 D and 2 D separations under different isothermal conditions. The carrier gas flow and oven temperature were selected according to initial results for 1D interconversion on a poly(ethyleneglycol) stationary phase, which was further used in both 1 D and 2 D separations to result in broad zones of oxime interconversion in both dimensions. The method involved repetitive injections of oxime sample, then sampling contiguous fractions of sample into a long 2 D column which is intended to promote considerable interconversion. Comprehensiveness arises from the fact that the whole sample is sampled from the 1 D to the 2 D column, with the long 2 D column replacing the short 2 D column used in classical comprehensive two-dimensional gas chromatography, where the latter will not promote sufficient interconversion. Data processing and presentation permits a 'rectangular' distribution corresponding to the separated compounds, characteristic of this experiment. Copyright © 2018 Elsevier B.V. All rights reserved.

The energy density distribution of an ideal gas and Bernoulli’s equations

NASA Astrophysics Data System (ADS)

Santos, Leonardo S. F.

2018-05-01

This work discusses the energy density distribution in an ideal gas and the consequences of Bernoulli’s equation and the corresponding relation for compressible fluids. The aim of this work is to study how Bernoulli’s equation determines the energy flow in a fluid, although Bernoulli’s equation does not describe the energy density itself. The model from molecular dynamic considerations that describes an ideal gas at rest with uniform density is modified to explore the gas in motion with non-uniform density and gravitational effects. The difference between the component of the speed of a particle that is parallel to the gas speed and the gas speed itself is called ‘parallel random speed’. The pressure from the ‘parallel random speed’ is denominated as parallel pressure. The modified model predicts that the energy density is the sum of kinetic and potential gravitational energy densities plus two terms with static and parallel pressures. The application of Bernoulli’s equation and the corresponding relation for compressible fluids in the energy density expression has resulted in two new formulations. For incompressible and compressible gas, the energy density expressions are written as a function of stagnation, static and parallel pressures, without any dependence on kinetic or gravitational potential energy densities. These expressions of the energy density are the main contributions of this work. When the parallel pressure was uniform, the energy density distribution for incompressible approximation and compressible gas did not converge to zero for the limit of null static pressure. This result is rather unusual because the temperature tends to zero for null pressure. When the gas was considered incompressible and the parallel pressure was equal to static pressure, the energy density maintained this unusual behaviour with small pressures. If the parallel pressure was equal to static pressure, the energy density converged to zero for the limit of the null pressure only if the gas was compressible. Only the last situation describes an intuitive behaviour for an ideal gas.

Characterization of metal adsorption kinetic properties in batch and fixed-bed reactors.

PubMed

Chen, J Paul; Wang, Lin

2004-01-01

Copper adsorption kinetic properties in batch and fixed-bed reactors were studied in this paper. The isothermal adsorption experiments showed that the copper adsorption capacity of a granular activated carbon (Filtrasorb 200) increased when ionic strength was higher. The presence of EDTA diminished the adsorption. An intraparticle diffusion model and a fixed-bed model were successfully used to describe the batch kinetic and fixed-bed operation behaviors. The kinetics became faster when the solution pH was not controlled, implying that the surface precipitation caused some metal uptake. The external mass transfer coefficient, the diffusivity and the dispersion coefficient were obtained from the modeling. It was found that both external mass transfer and dispersion coefficients increased when the flow rate was higher. Finally effects of kinetic parameters on simulation of fixed-bed operation were conducted.

Sickness behaviors in response to unusual external events in healthy cats and cats with feline interstitial cystitis

PubMed Central

Stella, Judi L.; Lord, Linda K.; Buffington, C. A. Tony

2013-01-01

Objective To compare sickness behaviors (SB) in response to unusual external events (UEE) in healthy cats with those of cats with feline interstitial cystitis (FIC). Design Prospective observational study. Animals 12 healthy cats and 20 donated cats with FIC. Procedures Cats were housed in a vivarium. Sickness behaviors referable to the gastrointestinal and urinary tracts, the skin, and behavior problems were recorded by a single observer for 77 weeks. Instances of UEE (eg, changes in caretakers, vivarium routine, and lack of interaction with the investigator) were identified during 11 of the 77 weeks. No instances of UEE were identified during the remaining 66 weeks, which were considered control weeks. Results An increase in age and exposure to UEE, but not disease status, significantly increased total number of SB when results were controlled for other factors. Evaluation of individual SB revealed a protective effect of food intake for healthy males. An increase in age conferred a small increase in relative risk (RR) for upper gastrointestinal tract signs (RR, 1.2) and avoidance behavior (1.7). Exposure to UEE significantly increased the RR for decreases in food intake (RR, 9.3) and for no eliminations in 24 hours (6.4). Exposure to UEE significantly increased the RR for defecation (RR, 9.8) and urination (1.6) outside the litter box. Conclusions and Clinical Relevance SB, including some of the most commonly observed abnormalities in client-owned cats, were observed after exposure to UEE in both groups. Because healthy cats and cats with FIC were comparably affected by UEE, clinicians should consider the possibility of exposure to UEE in cats evaluated for these signs. PMID:21194324

Kinetics of Molybdenum Adsorption and Desorption in Soils.

PubMed

Sun, Wenguang; Selim, H Magdi

2018-05-01

Much uncertainty exists in mechanisms and kinetics controlling the adsorption and desorption of molybdenum (Mo) in the soil environment. To investigate the characteristics of Mo adsorption and desorption and predict Mo behavior in the vadose zone, kinetic batch experiments were performed using three soils: Webster loam, Windsor sand and Mahan sand. Adsorption isotherms for Mo were strongly nonlinear for all three soils. Strong kinetic adsorption of Mo by all soils was also observed, where the rate of retention was rapid initially and was followed by slow retention behavior with time. The time-dependent Mo sorption rate was not influenced when constant pH was maintained. Desorption or release results indicated that there were significant fractions of Mo that appeared to be irreversible or slowly reversibly sorbed by Windsor and Mahan. X-ray absorption near edge structure (XANES) analysis for Windsor and Mahan soils indicated that most of Mo had been bound to kaolinite, whereas Webster had similar XANES features to those of Mo sorbed to montmorillonite. A sequential extraction procedure provided evidence that a significant amount of Mo was irreversibly sorbed. A multireaction model (MRM) with nonlinear equilibrium and kinetic sorption parameters was used to describe the adsorption-desorption kinetics of Mo on soils. Our results demonstrated that a formulation of MRM with two sorption sites (equilibrium and reversible) successfully described Mo adsorption-desorption data for Webster loam, and an additional irreversible reaction phase was recommended to describe Mo desorption or release with time for Windsor and Mahan soils. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Sex steroids and human behavior: prenatal androgen exposure and sex-typical play behavior in children.

PubMed

Hines, Melissa

2003-12-01

Gonadal hormones, particularly androgens, direct certain aspects of brain development and exert permanent influences on sex-typical behavior in nonhuman mammals. Androgens also influence human behavioral development, with the most convincing evidence coming from studies of sex-typical play. Girls exposed to unusually high levels of androgens prenatally, because they have the genetic disorder, congenital adrenal hyperplasia (CAH), show increased preferences for toys and activities usually preferred by boys, and for male playmates, and decreased preferences for toys and activities usually preferred by girls. Normal variability in androgen prenatally also has been related to subsequent sex-typed play behavior in girls, and nonhuman primates have been observed to show sex-typed preferences for human toys. These findings suggest that androgen during early development influences childhood play behavior in humans at least in part by altering brain development.

Neon diffusion kinetics and implications for cosmogenic neon paleothermometry in feldspars

NASA Astrophysics Data System (ADS)

Tremblay, Marissa M.; Shuster, David L.; Balco, Greg; Cassata, William S.

2017-05-01

Observations of cosmogenic neon concentrations in feldspars can potentially be used to constrain the surface exposure duration or surface temperature history of geologic samples. The applicability of cosmogenic neon to either application depends on the temperature-dependent diffusivity of neon isotopes. In this work, we investigate the kinetics of neon diffusion in feldspars of different compositions and geologic origins through stepwise degassing experiments on single, proton-irradiated crystals. To understand the potential causes of complex diffusion behavior that is sometimes manifest as nonlinearity in Arrhenius plots, we compare our results to argon stepwise degassing experiments previously conducted on the same feldspars. Many of the feldspars we studied exhibit linear Arrhenius behavior for neon whereas argon degassing from the same feldspars did not. This suggests that nonlinear behavior in argon experiments is an artifact of structural changes during laboratory heating. However, other feldspars that we examined exhibit nonlinear Arrhenius behavior for neon diffusion at temperatures far below any known structural changes, which suggests that some preexisting material property is responsible for the complex behavior. In general, neon diffusion kinetics vary widely across the different feldspars studied, with estimated activation energies (Ea) ranging from 83.3 to 110.7 kJ/mol and apparent pre-exponential factors (D0) spanning three orders of magnitude from 2.4 × 10-3 to 8.9 × 10-1 cm2 s-1. As a consequence of this variability, the ability to reconstruct temperatures or exposure durations from cosmogenic neon abundances will depend on both the specific feldspar and the surface temperature conditions at the geologic site of interest.

Emoticon-Based Ambivalent Expression: A Hidden Indicator for Unusual Behaviors in Weibo

PubMed Central

Hu, Yue; Zhao, Jichang; Wu, Junjie

2016-01-01

Recent decades have witnessed online social media being a big-data window for testifying conventional social theories quantitatively and exploring much detailed human behavioral patterns. In this paper, by tracing the emoticon use in Weibo, a group of hidden “ambivalent users” are disclosed for frequently posting ambivalent tweets containing both positive and negative emotions. Further investigation reveals that this ambivalent expression could be a novel indicator of many unusual social behaviors. For instance, ambivalent users with the female as the majority like to make a sound in midnights and at weekends. They mention their close friends frequently in ambivalent tweets, which attract more replies and serve as a more private communication way. Ambivalent users also respond differently to public affairs from others and demonstrate more interests in entertainment and sports events. Moreover, the sentiment shift in ambivalent tweets is more evident than usual and exhibits a clear “negative to positive” pattern. The above observations, though being promiscuous seemingly, actually point to the self-regulation of negative mood in Weibo, which could find its basis from the traditional emotion management theories in sociology but makes an important extension to the online environment in this study. Finally, as an interesting corollary, ambivalent users are found connected with compulsive buyers and turn out to be perfect targets for online marketing. PMID:26800119

Unusual early-onset Huntingtons disease.

PubMed

Vargas, Antonio P; Carod-Artal, Francisco J; Bomfim, Denise; Vázquez-Cabrera, Carolina; Dantas-Barbosa, Carmela

2003-06-01

Huntington's disease is an autosomal dominant progressive neurodegenerative disorder characterized by involuntary movements, cognitive decline, and behavioral disorders leading to functional disability. In contrast to patients with adult onset, in which chorea is the major motor abnormality, children often present with spasticity, rigidity, and significant intellectual decline associated with a more rapidly progressive course. An unusual early-onset Huntington's disease case of an 11-year-old boy with severe hypokinetic/rigid syndrome appearing at the age of 2.5 years is presented. Clinical diagnosis was confirmed by polymerase chain reaction study of the expanded IT-15 allele with a compatible size of 102 cytosine-adenosine-guanosine repeats L-Dopa mildly ameliorated rigidity, bradykinesia, and dystonia. We conclude that Huntington's disease should be included in the differential diagnoses of regressive syndromes of early childhood.

Late Neandertals and the intentional removal of feathers as evidenced from bird bone taphonomy at Fumane Cave 44 ky B.P., Italy

PubMed Central

Peresani, Marco; Fiore, Ivana; Gala, Monica; Romandini, Matteo; Tagliacozzo, Antonio

2011-01-01

A large and varied avifaunal bone assemblage from the final Mousterian levels of Grotta di Fumane, northern Italy, reveals unusual human modifications on species that are not clearly relatable to feeding or utilitarian uses (i.e., lammergeier, Eurasian black vulture, golden eagle, red-footed falcon, common wood pigeon, and Alpine chough). Cut, peeling, and scrape marks, as well as diagnostic fractures and a breakthrough, are observed exclusively on wings, indicating the intentional removal of large feathers by Neandertals. The species involved, the anatomical elements affected, and the unusual type and location of the human modifications indicate an activity linked to the symbolic sphere and the behavioral modernity of this European autochthonous population. PMID:21368129

Synthesis and characterization of some low and negative thermal expansion materials

NASA Astrophysics Data System (ADS)

Varga, Tamas

2005-12-01

The high-pressure behavior of several negative thermal expansion materials was studied by different methods. In-situ high-pressure x-ray and neutron diffraction studies on several compounds of the orthorhombic Sc 2W3O12 structure revealed an unusual "bulk modulus collapse" at the orthorhombic to monoclinic phase transition. In some members of the A2M3O12 family, a second phase transition and/or pressure-induced amorphization were also seen at higher pressure. The mechanism for volume contraction on compression is different from that on heating. A combined in-situ high pressure x-ray diffraction and absorption spectroscopic study has been carried out for the first time. The pressure-induced amorphization in cubic ZrW2O8 and ZrMo 2O8 was studied by following the changes in the local coordination environments of the metals. A significant change in the average tungsten coordination was found in ZrW2O8, and a less pronounced change in the molybdenum coordination in ZrMo2O8 on amorphization. A kinetically frustrated phase transition to a high-pressure crystalline phase or a kinetically hindered decomposition, are likely driving forces of the amorphization. A complementary ex-situ study confirmed the greater distortion of the framework tetrahedra in ZrW2O8, and revealed a similar distortion of the octahedra in both compounds. The possibility of stabilizing the low thermal expansion high-temperature structure in AM2O7 compounds to lower temperatures through stuffing of ZrP2O7 was explored. Although the phase transition temperature was suppressed in MIxZr 1-xMIIIxP2O7 compositions, the chemical modification employed was not successful in stabilizing the high-temperature structure to around room temperature. An attempt has been made to control the thermal expansion properties in materials of the (MIII0.5MV 0.5)P2O7-type through the choice of the metal cations and through manipulating the ordering of the cations by different heat treatment conditions. Although controlled heat treatment resulted in only short-range cation ordering, the choice of the MIII cation had a marked effect on the thermal expansion behavior of the materials. Different grades of fluorinert were examined as pressure-transmitting media for high-pressure diffraction studies. All of the fluorinerts studied became nonhydrostatic at relatively low pressures (˜1 GPa).

Hanging out at the airport: Unusual upside-down perching behavior by Eurasian Jackdaws (Corvus monedula) in a human-dominated environment

USGS Publications Warehouse

Katzner, Todd E.

2016-01-01

Animals occupying human-dominated environments show the capacity for behavioral flexibility. Corvids are among the most intelligent synanthropic bird species. During a layover at Schipol Airport in Amsterdam, Netherlands, I photographically documented Eurasian Jackdaws (Corvus monedula) perching upside down from a building cornice. In contrast to other reports of hanging birds, these jackdaws did not forage or play while upside down and appeared to use the perching spot to observe their surroundings. Although Corvids and Psittacines are known to hang upside down, especially in captive situations, such behaviors are rarely documented in the wild, and never before in association with human-built structures.

One step sintering of homogenized bauxite raw material and kinetic study

NASA Astrophysics Data System (ADS)

Gao, Chang-he; Jiang, Peng; Li, Yong; Sun, Jia-lin; Zhang, Jun-jie; Yang, Huan-ying

2016-10-01

A one-step sintering process of bauxite raw material from direct mining was completed, and the kinetics of this process was analyzed thoroughly. The results show that the sintering kinetics of bauxite raw material exhibits the liquid-phase sintering behavior. A small portion of impurities existed in the raw material act as a liquid phase. After X-ray diffraction analyses, scanning electron microscopy observations, and kinetics calculations, sintering temperature and heating duration were determined as the two major factors contributing to the sintering process and densification of bauxite ore. An elevated heating temperature and longer duration favor the densification process. The major obstacle for the densification of bauxite material is attributed to the formation of the enclosed blowhole during liquid-phase sintering.

Femtosecond laser pulse driven melting in gold nanorod aqueous colloidal suspension: Identification of a transition from stretched to exponential kinetics

DOE PAGES

Li, Yuelin; Jiang, Zhang; Lin, Xiao -Min; ...

2015-01-30

Many potential industrial, medical, and environmental applications of metal nanorods rely on the physics and resultant kinetics and dynamics of the interaction of these particles with light. We report a surprising kinetics transition in the global melting of femtosecond laser-driven gold nanorod aqueous colloidal suspension. At low laser intensity, the melting exhibits a stretched exponential kinetics, which abruptly transforms into a compressed exponential kinetics when the laser intensity is raised. It is found the relative formation and reduction rate of intermediate shapes play a key role in the transition. Supported by both molecular dynamics simulations and a kinetic model, themore » behavior is traced back to the persistent heterogeneous nature of the shape dependence of the energy uptake, dissipation and melting of individual nanoparticles. These results could have significant implications for various applications such as water purification and electrolytes for energy storage that involve heat transport between metal nanorod ensembles and surrounding solvents.« less

Chloroperoxidase-catalyzed oxidation of 4,6-dimethyldibenzothiophene as dimer complexes: evidence for kinetic cooperativity.

PubMed

Torres, Eduardo; Aburto, Jorge

2005-05-15

A sigmoidal kinetic behavior of chloroperoxidase for the oxidation of 4,6-dimethyldibenzothiophene (4,6-DMDBT) in water-miscible organic solvent is for the first time reported. Kinetics of 4,6-DMDBT oxidation showed a cooperative profile probably due to the capacity of chloroperoxidase to recognize a substrate dimer (pi-pi dimer) in its active site. Experimental evidence is given for dimer formation and its presence in the active site of chloroperoxidase. The kinetic data were adjusted for a binding site able to interact with either monomer or dimer substrates, producing a cooperative model describing a one-site binding of two related species. Determination of kinetics constants by iterative calculations of possible oxidation paths of 4,6-DMDBT suggests that kinetics oxidation of dimer substrate is preferred when compared to monomer oxidation. Steady-state fluorometry of substrate in the absence and presence of chloroperoxidase, described by the spectral center of mass, supports this last conclusion.

GEOTHERMAL ENVIRONMENTAL ASSESSMENT: BEHAVIOR OF SELECTED GEOTHERMAL BRINE CONTAMINANTS IN PLANTS AND SOILS

EPA Science Inventory

The behavior of selected elements found in the Roosevelt Hot Springs KGRA geothermal fluids was investigated in both plant and soil systems. The kinetics of these potential environmental containments were studied by using soil columns and selected cultivated and native plant spec...

Kinetic analyses and pyrolytic behavior of Para grass (Urochloa mutica) for its bioenergy potential.

PubMed

Ahmad, Muhammad Sajjad; Mehmood, Muhammad Aamer; Al Ayed, Omar S; Ye, Guangbin; Luo, Huibo; Ibrahim, Muhammad; Rashid, Umer; Arbi Nehdi, Imededdine; Qadir, Ghulam

2017-01-01

The biomass of Urochloa mutica was subjected to thermal degradation analyses to understand its pyrolytic behavior for bioenergy production. Thermal degradation experiments were performed at three different heating rates, 10, 30 and 50°Cmin -1 using simultaneous thermogravimetric-differential scanning calorimetric analyzer, under an inert environment. The kinetic analyses were performed using isoconversional models of Kissenger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO). The high heating value was calculated as 15.04MJmol -1 . The activation energy (E) values were shown to be ranging from 103 through 233 kJmol -1 . Pre-exponential factors (A) indicated the reaction to follow first order kinetics. Gibbs free energy (ΔG) was measured to be ranging from 169 to 173kJmol -1 and 168 to 172kJmol -1 , calculated by KAS and FWO methods, respectively. We have shown that Para grass biomass has considerable bioenergy potential comparable to established bioenergy crops such as switchgrass and miscanthus. Copyright © 2016 Elsevier Ltd. All rights reserved.

A numerical study of attraction/repulsion collective behavior models: 3D particle analyses and 1D kinetic simulations

NASA Astrophysics Data System (ADS)

Vecil, Francesco; Lafitte, Pauline; Rosado Linares, Jesús

2013-10-01

We study at particle and kinetic level a collective behavior model based on three phenomena: self-propulsion, friction (Rayleigh effect) and an attractive/repulsive (Morse) potential rescaled so that the total mass of the system remains constant independently of the number of particles N. In the first part of the paper, we introduce the particle model: the agents are numbered and described by their position and velocity. We identify five parameters that govern the possible asymptotic states for this system (clumps, spheres, dispersion, mills, rigid-body rotation, flocks) and perform a numerical analysis on the 3D setting. Then, in the second part of the paper, we describe the kinetic system derived as the limit from the particle model as N tends to infinity; we propose, in 1D, a numerical scheme for the simulations, and perform a numerical analysis devoted to trying to recover asymptotically patterns similar to those emerging for the equivalent particle systems, when particles originally evolved on a circle.

Kinetic Behavior and Microstructure of Pearlite Isothermal Transformation Under High Undercooling

NASA Astrophysics Data System (ADS)

Liang, Yu; Xu, Pingwei; Xiang, Song; Liang, Yilong; Xiong, Hu; Li, Jing

2018-06-01

The kinetic behavior of highly undercooled austenite and its effects on the microstructural evolution and mechanical properties of high-carbon steel are studied. The undercooling degree is increased through a temporary undercooling treatment at the bainite transformation temperature of 380 °C to 450 °C before the pearlite isothermal transformation at 500 °C to 620 °C. The transformation kinetics reveals an increased nose temperature and a rightward shift of the transformation curve under high undercooling conditions. In addition, the undercooling treatment leads to an increased driving force during pearlite transformation, which is responsible for the refined hierarchical structures of pearlite. As a result, a 20 to 40 pct size reduction is achieved for pearlite colonies and lamellae. Such refinement is in turn attributed to an 26 pct increase in reduction in area. This work provides both a new understanding of high-performance fully pearlitic steels for practical applications and new perspectives for potential technological applications in drawing processes for hypoeutectoid steels.

Model colloid system for interfacial sorption kinetics

NASA Astrophysics Data System (ADS)

Salipante, Paul; Hudson, Steven

2014-11-01

Adsorption kinetics of nanometer scale molecules, such as proteins at interfaces, is usually determined through measurements of surface coverage. Their small size limits the ability to directly observe individual molecule behavior. To better understand the behavior of nanometer size molecules and the effect on interfacial kinetics, we use micron size colloids with a weak interfacial interaction potential as a model system. Thus, the interaction strength is comparable to many nanoscale systems (less than 10 kBT). The colloid-interface interaction potential is tuned using a combination of depletion, electrostatic, and gravitational forces. The colloids transition between an entropically trapped adsorbed state and a desorbed state through Brownian motion. Observations are made using an LED-based Total Internal Reflection Microscopy (TIRM) setup. The observed adsorption and desorption rates are compared theoretical predictions based on the measured interaction potential and near wall particle diffusivity. This experimental system also allows for the study of more complex dynamics such as nonspherical colloids and collective effects at higher concentrations.

Focus: Nucleation kinetics of shear bands in metallic glass.

PubMed

Wang, J Q; Perepezko, J H

2016-12-07

The development of shear bands is recognized as the primary mechanism in controlling the plastic deformability of metallic glasses. However, the kinetics of the nucleation of shear bands has received limited attention. The nucleation of shear bands in metallic glasses (MG) can be investigated using a nanoindentation method to monitor the development of the first pop-in event that is a signature of shear band nucleation. The analysis of a statistically significant number of first pop-in events demonstrates the stochastic behavior that is characteristic of nucleation and reveals a multimodal behavior associated with local spatial heterogeneities. The shear band nucleation rate of the two nucleation modes and the associated activation energy, activation volume, and site density were determined by loading rate experiments. The nucleation activation energy is very close to the value that is characteristic of the β relaxation in metallic glass. The identification of the rate controlling kinetics for shear band nucleation offers guidance for promoting plastic flow in metallic glass.

Scaling in the aggregation dynamics of a magnetorheological fluid.

PubMed

Domínguez-García, P; Melle, Sonia; Pastor, J M; Rubio, M A

2007-11-01

We present experimental results on the aggregation dynamics of a magnetorheological fluid, namely, an aqueous suspension of micrometer-sized superparamagnetic particles, under the action of a constant uniaxial magnetic field using video microscopy and image analysis. We find a scaling behavior in several variables describing the aggregation kinetics. The data agree well with the Family-Vicsek scaling ansatz for diffusion-limited cluster-cluster aggregation. The kinetic exponents z and z' are obtained from the temporal evolution of the mean cluster size S(t) and the number of clusters N(t), respectively. The crossover exponent Delta is calculated in two ways: first, from the initial slope of the scaling function; second, from the evolution of the nonaggregated particles, n1(t). We report on results of Brownian two-dimensional dynamics simulations and compare the results with the experiments. Finally, we discuss the differences obtained between the kinetic exponents in terms of the variation in the crossover exponent and relate this behavior to the physical interpretation of the crossover exponent.

Competitive Adsorption and Oxidation Behavior of Heavy Metals on nZVI Coated with TEOS.

PubMed

Eglal, Mahmoud M; Ramamurthy, Amruthur S

2015-11-01

Zero valent iron nanoparticle (nanofer ZVI) is a powerful substance due to its coating with tetraethyl orthosilicate (TEOS). Tetraethyl orthosilicate imparts higher reactivity and decreases particle agglomeration. The competitive removal and displacement of multi-metals are influenced by time, pH, and initial concentration, the presence and properties of competing metals ion in the solution. For both the isotherm and kinetic studies performed for multi-metal removal experiments, compared to Pb II and Cd II, Cu II experienced a higher removal rate during the initial 5 minutes. After 120 minutes, all metals achieved removal efficiency in the range of 95 to 99%. The results of single and competitive kinetic tests for all three metals during the initial 5 minutes indicated that the presence of other metals generally reduce removal efficiency of metals. Both kinetic test and electron dispersive spectroscope (EDS) studies found that Cu II gets removed faster than the other metals. Pseudo-second order behavior was noted for the multi-metal removal systems.

Approximate models for the ion-kinetic regime in inertial-confinement-fusion capsule implosions

DOE PAGES

Hoffman, Nelson M.; Zimmerman, George B.; Molvig, Kim; ...

2015-05-19

“Reduced” (i.e., simplified or approximate) ion-kinetic (RIK) models in radiation-hydrodynamic simulations permit a useful description of inertial-confinement-fusion (ICF) implosions where kinetic deviations from hydrodynamic behavior are important. For implosions in or near the kinetic regime (i.e., when ion mean free paths are comparable to the capsule size), simulations using a RIK model give a detailed picture of the time- and space-dependent structure of imploding capsules, allow an assessment of the relative importance of various kinetic processes during the implosion, enable explanations of past and current observations, and permit predictions of the results of future experiments. The RIK simulation method describedmore » here uses moment-based reduced kinetic models for transport of mass, momentum, and energy by long-mean-free-path ions, a model for the decrease of fusion reactivity owing to the associated modification of the ion distribution function, and a model of hydrodynamic turbulent mixing. Transport models are based on local gradient-diffusion approximations for the transport of moments of the ion distribution functions, with coefficients to impose flux limiting or account for transport modification. After calibration against a reference set of ICF implosions spanning the hydrodynamic-to-kinetic transition, the method has useful, quantifiable predictive ability over a broad range of capsule parameter space. Calibrated RIK simulations show that an important contributor to ion species separation in ICF capsule implosions is the preferential flux of longer-mean-free-path species out of the fuel and into the shell, leaving the fuel relatively enriched in species with shorter mean free paths. Also, the transport of ion thermal energy is enhanced in the kinetic regime, causing the fuel region to have a more uniform, lower ion temperature, extending over a larger volume, than implied by clean simulations. Furthermore, we expect that the success of our simple approach will motivate continued theoretical research into the development of first-principles-based, comprehensive, self-consistent, yet useable models of kinetic multispecies ion behavior in ICF plasmas.« less

Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism.

PubMed

Puri, Mayank; Company, Anna; Sabenya, Gerard; Costas, Miquel; Que, Lawrence

2016-06-20

Detailed studies of oxygen atom exchange (OAE) between H2(18)O and synthetic non-heme oxoiron(IV) complexes supported by tetradentate and pentadentate ligands provide evidence that they proceed by a common mechanism but within two different kinetic regimes, with OAE rates that span 2 orders of magnitude. The first kinetic regime involves initial reversible water association to the Fe(IV) complex, which is evidenced by OAE rates that are linearly dependent on [H2(18)O] and H2O/D2O KIEs of 1.6, while the second kinetic regime involves a subsequent rate determining proton-transfer step between the bound aqua and oxo ligands that is associated with saturation behavior with [H2(18)O] and much larger H2O/D2O KIEs of 5-6. [Fe(IV)(O)(TMC)(MeCN)](2+) (1) and [Fe(IV)(O)(MePy2TACN)](2+) (9) are examples of complexes that exhibit kinetic behavior in the first regime, while [Fe(IV)(O)(N4Py)](2+) (3), [Fe(IV)(O)(BnTPEN)](2+) (4), [Fe(IV)(O)(1Py-BnTPEN)](2+) (5), [Fe(IV)(O)(3Py-BnTPEN)](2+) (6), and [Fe(IV)(O)(Me2Py2TACN)](2+) (8) represent complexes that fall in the second kinetic regime. Interestingly, [Fe(IV)(O)(PyTACN)(MeCN)](2+) (7) exhibits a linear [H2(18)O] dependence below 0.6 M and saturation above 0.6 M. Analysis of the temperature dependence of the OAE rates shows that most of these complexes exhibit large and negative activation entropies, consistent with the proposed mechanism. One exception is complex 9, which has a near-zero activation entropy and is proposed to undergo ligand-arm dissociation during the RDS to accommodate H2(18)O binding. These results show that the observed OAE kinetic behavior is highly dependent on the nature of the supporting ligand and are of relevance to studies of non-heme oxoiron(IV) complexes in water or acetonitrile/water mixtures for applications in photocatalysis and water oxidation chemistry.

Effects of Convective Transport of Solute and Impurities on Defect-Causing Kinetics Instabilities in Protein Crystallization

NASA Technical Reports Server (NTRS)

Vekilov, Peter G.

2002-01-01

The objective of the proposed research is to obtain further insight into the onset and development of the defect-causing instabilities that anise due to the coupling of the bulk transport and nonlinear-interfacial kinetics during growth in the mixed regime, utilizing the reduction of the convective contribution to the bulk transport under microgravity. These studies will build upon the data on the effects of quantitative variations of the forced convection velocity on the averaged and time-dependent kinetic behavior of protein crystal growth systems that have recently been obtained in our laboratory.

Comparison between different adsorption-desorption kinetics schemes in two dimensional lattice gas

NASA Astrophysics Data System (ADS)

Huespe, V. J.; Belardinelli, R. E.; Pereyra, V. D.; Manzi, S. J.

2017-12-01

Monte Carlo simulation is used to study the adsorption-desorption kinetics in the framework of the kinetic lattice-gas model. Three schemes of the so-called hard dynamics and five schemes of the so called soft dynamics were used for this purpose. It is observed that for the hard dynamic schemes, the equilibrium and non-equilibrium observable, such as adsorption isotherms, sticking coefficients, and thermal desorption spectra, have a normal or physical sustainable behavior. While for the soft dynamics schemes, with the exception of the transition state theory, the equilibrium and non-equilibrium observables have several problems.

Bowhead whale behavior in relation to seismic exploration, Alaskan Beaufort Sea, Autumn 1981. Study report (Final)

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

Fraker, M.A.; Ljungblad, D.K.; Richardson, W.J.

1985-10-01

Behavior of bowhead whales (Balsena mysticetus) in the eastern part of the Alaskan Beaufort Sea or near the Alaska/Yukon border was observed from a circling turbine-powered Goose aircraft on 10 dates from 12 September to 5 October 1981. On three of these dates, the whales were exposed t, noise impulses from seismic vessels 13 km or more away. Some behavioral data were acquired. In both the presence and the absence of seismic impulses, most bowheads appeared to be feeding in the water column, although slow travel and active socializing were sometimes detected. Sonobuoys detected bowhead calls both in the presencemore » and the absence of seismic impulses. There was no clear evidence of unusual behavior in the presence of seismic impulses.« less

Tuning the surface anisotropy in Fe-doped NiO nanoparticles.

PubMed

Moura, K O; Lima, R J S; Coelho, A A; Souza-Junior, E A; Duque, J G S; Meneses, C T

2014-01-07

Ni(1-x)FexO nanoparticles have been obtained by the co-precipitation chemical route. X-ray diffraction analyses using Rietveld refinement have shown a slight decrease in the microstrain and mean particle size as a function of the Fe content. The zero-field-cooling (ZFC) and field-cooling (FC) magnetization curves show superparamagnetic behavior at high temperatures and a low temperature peak (at T = 11 K), which is enhanced with increasing Fe concentration. Unusual behavior of the coercive field in the low temperature region and an exchange bias behavior were also observed. A decrease in the Fe concentration induces an increase in the exchange bias field. We argue that these behaviors can be linked with the strengthening of surface anisotropy caused by the incorporation of Fe ions.

Dynamic Recrystallization Behavior of Zr-1Sn-0.3Nb Alloy During Hot Rolling Process

NASA Astrophysics Data System (ADS)

Zhao, Siyu; Liu, Huiqun; Lin, Gaoyong; Jiang, Yilan; Xun, Jian

2017-11-01

Zirconium alloys are advanced materials with properties that are greatly affected by their crystalline structure. To investigate this, sheets of Zr-1Sn-0.3Nb alloy were hot rolled with different reductions (10%, 30%, 50%, and 60%) at 1023 K and 1073 K to investigate the alloy's dynamic recrystallization behavior. Recrystallization kinetics was observed via electron backscattering diffraction and transmission electron microscopy, and the results were compared with estimates based on the Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation. The values of the JMAK exponent n and k increased with the rolling temperature. The estimates and microstructural observations of dynamic recrystallization (DRX) kinetics were in good agreement.

Steady state current fluctuations and dynamical control in a nonequilibrium single-site Bose-Hubbard system

NASA Astrophysics Data System (ADS)

Chen, Xu-Min; Wang, Chen; Sun, Ke-Wei

2018-02-01

We investigate nonequilibrium energy transfer in a single-site Bose-Hubbard model coupled to two thermal baths. By including a quantum kinetic equation combined with full counting statistics, we investigate the steady state energy flux and noise power. The influence of the nonlinear Bose-Hubbard interaction on the transfer behaviors is analyzed, and the nonmonotonic features are clearly exhibited. Particularly, in the strong on-site repulsion limit, the results become identical with the nonequilibrium spin-boson model. We also extend the quantum kinetic equation to study the geometric-phase-induced energy pump. An interesting reversal behavior is unraveled by enhancing the Bose-Hubbard repulsion strength.

Research opportunities in salt hydrates for thermal energy storage

NASA Astrophysics Data System (ADS)

Braunstein, J.

1983-11-01

The state of the art of salt hydrates as phase change materials for low temperature thermal energy storage is reviewed. Phase equilibria, nucleation behavior and melting kinetics of the commonly used hydrate are summarized. The development of efficient, reliable inexpensive systems based on phase change materials, especially salt hydrates for the storage (and retrieval) of thermal energy for residential heating is outlined. The use of phase change material thermal energy storage systems is not yet widespread. Additional basic research is needed in the areas of crystallization and melting kinetics, prediction of phase behavior in ternary systems, thermal diffusion in salt hydrate systems, and in the physical properties pertinent to nonequilibrium and equilibrium transformations in these systems.

Kinetic signature of fractal-like filament networks formed by orientational linear epitaxy.

PubMed

Hwang, Wonmuk; Eryilmaz, Esma

2014-07-11

We study a broad class of epitaxial assembly of filament networks on lattice surfaces. Over time, a scale-free behavior emerges with a 2.5-3 power-law exponent in filament length distribution. Partitioning between the power-law and exponential behaviors in a network can be used to find the stage and kinetic parameters of the assembly process. To analyze real-world networks, we develop a computer program that measures the network architecture in experimental images. Application to triaxial networks of collagen fibrils shows quantitative agreement with our model. Our unifying approach can be used for characterizing and controlling the network formation that is observed across biological and nonbiological systems.

Wave kinetics of drift-wave turbulence and zonal flows beyond the ray approximation

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

Zhu, Hongxuan; Zhou, Yao; Ruiz, D. E.

Inhomogeneous drift-wave turbulence can be modeled as an effective plasma where drift waves act as quantumlike particles and the zonal-flow velocity serves as a collective field through which they interact. This effective plasma can be described by a Wigner-Moyal equation (WME), which generalizes the quasilinear wave-kinetic equation (WKE) to the full-wave regime, i.e., resolves the wavelength scale. Unlike waves governed by manifestly quantumlike equations, whose WMEs can be borrowed from quantum mechanics and are commonly known, drift waves have Hamiltonians very different from those of conventional quantum particles. This causes unusual phase-space dynamics that is typically not captured by themore » WKE. We demonstrate how to correctly model this dynamics with the WME instead. Specifically, we report full-wave phase-space simulations of the zonal-flow formation (zonostrophic instability), deterioration (tertiary instability), and the so-called predator-prey oscillations. We also show how the WME facilitates analysis of these phenomena, namely, (i) we show that full-wave effects critically affect the zonostrophic instability, particularly its nonlinear stage and saturation; (ii) we derive the tertiary-instability growth rate; and (iii) we demonstrate that, with full-wave effects retained, the predator-prey oscillations do not require zonal-flow collisional damping, contrary to previous studies. In conclusion, we also show how the famous Rayleigh-Kuo criterion, which has been missing in wave-kinetic theories of drift-wave turbulence, emerges from the WME.« less

High growth rate hydride vapor phase epitaxy at low temperature through use of uncracked hydrides

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

Schulte, Kevin L.; Braun, Anna; Simon, John

We demonstrate hydride vapor phase epitaxy (HVPE) of GaAs with unusually high growth rates (RG) at low temperature and atmospheric pressure by employing a hydride-enhanced growth mechanism. Under traditional HVPE growth conditions that involve growth from Asx species, RG exhibits a strong temperature dependence due to slow kinetics at the surface, and growth temperatures >750 degrees C are required to obtain RG > 60 um/h. We demonstrate that when the group V element reaches the surface in a hydride, the kinetic barrier is dramatically reduced and surface kinetics no longer limit RG. In this regime, RG is dependent on massmore » transport of uncracked AsH3 to the surface. By controlling the AsH3 velocity and temperature profile of the reactor, which both affect the degree of AsH3 decomposition, we demonstrate tuning of RG. We achieve RG above 60 um/h at temperatures as low as 560 degrees C and up to 110 um/h at 650 degrees C. We incorporate high-RG GaAs into solar cell devices to verify that the electronic quality does not deteriorate as RG is increased. The open circuit voltage (VOC), which is a strong function of non-radiative recombination in the bulk material, exhibits negligible variance in a series of devices grown at 650 degrees C with RG = 55-110 um/h. The implications of low temperature growth for the formation of complex heterostructure devices by HVPE are discussed.« less

High growth rate hydride vapor phase epitaxy at low temperature through use of uncracked hydrides

DOE PAGES

Schulte, Kevin L.; Braun, Anna; Simon, John; ...

2018-01-22

We demonstrate hydride vapor phase epitaxy (HVPE) of GaAs with unusually high growth rates (RG) at low temperature and atmospheric pressure by employing a hydride-enhanced growth mechanism. Under traditional HVPE growth conditions that involve growth from Asx species, RG exhibits a strong temperature dependence due to slow kinetics at the surface, and growth temperatures >750 degrees C are required to obtain RG > 60 um/h. We demonstrate that when the group V element reaches the surface in a hydride, the kinetic barrier is dramatically reduced and surface kinetics no longer limit RG. In this regime, RG is dependent on massmore » transport of uncracked AsH3 to the surface. By controlling the AsH3 velocity and temperature profile of the reactor, which both affect the degree of AsH3 decomposition, we demonstrate tuning of RG. We achieve RG above 60 um/h at temperatures as low as 560 degrees C and up to 110 um/h at 650 degrees C. We incorporate high-RG GaAs into solar cell devices to verify that the electronic quality does not deteriorate as RG is increased. The open circuit voltage (VOC), which is a strong function of non-radiative recombination in the bulk material, exhibits negligible variance in a series of devices grown at 650 degrees C with RG = 55-110 um/h. The implications of low temperature growth for the formation of complex heterostructure devices by HVPE are discussed.« less

Wave kinetics of drift-wave turbulence and zonal flows beyond the ray approximation

DOE PAGES

Zhu, Hongxuan; Zhou, Yao; Ruiz, D. E.; ...

2018-05-29

Inhomogeneous drift-wave turbulence can be modeled as an effective plasma where drift waves act as quantumlike particles and the zonal-flow velocity serves as a collective field through which they interact. This effective plasma can be described by a Wigner-Moyal equation (WME), which generalizes the quasilinear wave-kinetic equation (WKE) to the full-wave regime, i.e., resolves the wavelength scale. Unlike waves governed by manifestly quantumlike equations, whose WMEs can be borrowed from quantum mechanics and are commonly known, drift waves have Hamiltonians very different from those of conventional quantum particles. This causes unusual phase-space dynamics that is typically not captured by themore » WKE. We demonstrate how to correctly model this dynamics with the WME instead. Specifically, we report full-wave phase-space simulations of the zonal-flow formation (zonostrophic instability), deterioration (tertiary instability), and the so-called predator-prey oscillations. We also show how the WME facilitates analysis of these phenomena, namely, (i) we show that full-wave effects critically affect the zonostrophic instability, particularly its nonlinear stage and saturation; (ii) we derive the tertiary-instability growth rate; and (iii) we demonstrate that, with full-wave effects retained, the predator-prey oscillations do not require zonal-flow collisional damping, contrary to previous studies. In conclusion, we also show how the famous Rayleigh-Kuo criterion, which has been missing in wave-kinetic theories of drift-wave turbulence, emerges from the WME.« less

Synthesis and Properties of "Sandwich" Diimine-Coinage Metal Ethylene Complexes.

PubMed

Klimovica, Kristine; Kirschbaum, Kristin; Daugulis, Olafs

2016-09-12

Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a . The upper limit of Δ G ‡ , assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with Δ G 298 ‡ = 12.9 ± 0.1 kcal/mol, while the exchange is the slowest in Au complex 9 , with Δ G 298 ‡ = 16.7 ± 0.1 kcal/mol. Copper complex 7b is unusually stable and can survive in air for years.

Fundamental studies of gas phase ionic reactions by ion mobility spectrometry

NASA Technical Reports Server (NTRS)

Giles, K.; Knighton, W. B.; Sahlstrom, K. E.; Grimsrud, E. P.

1995-01-01

Ion mobility spectrometry (IMS) provides a promising approach to the study of gas phase ionic reactions in buffer gases at unusually high pressures. This point is illustrated here by studies of the Sn2 nucleophilic displacement reaction, Cl(-) + CH3Br yields Br + CH3Br, using IMS at atmospheric pressure. The equilibrium clustering reaction, Cl(-)(CHCI3)(n - 1) + CHCI3 yields Cl(-)(CHCI3)(n), where n = 1 and 2, and the effect of clustering on the Sn2 reaction with CH3Br have also been characterized by this IMS-based kinetic method. Present problems and anticipated improvements in the application of ion mobility spectrometry to studies of other gas phase ionic processes are discussed.

Ab initio modeling of zincblende AlN layer in Al-AlN-TiN multilayers

DOE PAGES

Yadav, S. K.; Wang, J.; Liu, X. -Y.

2016-06-13

An unusual growth mechanism of metastable zincblende AlN thin film by diffusion of nitrogen atoms into Al lattice is established. Using first-principles density functional theory, we studied the possibility of thermodynamic stability of AlN as a zincblende phase due to epitaxial strains and interface effect, which fails to explain the formation of zincblende AlN. We then compared the formation energetics of rocksalt and zincblende AlN in fcc Al through direct diffusion of nitrogen atoms to Al octahedral and tetrahedral interstitials. Furthermore, the formation of a zincblende AlN thin film is determined to be a kinetically driven process, not a thermodynamicallymore » driven process.« less

Anti-correlated spectral motion in bisphthalocyanines: evidence for vibrational modulation of electronic mixing.

PubMed

Prall, Bradley S; Parkinson, Dilworth Y; Ishikawa, Naoto; Fleming, Graham R

2005-12-08

We exploit a coherently excited nuclear wave packet to study nuclear motion modulation of electronic structure in a metal bridged phthalocyanine dimer, lutetium bisphthalocyanine, which displays two visible absorption bands. We find that the nuclear coordinate influences the energies of the underlying exciton and charge resonance states as well as their interaction; the interplay of the various couplings creates unusual anti-correlated spectral motion in the two bands. Excited state relaxation dynamics are the same regardless of which transition is pumped, with decay time constants of 1.5 and 11 ps. The dynamics are analyzed using a three-state kinetic model after relaxation from one or two additional states faster than the experimental time resolution of 50-100 fs.

Schizosaccharomyces pombe possesses an unusual and a conventional hexokinase: biochemical and molecular characterization of both hexokinases.

PubMed

Petit, T; Blázquez, M A; Gancedo, C

1996-01-08

Two hexokinases were characterized in Schizosaccharomyces pombe: hexokinase 1, with a low phosphorylation coefficient on glucose (Km 8.5 mM) and hexokinase 2, a kinetically conventional hexokinase. Genes hxk1+ and hxk2+ encoding these enzymes were cloned and sequenced. Disruption of hxk1+ had no effect on growth but disruption of hxk2+ doubled the generation time in glucose. Spores carrying the double disruption hxk1+ hxk2+ did not grow on glucose or fructose after one week. Expression of hxk1+ increased strongly during growth in fructose or glycerol. Expression of hxk2+ was highest during growth in glycerol. A NADP-dependent glucose dehydrogenase was detected, but not a glucokinase.

General theory of the multistage geminate reactions of the isolated pairs of reactants. II. Detailed balance and universal asymptotes of kinetics.

PubMed

Kipriyanov, Alexey A; Doktorov, Alexander B

2014-10-14

The analysis of general (matrix) kinetic equations for the mean survival probabilities of any of the species in a sample (or mean concentrations) has been made for a wide class of the multistage geminate reactions of the isolated pairs. These kinetic equations (obtained in the frame of the kinetic approach based on the concept of "effective" particles in Paper I) take into account various possible elementary reactions (stages of a multistage reaction) excluding monomolecular, but including physical and chemical processes of the change in internal quantum states carried out with the isolated pairs of reactants (or isolated reactants). The general basic principles of total and detailed balance have been established. The behavior of the reacting system has been considered on macroscopic time scales, and the universal long-term kinetics has been determined.

The role of latent heat in kinetic energy conversions of South Pacific cyclones

NASA Technical Reports Server (NTRS)

Kann, Deirdre M.; Vincent, Dayton G.

1986-01-01

The four-dimensional behavior of cyclone systems in the South Pacific Convergence Zone (SPCZ) is analyzed. Three cyclone systems, which occurred during the period from January 10-16, 1979, are examined using the data collected during the first special observing period of the FGGE. The effects of latent heating on the life cycles of the cyclones are investigated. Particular attention is given to the conversions of eddy available potential energy to eddy kinetic energy and of mean kinetic energy to eddy kinetic energy. The net radiation profile, sensible heat flux, total field of vertical motion, and latent heat component were computed. The life cycles of the cyclones are described. It is observed that the latent heating component accounts for nearly all the conversion in the three cyclones, and latent heating within the SPCZ is the major source of eddy kinetic energy for the cyclones.

Anisotropic kinetic energy release and gyroscopic behavior of CO2 super rotors from an optical centrifuge.

PubMed

Murray, Matthew J; Ogden, Hannah M; Mullin, Amy S

2017-10-21

An optical centrifuge is used to generate an ensemble of CO 2 super rotors with oriented angular momentum. The collision dynamics and energy transfer behavior of the super rotor molecules are investigated using high-resolution transient IR absorption spectroscopy. New multipass IR detection provides improved sensitivity to perform polarization-dependent transient studies for rotational states with 76 ≤ J ≤ 100. Polarization-dependent measurements show that the collision-induced kinetic energy release is spatially anisotropic and results from both near-resonant energy transfer between super rotor molecules and non-resonant energy transfer between super rotors and thermal molecules. J-dependent studies show that the extent and duration of the orientational anisotropy increase with rotational angular momentum. The super rotors exhibit behavior akin to molecular gyroscopes, wherein molecules with larger amounts of angular momentum are less likely to change their angular momentum orientation through collisions.

Anisotropic kinetic energy release and gyroscopic behavior of CO2 super rotors from an optical centrifuge

NASA Astrophysics Data System (ADS)

Murray, Matthew J.; Ogden, Hannah M.; Mullin, Amy S.

2017-10-01

An optical centrifuge is used to generate an ensemble of CO2 super rotors with oriented angular momentum. The collision dynamics and energy transfer behavior of the super rotor molecules are investigated using high-resolution transient IR absorption spectroscopy. New multipass IR detection provides improved sensitivity to perform polarization-dependent transient studies for rotational states with 76 ≤ J ≤ 100. Polarization-dependent measurements show that the collision-induced kinetic energy release is spatially anisotropic and results from both near-resonant energy transfer between super rotor molecules and non-resonant energy transfer between super rotors and thermal molecules. J-dependent studies show that the extent and duration of the orientational anisotropy increase with rotational angular momentum. The super rotors exhibit behavior akin to molecular gyroscopes, wherein molecules with larger amounts of angular momentum are less likely to change their angular momentum orientation through collisions.

Kinetics of Social Contagion

NASA Astrophysics Data System (ADS)

Ruan, Zhongyuan; Iñiguez, Gerardo; Karsai, Márton; Kertész, János

2015-11-01

Diffusion of information, behavioral patterns or innovations follows diverse pathways depending on a number of conditions, including the structure of the underlying social network, the sensitivity to peer pressure and the influence of media. Here we study analytically and by simulations a general model that incorporates threshold mechanism capturing sensitivity to peer pressure, the effect of "immune" nodes who never adopt, and a perpetual flow of external information. While any constant, nonzero rate of dynamically introduced spontaneous adopters leads to global spreading, the kinetics by which the asymptotic state is approached shows rich behavior. In particular, we find that, as a function of the immune node density, there is a transition from fast to slow spreading governed by entirely different mechanisms. This transition happens below the percolation threshold of network fragmentation, and has its origin in the competition between cascading behavior induced by adopters and blocking due to immune nodes. This change is accompanied by a percolation transition of the induced clusters.

MESOSCOPIC MODELING OF STOCHASTIC REACTION-DIFFUSION KINETICS IN THE SUBDIFFUSIVE REGIME

PubMed Central

BLANC, EMILIE; ENGBLOM, STEFAN; HELLANDER, ANDREAS; LÖTSTEDT, PER

2017-01-01

Subdiffusion has been proposed as an explanation of various kinetic phenomena inside living cells. In order to fascilitate large-scale computational studies of subdiffusive chemical processes, we extend a recently suggested mesoscopic model of subdiffusion into an accurate and consistent reaction-subdiffusion computational framework. Two different possible models of chemical reaction are revealed and some basic dynamic properties are derived. In certain cases those mesoscopic models have a direct interpretation at the macroscopic level as fractional partial differential equations in a bounded time interval. Through analysis and numerical experiments we estimate the macroscopic effects of reactions under subdiffusive mixing. The models display properties observed also in experiments: for a short time interval the behavior of the diffusion and the reaction is ordinary, in an intermediate interval the behavior is anomalous, and at long times the behavior is ordinary again. PMID:29046618

A Study Of High Speed Friction Behavior Under Elastic Loading Conditions

NASA Astrophysics Data System (ADS)

Crawford, P. J.; Hammerberg, J. E.

2005-03-01

The role of interfacial dynamics under high strain-rate conditions is an important constitutive relationship in modern modeling and simulation studies of dynamic events (<100 μs in length). The frictional behavior occurring at the interface between two metal surfaces under high elastic loading and sliding speed conditions is studied using the Rotating Barrel Gas Gun (RBGG) facility. The RBGG utilizes a low-pressure gas gun to propel a rotating annular projectile towards an annular target rod. Upon striking the target, the projectile imparts both an axial and a torsional impulse into the target. Resulting elastic waves are measured using strain gauges attached to the target rod. The kinetic coefficient of friction is obtained through an analysis of the resulting strain wave data. Experiments performed using Cu/Cu, Cu/Stainless steel and Cu/Al interfaces provide some insight into the kinetic coefficient of friction behavior at varying sliding speeds and impact loads.

Cure Kinetics of Benzoxazine/Cycloaliphatic Epoxy Resin by Differential Scanning Calorimetry

NASA Astrophysics Data System (ADS)

Gouni, Sreeja Reddy

Understanding the curing kinetics of a thermoset resin has a significant importance in developing and optimizing curing cycles in various industrial manufacturing processes. This can assist in improving the quality of final product and minimizing the manufacturing-associated costs. One approach towards developing such an understanding is to formulate kinetic models that can be used to optimize curing time and temperature to reach a full cure state or to determine time to apply pressure in an autoclave process. Various phenomenological reaction models have been used in the literature to successfully predict the kinetic behavior of a thermoset system. The current research work was designed to investigate the cure kinetics of Bisphenol-A based Benzoxazine (BZ-a) and Cycloaliphatic epoxy resin (CER) system under isothermal and nonisothermal conditions by Differential Scanning Calorimetry (DSC). The cure characteristics of BZ-a/CER copolymer systems with 75/25 wt% and 50/50 wt% have been studied and compared to that of pure benzoxazine under nonisothermal conditions. The DSC thermograms exhibited by these BZ-a/CER copolymer systems showed a single exothermic peak, indicating that the reactions between benzoxazine-benzoxazine monomers and benzoxazine-cycloaliphatic epoxy resin were interactive and occurred simultaneously. The Kissinger method and isoconversional methods including Ozawa-Flynn-Wall and Freidman were employed to obtain the activation energy values and determine the nature of the reaction. The cure behavior and the kinetic parameters were determined by adopting a single step autocatalytic model based on Kamal and Sourour phenomenological reaction model. The model was found to suitably describe the cure kinetics of copolymer system prior to the diffusion-control reaction. Analyzing and understanding the thermoset resin system under isothermal conditions is also important since it is the most common practice in the industry. The BZ-a/CER copolymer system with 75/25 wt% ratio which exhibited high glass transition temperature compared to polybenzoxazine was investigated under isothermal conditions. The copolymer system exhibited the maximum reaction rate at an intermediate degree of cure (20 to 40%), indicating that the reaction was autocatalytic. Similar to the nonisothermal cure kinetics, Kamal and Sourour phenomenological reaction model was adopted to determine the kinetic behavior of the system. The theoretical values based on the developed model showed a deviation from the obtained experimental values, which indicated the change in kinetics from a reaction-controlled mechanism to a diffusion-controlled mechanism with increasing reaction conversion. To substantiate the hypothesis, Fournier et al's diffusion factor was introduced into the model, resulting in an agreement between the theoretical and experimental values. The changes in cross-linking density and the glass transition temperature (Tg) with increasing epoxy concentration were investigated under Dynamic Mechanical Analyzer (DMA). The BZ-a/CER copolymer system with the epoxy content of less than 40 wt% exhibited the greatest Tg and cross-linking density compared to benzoxazine homopolymer and other ratios.

A realistic chemical system presenting a self-organized critical behavior

NASA Astrophysics Data System (ADS)

Gaveau, Bernard; Latrémolière, Daniel; Moreau, Michel

2003-04-01

We consider a realistic example of chemical system which presents self-organized criticality. We can study the kinetic equations analytically, and show that the conditions for self-organized criticality are satisfied. We find power relaxation laws for certain variables near the critical state, confirming the self-organized critical behavior.

"Why Is That Child So Rude?"

ERIC Educational Resources Information Center

Templeton, Beth Lindsay

2013-01-01

Why is that child so rude? Why does that mother let her daughter come to school dressed like that? Why doesn't he ever do his homework? That child is so lazy that he sleeps in class every day! It's not unusual for teachers to express frustration with students' behavior by making comments like these. But do these teachers really know…

Cyclam Derivatives with a Bis(phosphinate) or a Phosphinato-Phosphonate Pendant Arm: Ligands for Fast and Efficient Copper(II) Complexation for Nuclear Medical Applications.

PubMed

David, Tomáš; Kubíček, Vojtěch; Gutten, Ondrej; Lubal, Přemysl; Kotek, Jan; Pietzsch, Hans-Jürgen; Rulíšek, Lubomír; Hermann, Petr

2015-12-21

Cyclam derivatives bearing one geminal bis(phosphinic acid), -CH2PO2HCH2PO2H2 (H2L(1)), or phosphinic-phosphonic acid, -CH2PO2HCH2PO3H2 (H3L(2)), pendant arm were synthesized and studied as potential copper(II) chelators for nuclear medical applications. The ligands showed good selectivity for copper(II) over zinc(II) and nickel(II) ions (log KCuL = 25.8 and 27.7 for H2L(1) and H3L(2), respectively). Kinetic study revealed an unusual three-step complex formation mechanism. The initial equilibrium step leads to out-of-cage complexes with Cu(2+) bound by the phosphorus-containing pendant arm. These species quickly rearrange to an in-cage complex with cyclam conformation II, which isomerizes to another in-cage complex with cyclam conformation I. The first in-cage complex is quantitatively formed in seconds (pH ≈5, 25 °C, Cu:L = 1:1, cM ≈ 1 mM). At pH >12, I isomers undergo nitrogen atom inversion, leading to III isomers; the structure of the III-[Cu(HL(2))] complex in the solid state was confirmed by X-ray diffraction analysis. In an alkaline solution, interconversion of the I and III isomers is mutual, leading to the same equilibrium isomeric mixture; such behavior has been observed here for the first time for copper(II) complexes of cyclam derivatives. Quantum-chemical calculations showed small energetic differences between the isomeric complexes of H3L(2) compared with analogous data for isomeric complexes of cyclam derivatives with one or two methylphosphonic acid pendant arm(s). Acid-assisted dissociation proved the kinetic inertness of the complexes. Preliminary radiolabeling of H2L(1) and H3L(2) with (64)Cu was fast and efficient, even at room temperature, giving specific activities of around 70 GBq of (64)Cu per 1 μmol of the ligand (pH 6.2, 10 min, ca. 90 equiv of the ligand). These specific activities were much higher than those of H3nota and H4dota complexes prepared under identical conditions. The rare combination of simple ligand synthesis, very fast copper(II) complex formation, high thermodynamic stability, kinetic inertness, efficient radiolabeling, and expected low bone tissue affinity makes such ligands suitably predisposed to serve as chelators of copper radioisotopes in nuclear medicine.

Effects of functional group mass variance on vibrational properties and thermal transport in graphene

DOE PAGES

Lindsay, L.; Kuang, Y.

2017-03-13

Intrinsic thermal resistivity critically depends on features of phonon dispersions dictated by harmonic interatomic forces and masses. We present the effects of functional group mass variance on vibrational properties and thermal conductivity (κ ) of functionalized graphene from first principles calculations. We also use graphane, a buckled graphene backbone with covalently bonded Hydrogen atoms on both sides, as the base material and vary the mass of the Hydrogen atoms to simulate the effect of mass variance from other functional groups. We find non-monotonic behavior of κ with increasing mass of the functional group and an unusual cross-over from acoustic-dominated tomore » optic-dominated thermal transport behavior. We connect this cross-over to changes in the phonon dispersion with varying mass which suppress acoustic phonon velocities, but also give unusually high velocity optic modes. Further, we show that out-of-plane acoustic vibrations contribute significantly more to thermal transport than in-plane acoustic modes despite breaking of a reflection symmetry based scattering selection rule responsible for their large contributions in graphene. Our work demonstrates the potential for manipulation and engineering of thermal transport properties in two dimensional materials toward targeted applications.« less

Unusual ZFC and FC magnetic behavior in thin Co multi-layered structure

NASA Astrophysics Data System (ADS)

Ben Dor, Oren; Yochelis, Shira; Felner, Israel; Paltiel, Yossi

2017-04-01

The observation of unusual magnetic phenomena in a Ni -based magnetic memory device ([4] O. Ben-Dor et al., 2013) encouraged us to conduct a systematic research on Co based multi-layered structure which contains a α-helix L polyalanine (AHPA-L) organic compound. The constant Co thickness is 7 nm and AHPA-L was also replaced by non-chiral 1-Decanethiol organic molecules. Both organic compounds were chemisorbed on gold by a thiol group. The dc magnetic field (H) was applied parallel and perpendicular to the surface layers. The perpendicular direction is the easy magnetization axis and along this orientation only, the zero-field-cooled (ZFC) plots exhibit a pronounced peak around 55-58 K. This peak is suppressed in the second ZFC and field-cooled (FC) runs performed shortly after the virgin ZFC one. Thus, around the peak position ZFC>FC a phenomenon seldom observed. This peak reappears after measuring the same material six months later. This behavior appears in layers with the non-chiral 1-Decanethiol and it is very similar to that obtained in sulfur doped amorphous carbon. The peak origin and the peculiar ZFC>FC case are qualitatively explained.

Effects of functional group mass variance on vibrational properties and thermal transport in graphene

NASA Astrophysics Data System (ADS)

Lindsay, L.; Kuang, Y.

2017-03-01

Intrinsic thermal resistivity critically depends on features of phonon dispersions dictated by harmonic interatomic forces and masses. Here we present the effects of functional group mass variance on vibrational properties and thermal conductivity (κ ) of functionalized graphene from first-principles calculations. We use graphane, a buckled graphene backbone with covalently bonded hydrogen atoms on both sides, as the base material and vary the mass of the hydrogen atoms to simulate the effect of mass variance from other functional groups. We find nonmonotonic behavior of κ with increasing mass of the functional group and an unusual crossover from acoustic-dominated to optic-dominated thermal transport behavior. We connect this crossover to changes in the phonon dispersion with varying mass which suppress acoustic phonon velocities, but also give unusually high velocity optic modes. Further, we show that out-of-plane acoustic vibrations contribute significantly more to thermal transport than in-plane acoustic modes despite breaking of a reflection-symmetry-based scattering selection rule responsible for their large contributions in graphene. This work demonstrates the potential for manipulation and engineering of thermal transport properties in two-dimensional materials toward targeted applications.

Effects of functional group mass variance on vibrational properties and thermal transport in graphene

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

Lindsay, L.; Kuang, Y.

Intrinsic thermal resistivity critically depends on features of phonon dispersions dictated by harmonic interatomic forces and masses. We present the effects of functional group mass variance on vibrational properties and thermal conductivity (κ ) of functionalized graphene from first principles calculations. We also use graphane, a buckled graphene backbone with covalently bonded Hydrogen atoms on both sides, as the base material and vary the mass of the Hydrogen atoms to simulate the effect of mass variance from other functional groups. We find non-monotonic behavior of κ with increasing mass of the functional group and an unusual cross-over from acoustic-dominated tomore » optic-dominated thermal transport behavior. We connect this cross-over to changes in the phonon dispersion with varying mass which suppress acoustic phonon velocities, but also give unusually high velocity optic modes. Further, we show that out-of-plane acoustic vibrations contribute significantly more to thermal transport than in-plane acoustic modes despite breaking of a reflection symmetry based scattering selection rule responsible for their large contributions in graphene. Our work demonstrates the potential for manipulation and engineering of thermal transport properties in two dimensional materials toward targeted applications.« less

Stepwise crystallization and the layered distribution in crystallization kinetics of ultra-thin poly(ethylene terephthalate) film

NASA Astrophysics Data System (ADS)

Zuo, Biao; Xu, Jianquan; Sun, Shuzheng; Liu, Yue; Yang, Juping; Zhang, Li; Wang, Xinping

2016-06-01

Crystallization is an important property of polymeric materials. In conventional viewpoint, the transformation of disordered chains into crystals is usually a spatially homogeneous process (i.e., it occurs simultaneously throughout the sample), that is, the crystallization rate at each local position within the sample is almost the same. Here, we show that crystallization of ultra-thin poly(ethylene terephthalate) (PET) films can occur in the heterogeneous way, exhibiting a stepwise crystallization process. We found that the layered distribution of glass transition dynamics of thin film modifies the corresponding crystallization behavior, giving rise to the layered distribution of the crystallization kinetics of PET films, with an 11-nm-thick surface layer having faster crystallization rate and the underlying layer showing bulk-like behavior. The layered distribution in crystallization kinetics results in a particular stepwise crystallization behavior during heating the sample, with the two cold-crystallization temperatures separated by up to 20 K. Meanwhile, interfacial interaction is crucial for the occurrence of the heterogeneous crystallization, as the thin film crystallizes simultaneously if the interfacial interaction is relatively strong. We anticipate that this mechanism of stepwise crystallization of thin polymeric films will allow new insight into the chain organization in confined environments and permit independent manipulation of localized properties of nanomaterials.

Curing behavior and reaction kinetics of binder resins for 3D-printing investigated by dielectric analysis (DEA)

NASA Astrophysics Data System (ADS)

Möginger, B.; Kehret, L.; Hausnerova, B.; Steinhaus, J.

2016-05-01

3D-Printing is an efficient method in the field of additive manufacturing. In order to optimize the properties of manufactured parts it is essential to adapt the curing behavior of the resin systems with respect to the requirements. Thus, effects of resin composition, e.g. due to different additives such as thickener and curing agents, on the curing behavior have to be known. As the resin transfers from a liquid to a solid glass the time dependent ion viscosity was measured using DEA with flat IDEX sensors. This allows for a sensitive measurement of resin changes as the ion viscosity changes two to four decades. The investigated resin systems are based on the monomers styrene and HEMA. To account for the effects of copolymerization in the calculation of the reaction kinetics it was assumed that the reaction can be considered as a homo-polymerization having a reaction order n≠1. Then the measured ion viscosity curves are fitted with the solution of the reactions kinetics - the time dependent degree of conversion (DC-function) - for times exceeding the initiation phase representing the primary curing. The measured ion viscosity curves can nicely be fitted with the DC-function and the determined fit parameters distinguish distinctly between the investigated resin compositions.

Stepwise crystallization and the layered distribution in crystallization kinetics of ultra-thin poly(ethylene terephthalate) film

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

Zuo, Biao, E-mail: chemizuo@zstu.edu.cn, E-mail: wxinping@yahoo.com; Xu, Jianquan; Sun, Shuzheng

2016-06-21

Crystallization is an important property of polymeric materials. In conventional viewpoint, the transformation of disordered chains into crystals is usually a spatially homogeneous process (i.e., it occurs simultaneously throughout the sample), that is, the crystallization rate at each local position within the sample is almost the same. Here, we show that crystallization of ultra-thin poly(ethylene terephthalate) (PET) films can occur in the heterogeneous way, exhibiting a stepwise crystallization process. We found that the layered distribution of glass transition dynamics of thin film modifies the corresponding crystallization behavior, giving rise to the layered distribution of the crystallization kinetics of PET films,more » with an 11-nm-thick surface layer having faster crystallization rate and the underlying layer showing bulk-like behavior. The layered distribution in crystallization kinetics results in a particular stepwise crystallization behavior during heating the sample, with the two cold-crystallization temperatures separated by up to 20 K. Meanwhile, interfacial interaction is crucial for the occurrence of the heterogeneous crystallization, as the thin film crystallizes simultaneously if the interfacial interaction is relatively strong. We anticipate that this mechanism of stepwise crystallization of thin polymeric films will allow new insight into the chain organization in confined environments and permit independent manipulation of localized properties of nanomaterials.« less

Two-year performance study of porous, thermoset, shape memory polyurethanes intended for vascular medical devices

NASA Astrophysics Data System (ADS)

Weems, Andrew C.; Boyle, Anthony J.; Maitland, Duncan J.

2017-03-01

The long-term shape-recovery behavior of shape memory polymers has often been shown to be dependent on the length of time the material has been stored in the secondary shape. Typically, recovery performance and shape fixity will decrease with increased time in the secondary shape. In medical materials, a shelf-life is crucial to establish as it sets the upper threshold for device performance in a clinical setting, and a reduction in shape recovery would limit the development of SMP medical devices. Here, we present a two-year study of strain recovery, strain fixity, and shape recovery kinetics for passively and actively actuated SMPs intended for vascular devices. While kinetic experiments using immersion DMA indicate slight material relaxation and a decrease in the time to recovery, these changes are not found for bulk recovery experiments. The results indicate that a two-year shelf-life for these SMPs is very reasonable, as there is no change in the recovery kinetics, strain recovery, or strain fixity associated with this aging time. Further, a thermal accelerated aging test is presented for more rapid testing of the shape memory behavior of these SMPs and is compared with the real time aging results, indicating that this test is a reasonable indicator of the two-year behavior.

[Effects of several low-molecular-weight organic acids on the release kinetic of endosulfan from red soil].

PubMed

Zhao, Zhen-hua; Wu, Yu; Jiang, Xin; Xia, Li-ling; Ni, Li-xiao

2009-10-15

The kinetic release behaviors of a-endosulfan from red soil with three kinds of low-molecular-weight organic acids (LMWOA: oxalate, tartrate and citrate) solution and water leaching were investigated by kinetic device designed by ourselves and batch method. The results show that: the release percentage of endosulfan from red soil by tartrate and citrate solution (10 mmol/L) can increase by 7%-18% more than that by distilled water and oxalate solution, especially for tartrate solution. There is no significant difference between distilled water and oxalate solution for the release percentage of endosulfan (p > 0.05). There are two stages of quick and slow for the release of endosulfan from red soil, and the leaching speed is quicker especially for the initial 200 mL leaching solution. When using distilled water or oxalate solution as leaching solution, the best equations that described the kinetic release behavior of endosulfan from red soil were parabola diffuse equation and double constant equation, and weren't the apparent first dynamics equation that represented the simple surface diffusion mechanism. The kinetic release behavior of endosulfan in tartrate or citrate leaching system can be described by Elovich equation (R2 > 0.99, p < 0.0001), it implied that the simple surface diffusion mechanism is not the primary factor that effected the release of endosulfan, which three-dimensional molecule structure is complex, from red soil in aqueous phase leaching systems, and it maybe related to the outward diffuse mechanism from soil particle, activation and deactivation function of soil particles surface, the dissolution of soil mineral surface and structure change of inherent organic matter that coating onto the soil mineral surface induced by LMW organic acid. It suggested that the tartrate and citrate induced the complication of the release mechanisms of the pesticides from red soil.

Detailed study of precipitation of a poorly water soluble test compound using methodologies as in activity and solubility screening - mixing and automation effects.

PubMed

Gillespie, Cheska; Kennedy, Alan R; Edwards, Darren; Dowden, Lee; Daublain, Pierre; Halling, Peter

2013-09-01

Storage of pharmaceutical discovery compounds dissolved in dimethylsulfoxide (DMSO) is commonplace within industry. Often, the DMSO stock solution is added to an aqueous system (e.g. in bioassay or kinetic solubility testing)- since most test compounds are hydrophobic, precipitation could occur. Little is known about the factors affecting this precipitation process at the low (µM) concentrations used in screening analyses. Here, a poorly water soluble test compound (tolnaftate) was used to compare manual and automated pipetting, and explore the effect of mixing variables on precipitation. The amount of drug present in the supernatant after precipitation and centrifugation of the samples was quantified. An unusual result was obtained in three different laboratories: results of experiments performed initially were statistically significantly higher than those performed after a few days in the same lab. No significant differences were found between automated and manual pipetting, including in variability. Vortex mixing was found to give significantly lower supernatant amounts compared to milder mixing types. The mixing employed affects the particle growth of the precipitate. These findings are of relevance to discovery stage bioassay and kinetic solubility analyses.

Steady-state shear flows via nonequilibrium molecular dynamics and smooth-particle applied mechanics

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

Posch, H.A.; Hoover, W.G.; Kum, O.

1995-08-01

We simulate both microscopic and macroscopic shear flows in two space dimensions using nonequilibrium molecular dynamics and smooth-particle applied mechanics. The time-reversible {ital microscopic} equations of motion are isomorphic to the smooth-particle description of inviscid {ital macroscopic} continuum mechanics. The corresponding microscopic particle interactions are relatively weak and long ranged. Though conventional Green-Kubo theory suggests instability or divergence in two-dimensional flows, we successfully define and measure a finite shear viscosity coefficient by simulating stationary plane Couette flow. The special nature of the weak long-ranged smooth-particle functions corresponds to an unusual kind of microscopic transport. This microscopic analog is mainly kinetic,more » even at high density. For the soft Lucy potential which we use in the present work, nearly all the system energy is potential, but the resulting shear viscosity is nearly all kinetic. We show that the measured shear viscosities can be understood, in terms of a simple weak-scattering model, and that this understanding is useful in assessing the usefulness of continuum simulations using the smooth-particle method. We apply that method to the Rayleigh-Benard problem of thermally driven convection in a gravitational field.« less

Alternative bases in the RNA world: the prebiotic synthesis of urazole and its ribosides

NASA Technical Reports Server (NTRS)

Kolb, V. M.; Dworkin, J. P.; Miller, S. L.

1994-01-01

Urazole is a five-membered heterocyclic compound which is isosteric with uracil's hydrogen-bonding segment. Urazole reacts spontaneoulsy with ribose (and other aldoses) to give a mixture of four ribosides: alpha and beta pyranosides and furanosides. This reaction occurs in aqueous solution at mild temperatures. Thermodynamic and kinetic parameters for the reaction of urazole with ribose were determined. In contrast, uracil is completely unreactive with ribose under these conditions. Urazole's unusual reactivity is ascribed to the hydrazine portion of the molecule. Urazole can be synthesized from biuret and hydrazine under prebiotic conditions. The prebiotic synthesis of guanazole, which is isosteric in part to diaminopyrimidine and cytosine, is accomplished from dicyandiamide and hydrazine. Kinetic parameters for both prebiotic reactions were measured. Urazole and guanazole are transparent in the UV, which would be a favorable property in the absence of an ozone layer on the early Earth. Urazole makes hydrogen bonds with adenine in DMSO similar to those of uracil, as established by H NMR. All of these properties make urazole an attractive potential precursor to uracil and guanazole a potential precursor to cytosine in the RNA or pre-RNA world.

The H + OCS hot atom reaction - CO state distributions and translational energy from time-resolved infrared absorption spectroscopy

NASA Technical Reports Server (NTRS)

Nickolaisen, Scott L.; Cartland, Harry E.

1993-01-01

Time-resolved infrared diode laser spectroscopy has been used to probe CO internal and translational excitation from the reaction of hot H atoms with OCS. Product distributions should be strongly biased toward the maximum 1.4 eV collision energy obtained from 278 nm pulsed photolysis of HI. Rotations and vibrations are both colder than predicted by statistical density of states theory, as evidenced by large positive surprisal parameters. The bias against rotation is stronger than that against vibration, with measurable population as high as v = 4. The average CO internal excitation is 1920/cm, accounting for only 13 percent of the available energy. Of the energy balance, time-resolved sub-Doppler line shape measurements show that more than 38 percent appears as relative translation of the separating CO and SH fragments. Studies of the relaxation kinetics indicate that some rotational energy transfer occurs on the time scale of our measurements, but the distributions do not relax sufficiently to alter our conclusions. Vibrational distributions are nascent, though vibrational relaxation of excited CO is unusually fast in the OCS bath, with rates approaching 3 percent of gas kinetic for v = 1.

Comparative Solid-State Stability of Perindopril Active Substance vs. Pharmaceutical Formulation

PubMed Central

Buda, Valentina; Andor, Minodora; Ledeti, Adriana; Ledeti, Ionut; Vlase, Gabriela; Vlase, Titus; Cristescu, Carmen; Voicu, Mirela; Suciu, Liana; Tomescu, Mirela Cleopatra

2017-01-01

This paper presents the results obtained after studying the thermal stability and decomposition kinetics of perindopril erbumine as a pure active pharmaceutical ingredient as well as a solid pharmaceutical formulation containing the same active pharmaceutical ingredient (API). Since no data were found in the literature regarding the spectroscopic description, thermal behavior, or decomposition kinetics of perindopril, our goal was the evaluation of the compatibility of this antihypertensive agent with the excipients in the tablet under ambient conditions and to study the effect of thermal treatment on the stability of perindopril erbumine. ATR-FTIR (Attenuated Total Reflectance Fourier Transform Infrared) spectroscopy, thermal analysis (thermogravimetric mass curve (TG—thermogravimetry), derivative thermogravimetric mass curve (DTG), and heat flow (HF)) and model-free kinetics were chosen as investigational tools. Since thermal behavior is a simplistic approach in evaluating the thermal stability of pharmaceuticals, in-depth kinetic studies were carried out by classical kinetic methods (Kissinger and ASTM E698) and later with the isoconversional methods of Friedman, Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa. It was shown that the main thermal degradation step of perindopril erbumine is characterized by activation energy between 59 and 69 kJ/mol (depending on the method used), while for the tablet, the values were around 170 kJ/mol. The used excipients (anhydrous colloidal silica, microcrystalline cellulose, lactose, and magnesium stearate) should be used in newly-developed generic solid pharmaceutical formulations, since they contribute to an increased thermal stability of perindopril erbumine. PMID:28098840

Multi-step cure kinetic model of ultra-thin glass fiber epoxy prepreg exhibiting both autocatalytic and diffusion-controlled regimes under isothermal and dynamic-heating conditions

NASA Astrophysics Data System (ADS)

Kim, Ye Chan; Min, Hyunsung; Hong, Sungyong; Wang, Mei; Sun, Hanna; Park, In-Kyung; Choi, Hyouk Ryeol; Koo, Ja Choon; Moon, Hyungpil; Kim, Kwang J.; Suhr, Jonghwan; Nam, Jae-Do

2017-08-01

As packaging technologies are demanded that reduce the assembly area of substrate, thin composite laminate substrates require the utmost high performance in such material properties as the coefficient of thermal expansion (CTE), and stiffness. Accordingly, thermosetting resin systems, which consist of multiple fillers, monomers and/or catalysts in thermoset-based glass fiber prepregs, are extremely complicated and closely associated with rheological properties, which depend on the temperature cycles for cure. For the process control of these complex systems, it is usually required to obtain a reliable kinetic model that could be used for the complex thermal cycles, which usually includes both the isothermal and dynamic-heating segments. In this study, an ultra-thin prepreg with highly loaded silica beads and glass fibers in the epoxy/amine resin system was investigated as a model system by isothermal/dynamic heating experiments. The maximum degree of cure was obtained as a function of temperature. The curing kinetics of the model prepreg system exhibited a multi-step reaction and a limited conversion as a function of isothermal curing temperatures, which are often observed in epoxy cure system because of the rate-determining diffusion of polymer chain growth. The modified kinetic equation accurately described the isothermal behavior and the beginning of the dynamic-heating behavior by integrating the obtained maximum degree of cure into the kinetic model development.

Origin of unusual bandgap shift and dual emission in organic-inorganic lead halide perovskites

PubMed Central

Dar, M. Ibrahim; Jacopin, Gwénolé; Meloni, Simone; Mattoni, Alessandro; Arora, Neha; Boziki, Ariadni; Zakeeruddin, Shaik Mohammed; Rothlisberger, Ursula; Grätzel, Michael

2016-01-01

Emission characteristics of metal halide perovskites play a key role in the current widespread investigations into their potential uses in optoelectronics and photonics. However, a fundamental understanding of the molecular origin of the unusual blueshift of the bandgap and dual emission in perovskites is still lacking. In this direction, we investigated the extraordinary photoluminescence behavior of three representatives of this important class of photonic materials, that is, CH3NH3PbI3, CH3NH3PbBr3, and CH(NH2)2PbBr3, which emerged from our thorough studies of the effects of temperature on their bandgap and emission decay dynamics using time-integrated and time-resolved photoluminescence spectroscopy. The low-temperature (<100 K) photoluminescence of CH3NH3PbI3 and CH3NH3PbBr3 reveals two distinct emission peaks, whereas that of CH(NH2)2PbBr3 shows a single emission peak. Furthermore, irrespective of perovskite composition, the bandgap exhibits an unusual blueshift by raising the temperature from 15 to 300 K. Density functional theory and classical molecular dynamics simulations allow for assigning the additional photoluminescence peak to the presence of molecularly disordered orthorhombic domains and also rationalize that the unusual blueshift of the bandgap with increasing temperature is due to the stabilization of the valence band maximum. Our findings provide new insights into the salient emission properties of perovskite materials, which define their performance in solar cells and light-emitting devices. PMID:27819049

Origin of unusual bandgap shift and dual emission in organic-inorganic lead halide perovskites.

PubMed

Dar, M Ibrahim; Jacopin, Gwénolé; Meloni, Simone; Mattoni, Alessandro; Arora, Neha; Boziki, Ariadni; Zakeeruddin, Shaik Mohammed; Rothlisberger, Ursula; Grätzel, Michael

2016-10-01

Emission characteristics of metal halide perovskites play a key role in the current widespread investigations into their potential uses in optoelectronics and photonics. However, a fundamental understanding of the molecular origin of the unusual blueshift of the bandgap and dual emission in perovskites is still lacking. In this direction, we investigated the extraordinary photoluminescence behavior of three representatives of this important class of photonic materials, that is, CH 3 NH 3 PbI 3 , CH 3 NH 3 PbBr 3 , and CH(NH 2 ) 2 PbBr 3 , which emerged from our thorough studies of the effects of temperature on their bandgap and emission decay dynamics using time-integrated and time-resolved photoluminescence spectroscopy. The low-temperature (<100 K) photoluminescence of CH 3 NH 3 PbI 3 and CH 3 NH 3 PbBr 3 reveals two distinct emission peaks, whereas that of CH(NH 2 ) 2 PbBr 3 shows a single emission peak. Furthermore, irrespective of perovskite composition, the bandgap exhibits an unusual blueshift by raising the temperature from 15 to 300 K. Density functional theory and classical molecular dynamics simulations allow for assigning the additional photoluminescence peak to the presence of molecularly disordered orthorhombic domains and also rationalize that the unusual blueshift of the bandgap with increasing temperature is due to the stabilization of the valence band maximum. Our findings provide new insights into the salient emission properties of perovskite materials, which define their performance in solar cells and light-emitting devices.

Displacement cascades and defect annealing in tungsten, Part III: The sensitivity of cascade annealing in tungsten to the values of kinetic parameters

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

Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.

2015-07-01

Object kinetic Monte Carlo (OKMC) simulations have been performed to investigate various aspects of cascade aging in bulk tungsten and to determine the sensitivity of the results to the kinetic parameters. The primary focus is on how the kinetic parameters affect the initial recombination of defects in the first few ns of a simulation. The simulations were carried out using the object kinetic Monte Carlo (OKMC) code KSOME (kinetic simulations of microstructure evolution), using a database of cascades obtained from results of molecular dynamics (MD) simulations at various primary knock-on atom (PKA) energies and directions at temperatures of 300, 1025more » and 2050 K. The OKMC model was parameterized using defect migration barriers and binding energies from ab initio calculations. Results indicate that, due to the disparate mobilities of SIA and vacancy clusters in tungsten, annealing is dominated by SIA migration even at temperatures as high as 2050 K. For 100 keV cascades initiated at 300 K recombination is dominated by annihilation of large defect clusters. But for all other PKA energies and temperatures most of the recombination is due to the migration and rotation of small SIA clusters, while all the large SIA clusters escape the cubic simulation cell. The inverse U-shape behavior exhibited by the annealing efficiency as a function of temperature curve, especially for cascades of large PKA energies, is due to asymmetry in SIA and vacancy clustering assisted by the large difference in mobilities of SIAs and vacancies. This annealing behavior is unaffected by the dimensionality of SIA migration persists over a broad range of relative mobilities of SIAs and vacancies.« less

On the Adult Behavioral Repertoire of the Sawfly Perreyia flavipes Konow, 1899 (Hymenoptera: Pergidae): Movement, Mating, and Thanatosis.

PubMed

Neves, F M; Pie, M R

2018-02-01

Perreyia flavipes Konow, 1899 (Pergidae: Perreyinae) is a sawfly species with gregarious larvae commonly found in open areas in southern Brazil through Uruguay and northern Argentina. The combination of highly gregarious larvae with the production of a variety of toxins in P. flavipes has led to severe cases of intoxication in a variety of livestock species. Over the years, considerable information was discovered on the larval natural history of P. flavipes; however, virtually nothing is known about the adult behavior, particularly because of its short life-span. In this study, we report on the first extensive study on the adult behavior of P. flavipes, including movement, mating (with oviposition and maternal care), and thanatosis. Our results show some unusual behavioral adaptations presented by P. flavipes, such as irregular activity behavior (i.e., deficient gait pattern), thanatosis behavior-like display, and primitive maternal care. Individual behavioral acts are described and compared among sexes, and their potential functions are discussed.

Influence of the Investor's Behavior on the Complexity of the Stock Market

NASA Astrophysics Data System (ADS)

Atman, A. P. F.; Gonçalves, Bruna Amin

2012-04-01

One of the pillars of the finance theory is the efficient-market hypothesis, which is used to analyze the stock market. However, in recent years, this hypothesis has been questioned by a number of studies showing evidence of unusual behaviors in the returns of financial assets ("anomalies") caused by behavioral aspects of the economic agents. Therefore, it is time to initiate a debate about the efficient-market hypothesis and the "behavioral finances." We here introduce a cellular automaton model to study the stock market complexity, considering different behaviors of the economical agents. From the analysis of the stationary standard of investment observed in the simulations and the Hurst exponents obtained for the term series of stock index, we draw conclusions concerning the complexity of the model compared to real markets. We also investigate which conditions of the investors are able to influence the efficient market hypothesis statements.

Self-Assembly of Human Serum Albumin: A Simplex Phenomenon

PubMed Central

Thakur, Garima; Prashanthi, Kovur; Jiang, Keren; Thundat, Thomas

2017-01-01

Spontaneous self-assemblies of biomolecules can generate geometrical patterns. Our findings provide an insight into the mechanism of self-assembled ring pattern generation by human serum albumin (HSA). The self-assembly is a process guided by kinetic and thermodynamic parameters. The generated protein ring patterns display a behavior which is geometrically related to a n-simplex model and is explained through thermodynamics and chemical kinetics. PMID:28930179

The kinetics and mechanism of the ferrate(VI) oxidation of hydroxylamines.

PubMed

Johnson, Michael D; Hornstein, Brooks J

2003-10-20

Aqueous solutions of potassium ferrate(VI) cleanly and rapidly oxidize hydroxylamine to nitrous oxide, N-methylhydroxylamine to nitrosomethane, N-phenylhydroxylamine to nitrosobenzene, and O-methylhydroxylamine to methanol and nitrogen. The kinetics show first-order behavior with respect to each reactant and a two term component representing acid dependent and independent pathways. A general mechanism involving intermediate formation coupled with a two-electron oxidation is proposed.

Chronic stress as a factor in aircraft mishaps

NASA Technical Reports Server (NTRS)

Alkov, Robert A.

1988-01-01

Naval aviation is an unusually stressful career because of the inherent demands of the work. Stress is recognized as a cause of mishaps which involve pilot error. A questionnaire was adapted from Rahe and Homes' list of stressful life events in order to determine the relationship between pilot behavioral, personality, and life change factors on the one hand and responsibility for accidents on the other. A number of factors regarding interpersonal relationships, changes in personal behavior, personality factors, and life changes were found to discriminate between pilots who were and were not at fault in accidents.

The Origin and Evolution of the Behavior Analysis Program at the University of Nevada, Reno.

PubMed

Hayes, Linda J; Houmanfar, Ramona A; Ghezzi, Patrick M; Williams, W Larry; Locey, Matthew; Hayes, Steven C

2016-05-01

The origins of the Behavior Analysis program at the University of Nevada, Reno by way of a self-capitalized model through its transition to a more typical graduate program is described. Details of the original proposal to establish the program and the funding model are described. Some of the unusual features of the program executed in this way are discussed, along with problems engendered by the model. Also included is the diversification of faculty interests over time. The status of the program, now, after 25 years of operation, is presented.

Scattering properties of natural snow and frost - Comparison with icy satellite photometry

NASA Technical Reports Server (NTRS)

Verbiscer, Anne J.; Veverka, Joseph

1990-01-01

The Hapke (1986) equation is presently fit to ascertain the single-scattering albedo of the icy satellites of Uranus and Neptune and the one-term Henyey-Greenstein particle-phase function g for each of the Middleton and Mungall (1952) goniophotometric data samples. There emerge both very high single-scattering albedos and strongly forward-scattering particle phase functions; while these are in keeping with Mie theory-based theoretical considerations, they contrast with the observed backscattering behavior of icy satellites. It is suggested the icy satellite frost grains are aggregated into particles of complex texture, which produce the unusual backscattering behavior.

Carbon reactivation kinetics in GaAs: Its dependence on dopant precursor, doping level, and layer thickness

NASA Astrophysics Data System (ADS)

Mimila-Arroyo, J.; Bland, S.; Barbé, M.

2002-05-01

The reactivation kinetics of the acceptor behavior of carbon, its dependence on dopant precursors, doping level, layer thickness, and annealing temperature, as well as the behavior of carbon-hydrogen complexes in GaAs grown by metalorganic chemical vapor deposition are studied. Independent of the carbon source, in the "as grown" material, systematically carbon hydrogen complexes are present and the hole concentration is lower than the corresponding carbon concentration. The carbon reactivation kinetics was achieved by ex situ rapid thermal annealing through a series of multistage annealing experiments and assessed at each annealing stage by infrared absorption, hydrogen secondary ion mass spectroscopy profiling, and hole concentration measurements. Carbon reactivation occurs solely by the debonding of hydrogen from the isolated carbon acceptor and its out-diffusion from the sample. The carbon reactivation kinetics can be treated as a first order one with an activation energy, Ea=1.42±0.01 eV, independent of doping precursors, doping level, and layer thickness. The reactivation constant results to decrease as doping level and layer thickness increase. An empirical formula has been obtained that allows one to calculate the reactivation constant as a function of the carbon doping, layer thickness, and annealing temperature, allowing one to determine the optimal carbon reactivation conditions for any C:GaAs layer.

A kinetic Monte Carlo simulation method of van der Waals epitaxy for atomistic nucleation-growth processes of transition metal dichalcogenides.

PubMed

Nie, Yifan; Liang, Chaoping; Cha, Pil-Ryung; Colombo, Luigi; Wallace, Robert M; Cho, Kyeongjae

2017-06-07

Controlled growth of crystalline solids is critical for device applications, and atomistic modeling methods have been developed for bulk crystalline solids. Kinetic Monte Carlo (KMC) simulation method provides detailed atomic scale processes during a solid growth over realistic time scales, but its application to the growth modeling of van der Waals (vdW) heterostructures has not yet been developed. Specifically, the growth of single-layered transition metal dichalcogenides (TMDs) is currently facing tremendous challenges, and a detailed understanding based on KMC simulations would provide critical guidance to enable controlled growth of vdW heterostructures. In this work, a KMC simulation method is developed for the growth modeling on the vdW epitaxy of TMDs. The KMC method has introduced full material parameters for TMDs in bottom-up synthesis: metal and chalcogen adsorption/desorption/diffusion on substrate and grown TMD surface, TMD stacking sequence, chalcogen/metal ratio, flake edge diffusion and vacancy diffusion. The KMC processes result in multiple kinetic behaviors associated with various growth behaviors observed in experiments. Different phenomena observed during vdW epitaxy process are analysed in terms of complex competitions among multiple kinetic processes. The KMC method is used in the investigation and prediction of growth mechanisms, which provide qualitative suggestions to guide experimental study.

Dynamic Recrystallization Kinetics of 690 Alloy During Hot Compression of Double-Cone Samples

NASA Astrophysics Data System (ADS)

Wang, Jue; Zhai, Shun-Chao

2017-03-01

Hot compression tests of double-cone samples were conducted for 690 alloy to study the kinetic behavior of the complete dynamic recrystallization (DRX) process under low deformation temperatures from 960 to 1080 °C. The microstructure of 82 points in the vertical section of every deformed sample was quantitatively analyzed to determine the DRX fraction. Corresponding strain of these points was calculated by finite element simulations. Kinetic curves of the specimens with different preheating temperatures were then constructed. The features of various boundaries with different misorientation angles were investigated by electron backscatter diffraction technology and transmission electron microscope. The results showed that the strain is continuously and symmetrically distributed along the centerline of the vertical section. Large strain of 1.84 was obtained when the compression amount is 12 mm for double-cone samples. All the fitted kinetic curves display an "S" type, which possess a low growth rate of DRX at the beginning and the end of compression. The critical strain of recrystallization decreases with the increase in preheating temperature, while the completion strain remains around 1.5 for all the samples. The initial and maximum growth rates of DRX fraction have the opposite trend with the change in temperature, which is considered to be attributed to the behaviors of different misorientation boundaries.

Pyrolysis kinetics and thermal behavior of waste sawdust biomass using thermogravimetric analysis.

PubMed

Mishra, Ranjeet Kumar; Mohanty, Kaustubha

2018-03-01

The present study reports pyrolysis behavior of three waste biomass using thermogravimetric analysis to determine kinetic parameters at five different heating rates. Physiochemical characterization confirmed that these biomass have the potential for fuel and energy production. Pyrolysis experiments were carried out at five different heating rates (5-25 °C min -1 ). Five model-free methods such as Kissinger-Akahira-Sunose (KAS), Ozawa-Flynn-Wall (OFW), Friedman, Coats-Redfern, and distributed activation energy (DAEM) were used to calculate the kinetic parameters. The activation energy was found to be 171.66 kJ mol -1 , 148.44 kJ mol -1 , and 171.24 kJ mol -1 from KAS model; 179.29 kJ mol -1 , 156.58 kJ mol -1 , and 179.47 kJ mol -1 from OFW model; 168.58 kJ mol -1 , 181.53 kJ mol -1 , and 184.61 kJ mol -1 from Friedman model; and 206.62 kJ mol -1 , 171.63 kJ mol -1 , and 160.45 kJ mol -1 from DAEM model for PW, SW, AN biomass respectively. The calculated kinetic parameters are in good agreement with other reported biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interaction of fullerene (C60) nanoparticles with humic acid and alginate coated silica surfaces: measurements, mechanisms, and environmental implications.

PubMed

Chen, Kai Loon; Elimelech, Menachem

2008-10-15

The deposition kinetics of fullerene (C60) nanoparticles onto bare silica surfaces and surfaces precoated with humic acid and alginate are investigated over a range of monovalent (NaCI) and divalent (CaCl2) salt concentrations using a quartz crystal microbalance. Because simultaneous aggregation of the fullerene nanoparticles occurs, especially at higher electrolyte concentrations, we normalize the observed deposition rates by the corresponding favorable (transport-limited) deposition rates to obtain the attachment efficiencies, alpha. The deposition kinetics of fullerene nanoparticles onto bare silica surfaces are shown to be controlled by electrostatic interactions and van der Waals attraction, consistent with the classical particle deposition behavior where both favorable and unfavorable deposition regimes are observed. The presence of dissolved humic acid and alginate in solution leads to significantly slower deposition kinetics due to steric repulsion. Precoating the silica surfaces with humic acid and alginate exerts similar steric stabilization in the presence of NaCl. In the presence of CaCl2, the deposition kinetics of fullerene nanoparticles onto both humic acid- and alginate-coated surfaces are relatively high, even at relatively low (0.3 mM) calcium concentration. This behavior is attributed to the macromolecules undergoing complex formation with calcium ions, which reduces the charge and steric influences of the adsorbed macromolecular layers.

Equilibrium and kinetic adsorption study of Basic Yellow 28 and Basic Red 46 by a boron industry waste.

PubMed

Olgun, Asim; Atar, Necip

2009-01-15

In this study, the adsorption characteristics of Basic Yellow 28 (BY 28) and Basic Red 46 (BR 46) onto boron waste (BW), a waste produced from boron processing plant were investigated. The equilibrium adsorption isotherms and kinetics were investigated. The adsorption equilibrium data were analyzed by using various adsorption isotherm models and the results have shown that adsorption behavior of two dyes could be described reasonably well by a generalized isotherm. Kinetic studies indicated that the kinetics of the adsorption of BY 28 and BR 46 onto BW follows a pseudo-second-order model. The result showed that the BW exhibited high-adsorption capacity for basic dyes and the capacity slightly decreased with increasing temperature. The maximum adsorption capacities of BY 28 and BR 46 are reported at 75.00 and 74.73mgg(-1), respectively. The dye adsorption depended on the initial pH of the solution with maximum uptake occurring at about pH 9 and electrokinetic behavior of BW. Activation energy of 15.23kJ/mol for BY 28 and 18.15kJ/mol for BR 46 were determined confirming the nature of the physisorption onto BW. These results indicate that BW could be employed as low-cost material for the removal of the textile dyes from effluents.

Electronic tuning of the lability of Pt(II) complexes through pi-acceptor effects. Correlations between thermodynamic, kinetic, and theoretical parameters.

PubMed

Hofmann, Andreas; Jaganyi, Deogratius; Munro, Orde Q; Liehr, Günter; van Eldik, Rudi

2003-03-10

pi-Acceptor effects are often used to account for the unusual high lability of [Pt(terpy)L]((2)(-)(n)+) (terpy = 2,2':6',2' '-terpyridine) complexes. To gain further insight into this phenomenon, the pi-acceptor effect was varied systematically by studying the lability of [Pt(diethylenetriamine)OH(2)](2+) (aaa), [Pt(2,6-bis-aminomethylpyridine)OH(2)](2+) (apa), [Pt(N-(pyridyl-2-methyl)-1,2-diamino-ethane)OH(2)](2+) (aap), [Pt(bis(2-pyridylmethyl)amine)OH(2)](2+) (pap), [Pt(2,2'-bipyridine)(NH(3))(OH(2))](2+) (app), and [Pt(terpy)OH(2)](2+) (ppp). The crystal structure of the apa precursor [Pt(2,6-bis-aminomethylpyridine)Cl]Cl.H(2)O was determined. The substitution of water by a series of nucleophiles, viz. thiourea, N,N-dimethylthiourea, N,N,N',N'-tetramethylthiourea, I(-), and SCN(-), was studied under pseudo-first-order conditions as a function of concentration, pH, temperature, and pressure, using stopped-flow techniques. The data enable an overall comparison of the substitution behavior of these complexes, emphasizing the role played by the kinetic cis and trans pi-acceptor effects. The results indicate that the cis pi-acceptor effect is larger than the trans pi-acceptor effect, and that the pi-acceptor effects are multiplicative. DFT calculations at the B3LYP/LACVP level of theory show that, by the addition of pi-acceptor ligands to the metal, the positive charge on the metal center increases, and the energy separation of the frontier molecular orbitals (E(LUMO) - E(HOMO)) of the ground state Pt(II) complexes decreases. The calculations collectively support the experimentally observed additional increase in reactivity when two pi-accepting rings are adjacent to each other (app and ppp), which is ascribed to "electronic communication" between the pyridine rings. The results furthermore indicate that the pK(a) value of the platinum bound water molecule is controlled by the pi-accepting nature of the chelate system and reflects the electron density around the metal center. This in turn controls the rate of the associative substitution reaction and was analyzed using the Hammett equation.

Transient-state kinetic approach to mechanisms of enzymatic catalysis.

PubMed

Fisher, Harvey F

2005-03-01

Transient-state kinetics by its inherent nature can potentially provide more directly observed detailed resolution of discrete events in the mechanistic time courses of enzyme-catalyzed reactions than its more widely used steady-state counterpart. The use of the transient-state approach, however, has been severely limited by the lack of any theoretically sound and applicable basis of interpreting the virtual cornucopia of time and signal-dependent phenomena that it provides. This Account describes the basic kinetic behavior of the transient state, critically examines some currently used analytic methods, discusses the application of a new and more soundly based "resolved component transient-state time-course method" to the L-glutamate-dehydrogenase reaction, and establishes new approaches for the analysis of both single- and multiple-step substituted transient-state kinetic isotope effects.

Kinetics of cluster-related defects in silicon sensors irradiated with monoenergetic electrons

NASA Astrophysics Data System (ADS)

Radu, R.; Pintilie, I.; Makarenko, L. F.; Fretwurst, E.; Lindstroem, G.

2018-04-01

This work focuses on the kinetic mechanisms responsible for the annealing behavior of radiation cluster-related defects with impact on the electrical performance of silicon sensors. Such sensors were manufactured on high resistivity n-type standard float-zone (STFZ) and oxygen enriched float-zone (DOFZ) material and had been irradiated with mono-energetic electrons of 3.5 MeV energy and fluences of 3 × 1014 cm-2 and 6 × 1014 cm-2. After irradiation, the samples were subjected either to isochronal or isothermal heat treatments in the temperature range from 80 °C to 300 °C. The specific investigated defects are a group of three deep acceptors [H(116 K), H(140 K), and H(152 K)] with energy levels in the lower half of the band gap and a shallow donor E(30 K) with a level at 0.1 eV below the conduction band. The stability and kinetics of these defects at high temperatures are discussed on the basis of the extracted activation energies and frequency factors. The annealing of the H defects takes place similarly in both types of materials, suggesting a migration rather than a dissociation mechanism. On the contrary, the E(30 K) defect shows a very different annealing behavior, being stable in STFZ even at 300 °C, but annealing-out quickly in DOFZ material at temperatures higher than 200 °C , with a high frequency factor of the order of 1013 s-1. Such a behavior rules out a dissociation process, and the different annealing behavior is suggested to be related to a bistable behavior of the defect.

Arrhenius-kinetics evidence for quantum tunneling in microbial "social" decision rates.

PubMed

Clark, Kevin B

2010-11-01

Social-like bacteria, fungi and protozoa communicate chemical and behavioral signals to coordinate their specializations into an ordered group of individuals capable of fitter ecological performance. Examples of microbial "social" behaviors include sporulation and dispersion, kin recognition and nonclonal or paired reproduction. Paired reproduction by ciliates is believed to involve intra- and intermate selection through pheromone-stimulated "courting" rituals. Such social maneuvering minimizes survival-reproduction tradeoffs while sorting superior mates from inferior ones, lowering the vertical spread of deleterious genes in geographically constricted populations and possibly promoting advantageous genetic innovations. In a previous article, I reported findings that the heterotrich Spirostomum ambiguum can out-complete mating rivals in simulated social trials by learning behavioral heuristics which it then employs to store and select sets of altruistic and deceptive signaling strategies. Frequencies of strategy use typically follow Maxwell-Boltzmann (MB), Fermi-Dirac (FD) or Bose-Einstein (BE) statistical distributions. For ciliates most adept at social decision making, a brief classical MB computational phase drives signaling behavior into a later quantum BE computational phase that condenses or favors the selection of a single fittest strategy. Appearance of the network analogue of BE condensation coincides with Hebbian-like trial-and-error learning and is consistent with the idea that cells behave as heat engines, where loss of energy associated with specific cellular machinery critical for mating decisions effectively reduces the temperature of intracellular enzymes cohering into weak Fröhlich superposition. I extend these findings by showing the rates at which ciliates switch serial behavioral strategies agree with principles of chemical reactions exhibiting linear and nonlinear Arrhenius kinetics during respective classical and quantum computations. Nonlinear Arrhenius kinetics in ciliate decision making suggest transitions from one signaling strategy to another result from a computational analogue of quantum tunneling in social information processing.

Neon diffusion kinetics and implications for cosmogenic neon paleothermometry in feldspars

DOE PAGES

Tremblay, Marissa M.; Shuster, David L.; Balco, Greg; ...

2017-02-20

Observations of cosmogenic neon concentrations in feldspars can potentially be used to constrain the surface exposure duration or surface temperature history of geologic samples. The applicability of cosmogenic neon to either application depends on the temperature-dependent diffusivity of neon isotopes. Here in this work, we investigate the kinetics of neon diffusion in feldspars of different compositions and geologic origins through stepwise degassing experiments on single, proton-irradiated crystals. To understand the potential causes of complex diffusion behavior that is sometimes manifest as nonlinearity in Arrhenius plots, we compare our results to argon stepwise degassing experiments previously conducted on the same feldspars.more » Many of the feldspars we studied exhibit linear Arrhenius behavior for neon whereas argon degassing from the same feldspars did not. This suggests that nonlinear behavior in argon experiments is an artifact of structural changes during laboratory heating. However, other feldspars that we examined exhibit nonlinear Arrhenius behavior for neon diffusion at temperatures far below any known structural changes, which suggests that some preexisting material property is responsible for the complex behavior. In general, neon diffusion kinetics vary widely across the different feldspars studied, with estimated activation energies (E a) ranging from 83.3 to 110.7 kJ/mol and apparent pre-exponential factors (D 0) spanning three orders of magnitude from 2.4 ×10 -3 to 8.9 × 10 -1 cm 2 s -1. Finally, as a consequence of this variability, the ability to reconstruct temperatures or exposure durations from cosmogenic neon abundances will depend on both the specific feldspar and the surface temperature conditions at the geologic site of interest.« less

Development and characterization of a dynamic lesion phantom for the quantitative evaluation of dynamic contrast-enhanced MRI.

PubMed

Freed, Melanie; de Zwart, Jacco A; Hariharan, Prasanna; Myers, Matthew R; Badano, Aldo

2011-10-01

To develop a dynamic lesion phantom that is capable of producing physiological kinetic curves representative of those seen in human dynamic contrast-enhanced MRI (DCE-MRI) data. The objective of this phantom is to provide a platform for the quantitative comparison of DCE-MRI protocols to aid in the standardization and optimization of breast DCE-MRI. The dynamic lesion consists of a hollow, plastic mold with inlet and outlet tubes to allow flow of a contrast agent solution through the lesion over time. Border shape of the lesion can be controlled using the lesion mold production method. The configuration of the inlet and outlet tubes was determined using fluid transfer simulations. The total fluid flow rate was determined using x-ray images of the lesion for four different flow rates (0.25, 0.5, 1.0, and 1.5 ml/s) to evaluate the resultant kinetic curve shape and homogeneity of the contrast agent distribution in the dynamic lesion. High spatial and temporal resolution x-ray measurements were used to estimate the true kinetic curve behavior in the dynamic lesion for benign and malignant example curves. DCE-MRI example data were acquired of the dynamic phantom using a clinical protocol. The optimal inlet and outlet tube configuration for the lesion molds was two inlet molds separated by 30° and a single outlet tube directly between the two inlet tubes. X-ray measurements indicated that 1.0 ml/s was an appropriate total fluid flow rate and provided truth for comparison with MRI data of kinetic curves representative of benign and malignant lesions. DCE-MRI data demonstrated the ability of the phantom to produce realistic kinetic curves. The authors have constructed a dynamic lesion phantom, demonstrated its ability to produce physiological kinetic curves, and provided estimations of its true kinetic curve behavior. This lesion phantom provides a tool for the quantitative evaluation of DCE-MRI protocols, which may lead to improved discrimination of breast cancer lesions.

Computation of restoration of ligand response in the random kinetics of a prostate cancer cell signaling pathway.

PubMed

Dana, Saswati; Nakakuki, Takashi; Hatakeyama, Mariko; Kimura, Shuhei; Raha, Soumyendu

2011-01-01

Mutation and/or dysfunction of signaling proteins in the mitogen activated protein kinase (MAPK) signal transduction pathway are frequently observed in various kinds of human cancer. Consistent with this fact, in the present study, we experimentally observe that the epidermal growth factor (EGF) induced activation profile of MAP kinase signaling is not straightforward dose-dependent in the PC3 prostate cancer cells. To find out what parameters and reactions in the pathway are involved in this departure from the normal dose-dependency, a model-based pathway analysis is performed. The pathway is mathematically modeled with 28 rate equations yielding those many ordinary differential equations (ODE) with kinetic rate constants that have been reported to take random values in the existing literature. This has led to us treating the ODE model of the pathways kinetics as a random differential equations (RDE) system in which the parameters are random variables. We show that our RDE model captures the uncertainty in the kinetic rate constants as seen in the behavior of the experimental data and more importantly, upon simulation, exhibits the abnormal EGF dose-dependency of the activation profile of MAP kinase signaling in PC3 prostate cancer cells. The most likely set of values of the kinetic rate constants obtained from fitting the RDE model into the experimental data is then used in a direct transcription based dynamic optimization method for computing the changes needed in these kinetic rate constant values for the restoration of the normal EGF dose response. The last computation identifies the parameters, i.e., the kinetic rate constants in the RDE model, that are the most sensitive to the change in the EGF dose response behavior in the PC3 prostate cancer cells. The reactions in which these most sensitive parameters participate emerge as candidate drug targets on the signaling pathway. 2011 Elsevier Ireland Ltd. All rights reserved.

High-pressure phase transitions of nitinol NiTi to a semiconductor with an unusual topological structure

NASA Astrophysics Data System (ADS)

Liu, Guangtao; Liu, Hanyu; Feng, Xiaolei; Redfern, Simon A. T.

2018-04-01

Systematic ab initio structure simulations have been used to explore the high-pressure behavior of nitinol (NiTi) at zero temperature. Our crystal structure prediction and first-principles calculations reveal that the known B 19 phase is dynamically unstable, and an orthorhombic structure (Pbcm) and a face-centered-cubic B 32 structure (F d 3 ¯m ) become stable above ˜4 and 29 GPa, respectively. The predicted, highest-pressure, B 32 phase is composed of two interpenetrating diamond structures, with a structural topology that is quite distinct from that of the other phases of NiTi. Interestingly, the B 32 phase shows an unusual semiconducting characteristic as a result of its unique band structure and the nature of 3 d orbitals localization, whose expected synthesis pressure is accessible to current experimental techniques.

Rare recurrence of a rare ovarian stromal tumor with luteinized cells: a case report.

PubMed

El Mehdi, Tazi; Essadi, Ismail; M'rabti, Hind; Errihani, Hassan

2011-08-04

Sex cord-stromal tumors of the ovary are uncommon. They behave unpredictably and often have a late recurrence, making counseling, management, and prediction of prognosis challenging. A 52-year-old Moroccan woman with an sex cord-stromal tumors underwent a bilateral oophorectomy. The histology was unusual but was likely to be a luteinized thecoma with suspicious features for invasion. Seven years later, after a gastrointestinal bleed, a metastasis within the small bowel mucosa was detected. This represents probable isolated hematogenous or lymphatic spread, which is highly unusual, especially in the absence of concurrent peritoneal disease. To the best of our knowledge, this is the second reported case of an sex cord-stromal tumors recurring in small bowel mucosa and mimicking a primary colorectal tumor. This highlights the diverse nature and behavior of these tumors.

Probing of barrier induced deviations in current-voltage characteristics of polymer devices by impedance spectroscopy

NASA Astrophysics Data System (ADS)

Khan, Motiur Rahman; Rao, K. S. R. Koteswara; Menon, R.

2017-05-01

Temperature dependent current-voltage measurements have been performed on poly(3-methylthiophene) based devices in metal/polymer/metal geometry in temperature range 90-300 K. Space charge limited current (SCLC) controlled by exponentially distributed traps is observed at all the measured temperatures at intermediate voltage range. At higher voltages, trap-free SCLC is observed at 90 K only while slope less than 2 is observed at higher temperatures which is quiet unusual in polymer devices. Impedance measurements were performed at different bias voltages. The unusual behavior observed in current-voltage characteristics is explained by Cole-Cole plot which gives the signature of interface dipole on electrode/polymer interface. Two relaxation mechanisms are obtained from the real part of impedance vs frequency spectra which confirms the interface related phenomena in the device

Anomalous frequency-dependent ionic conductivity of lesion-laden human-brain tissue

NASA Astrophysics Data System (ADS)

Emin, David; Akhtari, Massoud; Fallah, Aria; Vinters, Harry V.; Mathern, Gary W.

2017-10-01

We study the effect of lesions on our four-electrode measurements of the ionic conductivity of (˜1 cm3) samples of human brain excised from patients undergoing pediatric epilepsy surgery. For most (˜94%) samples, the low-frequency ionic conductivity rises upon increasing the applied frequency. We attributed this behavior to the long-range (˜0.4 mm) diffusion of solvated sodium cations before encountering intrinsic impenetrable blockages such as cell membranes, blood vessels, and cell walls. By contrast, the low-frequency ionic conductivity of some (˜6%) brain-tissue samples falls with increasing applied frequency. We attribute this unusual frequency-dependence to the electric-field induced liberation of sodium cations from traps introduced by the unusually severe pathology observed in samples from these patients. Thus, the anomalous frequency-dependence of the ionic conductivity indicates trap-producing brain lesions.

Thermal Analysis of Unusual Local-scale Features on the Surface of Vesta

NASA Technical Reports Server (NTRS)

Tosi, F.; Capria, M. T.; DeSanctis, M. C.; Capaccioni, F.; Palomba, E.; Zambon, F.; Ammannito, E.; Blewett, D. T.; Combe, J.-Ph.; Denevi, B. W.;

Unusual self-electrocution simulating judicial electrocution by an adolescent.

PubMed

Murty, O P

2008-06-01

Electrocution is one of the rarest modes of suicide. In this case, one school going adolescent committed suicide by electrocution using bare electric wire. This is a rare case of suicidal death by applying live wires around the wrists, simulating the act of judicial electrocution. He positioned himself on armed chair and placed the nude wire loops from a cable around both wrists and switched on the current by plugging in to nearest socket by foot. There were linear electric contact wounds completely encircling around the both wrists. In addition to these linear electric burns all around wrists, there were electrical burns over both hands. This death highlights the need of supervision and close watch on children for self-destructing activities and behavior. This case also highlights unusual method adopted by adolescent to end his life.

Topological interlocking provides stiffness to stochastically micro-cracked materials beyond the transport percolation limit

NASA Astrophysics Data System (ADS)

Pal, Anirban; Picu, Catalin; Lupulescu, Marian V.

We study the mechanical behavior of two-dimensional, stochastically microcracked continua in the range of crack densities close to, and above the transport percolation threshold. We show that these materials retain stiffness up to crack densities much larger than the transport percolation threshold, due to topological interlocking of sample sub-domains. Even with a linear constitutive law for the continuum, the mechanical behavior becomes non-linear in the range of crack densities bounded by the transport and stiffness percolation thresholds. The effect is due to the fractal nature of the fragmentation process and is not linked to the roughness of individual cracks. We associate this behavior to that of itacolumite, a sandstone that exhibits unusual flexibility.

Expansion of a Rarefied Gas Cloud in a Vacuum: Asymptotic Treatment

NASA Astrophysics Data System (ADS)

Zhuk, V. I.

2018-02-01

The unsteady expansion of a rarefied gas of finite mass in an unlimited space is studied. The long-time asymptotic behavior of the solution is examined at Knudsen numbers tending to zero. An asymptotic analysis shows that, in the limit of small Knudsen numbers, the behavior of the macroscopic parameters of the expanding gas cloud at long times (i.e., for small density values) has nothing to do with the free-molecular or continuum flow regimes. This conclusion is unexpected and not obvious, but follows from a uniformly suitable solution constructed by applying the method of outer and inner asymptotic expansions. In particular, the unusual temperature behavior is of interest as applied to remote sensing of rocket exhaust plumes.

WKB approximation and tunneling in theories with noncanonical kinetic terms

NASA Astrophysics Data System (ADS)

González, Mariana Carrillo; Masoumi, Ali; Solomon, Adam R.; Trodden, Mark

2017-09-01

Tunneling is a fascinating aspect of quantum mechanics that renders the local minima of a potential meta-stable, with important consequences for particle physics, for the early hot stage of the universe, and more speculatively, for the behavior of the putative multiverse. While this phenomenon has been studied extensively for systems which have canonical kinetic terms, many theories of fundamental physics contain fields with noncanonical kinetic structures. It is therefore desirable to have a detailed framework for calculating tunneling rates and initial states after tunneling for these theories. In this work we present such a rigorous formulation and illustrate its use by applying it to a number of examples.

First kinetic discrimination between carbon and oxygen reactivity of enols.

PubMed

García-Río, Luis; Mejuto, Juan C; Parajó, Mercedes; Pérez-Lorenzo, Moisés

2008-11-07

Nitrosation of enols shows a well-differentiated behavior depending on whether the reaction proceeds through the carbon (nucleophilic catalysis is observed) or the oxygen atom (general acid-base catalysis is observed). This is due to the different operating mechanisms for C- and O-nitrosation. Nitrosation of acetylacetone (AcAc) shows a simultaneous nucleophilic and acid-base catalysis. This simultaneous catalysis constitutes the first kinetic evidence of two independent reactions on the carbon and oxygen atom of an enol. The following kinetic study allows us to determine the rate constants for both reaction pathways. A similar reactivity of the nucleophilic centers with the nitrosonium ion is observed.

In situ synchrotron investigation of grain growth behavior of nano-grained UO 2

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

Miao, Yinbin; Yao, Tiankai; Lian, Jie

Here, we report on the study of grain growth kinetics in nano-grained UO 2 samples. Dense nano-grained UO 2 samples with well-controlled stoichiometry and grain size were fabricated using the spark plasma sintering technique. To determine the grain growth kinetics at elevated temperatures, a synchrotron wide-angle X-ray scattering (WAXS) study was performed in situ to measure the real-time grain size evolution based on the modified Williamson-Hall analysis. The unique grain growth kinetics of nanocrystalline UO 2 at 730 °C and 820 °C were observed and explained by the difference in mobility of various grain boundaries.

In situ synchrotron investigation of grain growth behavior of nano-grained UO 2

DOE PAGES

Miao, Yinbin; Yao, Tiankai; Lian, Jie; ...

2017-01-09

Here, we report on the study of grain growth kinetics in nano-grained UO 2 samples. Dense nano-grained UO 2 samples with well-controlled stoichiometry and grain size were fabricated using the spark plasma sintering technique. To determine the grain growth kinetics at elevated temperatures, a synchrotron wide-angle X-ray scattering (WAXS) study was performed in situ to measure the real-time grain size evolution based on the modified Williamson-Hall analysis. The unique grain growth kinetics of nanocrystalline UO 2 at 730 °C and 820 °C were observed and explained by the difference in mobility of various grain boundaries.

Nonlinear Constitutive Relations for High Temperature Applications

NASA Technical Reports Server (NTRS)

1983-01-01

The topics of discussion addressed were material behavior, design analysis, deformation kinetics, metallurgical characterization, mechanical subelement models, stress analysis, fracture mechanics, viscoplasticity, and thermal loading.

Crystallization, flow and thermal histories of lunar and terrestrial compositions

NASA Technical Reports Server (NTRS)

Uhlmann, D. R.

1979-01-01

Contents: a kinetic treatment of glass formation; effects of nucleating heterogeneities on glass formation; glass formation under continuous cooling conditions; crystallization statistics; kinetics of crystal nucleation; diffusion controlled crystal growth; crystallization of lunar compositions; crystallization between solidus and liquidus; crystallization on reheating a glass; temperature distributions during crystallization; crystallization of anorthite and anorthite-albite compositions; effect of oxidation state on viscosity; diffusive creep and viscous flow; high temperature flow behavior of glass-forming liquids, a free volume interpretation; viscous flow behavior of lunar compositions; thermal history of orange soil material; breccias formation by viscous sintering; viscous sintering; thermal histories of breccias; solute partitioning and thermal history of lunar rocks; heat flow in impact melts; and thermal histories of olivines.

On the evils of group averaging: commentary on Nevin's "Resistance to extinction and behavioral momentum".

PubMed

Gallistel, C R

2012-05-01

Except under unusually favorable circumstances, one can infer from functions obtained by averaging across the subjects neither the form of the function that describes the behavior of the individual subject nor the central tendencies of descriptive parameter values. We should restore the cumulative record to the place of honor as our means of visualizing behavioral change, and we should base our conclusions on analyses that measure where the change occurs in these response-by-response records of the behavior of individual subjects. When that is done, we may find that the extinction of responding to a continuously reinforced stimulus is faster than the extinction of responding to a partially reinforced stimulus in a within-subject design because the latter is signaled extinction. Copyright © 2012 Elsevier B.V. All rights reserved.

Gas-liquid nucleation at large metastability: unusual features and a new formalism

NASA Astrophysics Data System (ADS)

Santra, Mantu; Singh, Rakesh S.; Bagchi, Biman

2011-03-01

Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order to understand the large numerical discrepancy between simulation predictions and experimental results, we carried out a study of the dependence on the range of intermolecular interactions of both the surface tension of an equilibrium planar gas-liquid interface and the free energy barrier of nucleation. Both are found to depend significantly on the range of interaction for the Lennard-Jones potential, both in two and three dimensions. The value of surface tension and also the free energy difference between the gas and the liquid phase increase significantly and converge only when the range of interaction is extended beyond 6-7 molecular diameters. We find, with the full range of interaction potential, that the surface tension shows only a weak dependence on supersaturation, so the reason for the breakdown of CNT (with simulated values of surface tension and free energy gap) cannot be attributed to the supersaturation dependence of surface tension. This remains an unsettled issue at present because of the use of the value of surface tension obtained at coexistence.

From kinetic-structure analysis to engineering crystalline fiber networks in soft materials.

PubMed

Wang, Rong-Yao; Wang, Peng; Li, Jing-Liang; Yuan, Bing; Liu, Yu; Li, Li; Liu, Xiang-Yang

2013-03-07

Understanding the role of kinetics in fiber network microstructure formation is of considerable importance in engineering gel materials to achieve their optimized performances/functionalities. In this work, we present a new approach for kinetic-structure analysis for fibrous gel materials. In this method, kinetic data is acquired using a rheology technique and is analyzed in terms of an extended Dickinson model in which the scaling behaviors of dynamic rheological properties in the gelation process are taken into account. It enables us to extract the structural parameter, i.e. the fractal dimension, of a fibrous gel from the dynamic rheological measurement of the gelation process, and to establish the kinetic-structure relationship suitable for both dilute and concentrated gelling systems. In comparison to the fractal analysis method reported in a previous study, our method is advantageous due to its general validity for a wide range of fractal structures of fibrous gels, from a highly compact network of the spherulitic domains to an open fibrous network structure. With such a kinetic-structure analysis, we can gain a quantitative understanding of the role of kinetic control in engineering the microstructure of the fiber network in gel materials.

Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model.

PubMed

Tian, Lei; Shi, Zhenqing; Lu, Yang; Dohnalkova, Alice C; Lin, Zhang; Dang, Zhi

2017-09-19

Quantitative understanding the kinetics of toxic ion reactions with various heterogeneous ferrihydrite binding sites is crucial for accurately predicting the dynamic behavior of contaminants in environment. In this study, kinetics of As(V), Cr(VI), Cu(II), and Pb(II) adsorption and desorption on ferrihydrite was studied using a stirred-flow method, which showed that metal adsorption/desorption kinetics was highly dependent on the reaction conditions and varied significantly among four metals. High resolution scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy showed that all four metals were distributed within the ferrihydrite aggregates homogeneously after adsorption reactions. Based on the equilibrium model CD-MUSIC, we developed a novel unified kinetics model applicable for both cation and oxyanion adsorption and desorption on ferrihydrite, which is able to account for the heterogeneity of ferrihydrite binding sites, different binding properties of cations and oxyanions, and variations of solution chemistry. The model described the kinetic results well. We quantitatively elucidated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites and the formation of various surface complexes controlled the adsorption and desorption kinetics at different reaction conditions and time scales. Our study provided a unified modeling method for the kinetics of ion adsorption/desorption on ferrihydrite.

Reproduction and mating behavior of the atlantic flyingfish, Cheilopogon melanurus (Exocoetidae), off North Carolina

USGS Publications Warehouse

Casazza, Tara L.; Ross, Steve W.; Necaise, Ann Marie; Sulak, Kenneth J.

2005-01-01

The reproductive biology of Cheilopogon melanurus (Valenciennes, 1847) was examined off North Carolina during the summers of 1991–1992 and 1999–2003. Specimens were collected using a small mesh neuston net and dip nets. A spawning event, the first observation of mating behavior for this species, was recorded off Cape Fear, North Carolina, on 19 August 2003. It was considered to be a spawning event due to: 1) unusual coloration of both sexes, 2) unusual swimming behavior of both sexes, and 3) ready release of gametes by both sexes upon capture. The spawning event occurred in the presence of small clumps of floating Sargassum, but the fish did not appear to use the algae. Over all collections, female gonadosomatic indices were highest in June and July, but mature females were collected each month (June, July, and August). The overall female to male sex ratio did not vary significantly from 1:1. Number of ova increased with increasing fish size, but the relationship was not strong. Our data indicate a spawning season of at least June through August off North Carolina due to high female gonadosomatic indices, large egg diameters, presence of egg filaments, presence of spent females in July and August, and presence of small juveniles (≤ 25 mm) in July and August. This is the first report of single pair spawning for this family; other species reportedly spawn in large aggregations.

Chair interconversion and reactivity of mannuronic acid esters.

PubMed

Rönnols, Jerk; Walvoort, Marthe T C; van der Marel, Gijsbert A; Codée, Jeroen D C; Widmalm, Göran

2013-12-14

Mannopyranosyluronic acids display a very unusual conformation behavior in that they often prefer to adopt a (1)C4 chair conformation. They are endowed with a strikingly high reactivity when used in a glycosylation reaction as a glycosyl donor. To investigate the unusual conformational behavior a series of mannuronic acid ester derivatives, comprising anomeric triflate species and O-methyl glycosides, was examined by dynamic NMR experiments, through lineshape analysis of (1)H and (19)F NMR spectra at various temperatures from -80 °C to 0 °C. Exchange rates between (4)C1 and (1)C4 chair conformations were found to depend on the electronic properties and the size of the C2 substituent (F, N3 or OBn) and the aglycon, with higher exchange rates for the glycosyl triflates and smaller C2 substituents. Low temperature (19)F exchange spectroscopy experiments showed that the covalently bound anomeric triflates did not exchange with free triflate species present in the reaction mixture. To relate the conformational behavior of the intermediate triflates to their reactivity in a glycosylation reaction, their relative reactivity was determined via competition reactions monitored by (1)H NMR spectroscopy at low temperature. The 2-O-benzyl ether compound was found to be most reactive whereas the 2-fluoro compound - the most flexible of the studied compounds - was least reactive. Whereas the ring-flip of the mannuronic acids is important for the enhanced reactivity of the donors, the rate of the ring-flip has little influence on the relative reactivity.

Genetic Analysis of Collective Motility of Paenibacillus sp. NAIST15-1

PubMed Central

Kobayashi, Kazuo; Kanesaki, Yu

2016-01-01

Bacteria have developed various motility mechanisms to adapt to a variety of solid surfaces. A rhizosphere isolate, Paenibacillus sp. NAIST15-1, exhibited unusual motility behavior. When spotted onto 1.5% agar media, Paenibacillus sp. formed many colonies, each of which moved around actively at a speed of 3.6 μm/sec. As their density increased, each moving colony began to spiral, finally forming a static round colony. Despite its unusual motility behavior, draft genome sequencing revealed that both the composition and organization of flagellar genes in Paenibacillus sp. were very similar to those in Bacillus subtilis. Disruption of flagellar genes and flagellar stator operons resulted in loss of motility. Paenibacillus sp. showed increased transcription of flagellar genes and hyperflagellation on hard agar media. Thus, increased flagella and their rotation drive Paenibacillus sp. motility. We also identified a large extracellular protein, CmoA, which is conserved only in several Paenibacillus and related species. A cmoA mutant could neither form moving colonies nor move on hard agar media; however, motility was restored by exogenous CmoA. CmoA was located around cells and enveloped cell clusters. Comparison of cellular behavior between the wild type and cmoA mutant indicated that extracellular CmoA is involved in drawing water out of agar media and/or smoothing the cell surface interface. This function of CmoA probably enables Paenibacillus sp. to move on hard agar media. PMID:27764113

Multidither Adaptive Algorithms

DTIC Science & Technology

1976-09-01

Influence Function Profiles of Beryllium Mirror 32 11 Three-Dimensional View of Central-Actuator Influence for RADC Beryllium Mirror 33 12 Contour Lines...installed at this writing. Some preliminary tests on the mirror have determined its excur- sion sensitivity, influence function , and frequency...The frequency response shows some unusual resonance behavior, but is usable to at least 30 kHz. The 1 5 influence function has a shape given

Changes in Sensory Responsiveness in Behaving Primates.

DTIC Science & Technology

1986-07-14

controlled behavioral training and monitoring, and electrophysiological recording in awake , behaving monkeys. All I, research equipment listed in the original...recording from the sensorimotor cortices was conducted on May 21. Under general anesthesia, a craniotomy was performed over the pre- and postcentral cortices...Department of Neurosurgery at U.T. Dr. Klein is somewhat unusual in that he has had previous experience recording from awake , behaving monkeys. The experience

Telemicrobiology for Mission Support in the Field of Infectious Diseases

DTIC Science & Technology

2010-04-01

bacterial meningitis so that important additional verification was lacking. Microscopic diagnoses in the expert laboratory also rarely yield a...With bacterial infections, depending on the country of deployment, also unusual resistance behavior of the pathogens will occur because numerous...missions of the US Forces in the recent years, well-documented with respect to epidemiology , the weekly incidence of infectious diseases was always

Effect of cryopreservation on the pre-hatching behavior in the Mexican fruit fly Anastrepha ludens Loew (Diptera, Tephritidae)

USDA-ARS?s Scientific Manuscript database

In a sampling of untreated embryos of Mexican fruit fly, Anastrepha ludens, the cumulative hatch percentage was 84.77±7.8% of which ~70% of the larvae eclosed through the posterior pole of the egg. This is due to an unusual and seemingly energy demanding act of flipping of the fully developed pre-ha...

Wholesale Provisioning Models: Model Evaluation.

DTIC Science & Technology

1986-05-01

AN/UYK-21 lacked consistency. The reasons for such "unusual" behavior were not obvious to SPCC personnel. Fortunately, the impact of these...19 X(I)=O RISKO0.OI RSK(I)0O.O 20 BT=BT+C(I)*X(I) IF(BT.LE.B1)GO TO 99 C SINCE M4AX DEPTH COMSUMES MORE THAN THE AVAILABLE BUDGET THE C OTHER END OF

Examining the Impact of Covariates on Anchor Tests to Ascertain Quality over Time in a College Admissions Test

ERIC Educational Resources Information Center

Wiberg, Marie; von Davier, Alina A.

2017-01-01

We propose a comprehensive procedure for the implementation of a quality control process of anchor tests for a college admissions test with multiple consecutive administrations. We propose to examine the anchor tests and their items in connection with covariates to investigate if there was any unusual behavior in the anchor test results over time…

Generalized atrophic dells in a newborn.

PubMed

Buka, Robert L; Roberts, Brandie J; Resh, Brooke; Newbury, Robert; Cunningham, Bari B

2006-07-01

Infantile myofibromatosis (IM) is a nonmetastasizing locally invasive neoplasm. The behavior of the tumor is more hamartomatous than tumoral, and it is unclear whether the cell of origin is a fibroblast or a smooth muscle myocyte. Lesions typically present during infancy and range in size from a few millimeters to several centimeters. We present an unusual case of a patient with an atrophic variant of IM.

Stretched-to-compressed-exponential crossover observed in the electrical degradation kinetics of some spinel-metallic screen-printed structures

NASA Astrophysics Data System (ADS)

Balitska, V.; Shpotyuk, O.; Brunner, M.; Hadzaman, I.

2018-02-01

Thermally-induced (170 °C) degradation-relaxation kinetics is examined in screen-printed structures composed of spinel Cu0.1Ni0.1Co1.6Mn1.2O4 ceramics with conductive Ag or Ag-Pd layered electrodes. Structural inhomogeneities due to Ag and Ag-Pd diffusants in spinel phase environment play a decisive role in non-exponential kinetics of negative relative resistance drift. If Ag migration in spinel is inhibited by Pd addition due to Ag-Pd alloy, the kinetics attains stretched exponential behavior with ∼0.58 exponent, typical for one-stage diffusion in structurally-dispersive media. Under deep Ag penetration into spinel ceramics, as for thick films with Ag-layered electrodes, the degradation kinetics drastically changes, attaining features of two-step diffusing process governed by compressed-exponential dependence with power index of ∼1.68. Crossover from stretched- to compressed-exponential kinetics in spinel-metallic structures is mapped on free energy landscape of non-barrier multi-well system under strong perturbation from equilibrium, showing transition with a character downhill scenario resulting in faster than exponential decaying.

Decay of Solar Wind Turbulence behind Interplanetary Shocks

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

Pitňa, Alexander; Šafránková, Jana; Němeček, Zdeněk

We investigate the decay of magnetic and kinetic energies behind IP shocks with motivation to find a relaxation time when downstream turbulence reaches a usual solar wind value. We start with a case study that introduces computation techniques and quantifies a contribution of kinetic fluctuations to the general energy balance. This part of the study is based on high-time (31 ms) resolution plasma data provided by the Spektr-R spacecraft. On the other hand, a statistical part is based on 92 s Wind plasma and magnetic data and its results confirm theoretically established decay laws for kinetic and magnetic energies. Wemore » observe the power-law behavior of the energy decay profiles and we estimated the power-law exponents of both kinetic and magnetic energy decay rates as −1.2. We found that the decay of MHD turbulence does not start immediately after the IP shock ramp and we suggest that the proper decay of turbulence begins when a contribution of the kinetic processes becomes negligible. We support this suggestion with a detailed analysis of the decay of turbulence at the kinetic scale.« less

Thermal oxidative degradation kinetics of agricultural residues using distributed activation energy model and global kinetic model.

PubMed

Ren, Xiu'e; Chen, Jianbiao; Li, Gang; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi

2018-08-01

The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol -1 and 94.86-169.18 kJ mol -1 , respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.

Kinetic Energy Corrections for Slip-Stick Behavior in Brittle Adhesives

NASA Technical Reports Server (NTRS)

Macon, David J.; Anderson, Greg L.; McCool, Alex (Technical Monitor)

2001-01-01

Fracture mechanics is the study of the failure of a body that contains a flaw. In the energy balance approach to fracture mechanics, contributions from the external work and elastic strain energy are accounted for but rarely are corrections for the kinetic energy given. Under slip-stick conditions, part of the external work is expended as kinetic energy. The magnitude of this kinetic energy depends upon the shape of the crack. A specimen with a blunt crack will fail at a high load and the crack will catastrophically travel through the material until the kinetic energy is dissipated. Material with a sharp crack will fail at a lower load but will still be catastrophic in nature. A kinetic term is incorporated into the energy balance approach. This term accounts for the velocity of the crack after failure and how far the crack travels before arresting. This correction makes the shape of the initiation crack irrelevant. When applied to data generated by tapered double cantilever beam specimens under slip-stick conditions, the scatter in the measured critical strain energy release rate is significantly reduced.

Statistical Evaluations of Variations in Dairy Cows’ Milk Yields as a Precursor of Earthquakes

PubMed Central

Yamauchi, Hiroyuki; Hayakawa, Masashi; Asano, Tomokazu; Ohtani, Nobuyo; Ohta, Mitsuaki

2017-01-01

Simple Summary There are many reports of abnormal changes occurring in various natural systems prior to earthquakes. Unusual animal behavior is one of these abnormalities; however, there are few objective indicators and to date, reliability has remained uncertain. We found that milk yields of dairy cows decreased prior to an earthquake in our previous case study. In this study, we examined the reliability of decreases in milk yields as a precursor for earthquakes using long-term observation data. In the results, milk yields decreased approximately three weeks before earthquakes. We have come to the conclusion that dairy cow milk yields have applicability as an objectively observable unusual animal behavior prior to earthquakes, and dairy cows respond to some physical or chemical precursors of earthquakes. Abstract Previous studies have provided quantitative data regarding unusual animal behavior prior to earthquakes; however, few studies include long-term, observational data. Our previous study revealed that the milk yields of dairy cows decreased prior to an extremely large earthquake. To clarify whether the milk yields decrease prior to earthquakes, we examined the relationship between earthquakes of various magnitudes and daily milk yields. The observation period was one year. In the results, cross-correlation analyses revealed a significant negative correlation between earthquake occurrence and milk yields approximately three weeks beforehand. Approximately a week and a half beforehand, a positive correlation was revealed, and the correlation gradually receded to zero as the day of the earthquake approached. Future studies that use data from a longer observation period are needed because this study only considered ten earthquakes and therefore does not have strong statistical power. Additionally, we compared the milk yields with the subionospheric very low frequency/low frequency (VLF/LF) propagation data indicating ionospheric perturbations. The results showed that anomalies of VLF/LF propagation data emerged prior to all of the earthquakes following decreases in milk yields; the milk yields decreased earlier than propagation anomalies. We mention how ultralow frequency magnetic fields are a stimulus that could reduce milk yields. This study suggests that dairy cow milk yields decrease prior to earthquakes, and that they might respond to stimuli emerging earlier than ionospheric perturbations. PMID:28282889

The General Isothermal Oxidation Behavior of Cu-8Cr-4Nb

NASA Technical Reports Server (NTRS)

Thomas-Ogbuji, L. U.; Gray, Hugh R. (Technical Monitor)

2002-01-01

Oxidation kinetics of Cu-8Cr-4Nb was investigated by TGA (thermogravimetric) exposures between 500 and 900-C (at 25-50 C intervals) and the oxide scale morphologies examined by microscopy and micro-analysis. Because Cu-8Cr-4Nb is comprised of fine Cr2Nb precipitates in a Cu matrix, the results were interpreted by comparison with the behavior of copper (OFHC) and 'NARloy-Z' (a rival candidate material for thrust cell liner applications in advanced rocket engines) under the same conditions. While NARloy-Z and Cu exhibited identical oxidation behavior, Cu-8Cr-4Nb differed markedly in several respects: below approx. 700 C its oxidation rates were significantly lower than those of Cu; At higher temperatures its oxidation rates fell into two categories: an initial rate exceeding that of Cu, and a terminal rate comparable to that of Cu. Differences in oxide morphologies paralleled the kinetic differences at higher temperature: While NARloy-Z and Cu produced a uniform oxide scale of Cu2O inner layer and CuO outer layer, the inner (Cu2O) layer on Cu-8Cr-4Nb was stratified, with a highly porous/spongy inner stratum (responsible for the fast initial kinetics) and a dense/blocky outer stratum (corresponding to the slow terminal kinetics). Single and spinel oxides of Nb and Cr were found at the interface between the oxide scale and Cu-8Cr-4Nb substrate and it appears that these oxides were responsible for its suppressed oxidation rates at the intermediate temperatures. No difference was found between Cu-8Cr-4Nb oxidation in air and in oxygen at 1.0 atm.