Sample records for find favorable reactions

  1. Benefit Finding, Affective Reactions to Diabetes Stress, and Diabetes Management among Early Adolescents

    PubMed Central

    Tran, Vincent; Wiebe, Deborah J.; Fortenberry, Katherine T.; Butler, Jorie M.; Berg, Cynthia A.

    2011-01-01

    Objective To examine whether benefit finding was associated with better adjustment among adolescents with diabetes by buffering negative affective reactions to diabetes stress and by promoting positive affective reactions. Design Early adolescents aged 10-14 with type 1 diabetes (n=252) described recent diabetes stressors, affective reactions, and perceived coping effectiveness. They also completed measures of benefit finding, depressive symptoms, and adherence. Metabolic control (i.e., HbA1c) was obtained from medical records. Main Outcome Measures The main outcome measures were perceived coping effectiveness, depressive symptoms, adherence, and HbA1c. Results Benefit finding was associated with lower depressive symptoms, higher perceived coping effectiveness and better adherence, and with higher positive as well as negative affective reactions to diabetes stress. Benefit finding interacted with negative affective reactions to predict depressive symptoms and HbA1c. Negative affective reactions to stress were associated with poorer adjustment among those with low benefit finding, but were unrelated or more weakly related to poor adjustment among those with high benefit finding. Positive affective reactions did not mediate associations between benefit finding and any outcome. Conclusions Consistent with a stress-buffering process, benefit finding may be a resource that buffers the disruptive aspects of negative affective reactions to stress for adolescents’ diabetes management. PMID:21401255

  2. Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol

    PubMed Central

    2015-01-01

    Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al. J. Chem. Phys.2014, 140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum under DFT by several fold. The approach also shows promise for free energy calculations when thermal noise can be controlled. PMID:25516726

  3. Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol

    DOE PAGES

    Kale, Seyit; Sode, Olaseni; Weare, Jonathan; ...

    2014-11-07

    Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al. J. Chem. Phys. 2014, 140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum undermore » DFT by several fold. In conclusion, the approach also shows promise for free energy calculations when thermal noise can be controlled.« less

  4. Immunohistopathological Findings of Severe Cutaneous Adverse Drug Reactions

    PubMed Central

    2017-01-01

    Diagnosis of severe cutaneous adverse drug reactions should involve immunohistopathological examination, which gives insight into the pathomechanisms of these disorders. The characteristic histological findings of erythema multiforme (EM), Stevens–Johnson syndrome (SJS), and toxic epidermal necrolysis (TEN) provide conclusive evidence demonstrating that SJS/TEN can be distinguished from EM. Established SJS/TEN shows full-thickness, extensive keratinocyte necrosis that develops into subepidermal bullae. Drug-induced hypersensitivity syndrome (DIHS) and exanthema in drug reaction with eosinophilia and systemic symptoms (DRESS) each display a variety of histopathological findings, which may partly correlate with the clinical manifestations. Although the histopathology of DRESS is nonspecific, the association of two or more of the four patterns—eczematous changes, interface dermatitis, acute generalized exanthematous pustulosis- (AGEP-) like patterns, and EM-like patterns—might appear in a single biopsy specimen, suggesting the diagnosis and severe cutaneous manifestations of DRESS. Cutaneous dendritic cells may be involved in the clinical course. AGEP typically shows spongiform superficial epidermal pustules accompanied with edema of the papillary dermis and abundant mixed perivascular infiltrates. Mutations in IL36RN may have a definite effect on pathological similarities between AGEP and generalized pustular psoriasis. PMID:29226159

  5. Rethinking spontaneous giving: Extreme time pressure and ego-depletion favor self-regarding reactions

    PubMed Central

    Capraro, Valerio; Cococcioni, Giorgia

    2016-01-01

    Previous experimental studies suggest that cooperation in one-shot anonymous interactions is, on average, spontaneous, rather than calculative. To explain this finding, it has been proposed that people internalize cooperative heuristics in their everyday life and bring them as intuitive strategies in new and atypical situations. Yet, these studies have important limitations, as they promote intuitive responses using weak time pressure or conceptual priming of intuition. Since these manipulations do not deplete participants’ ability to reason completely, it remains unclear whether cooperative heuristics are really automatic or they emerge after a small, but positive, amount of deliberation. Consistent with the latter hypothesis, we report two experiments demonstrating that spontaneous reactions in one-shot anonymous interactions tend to be egoistic. In doing so, our findings shed further light on the cognitive underpinnings of cooperation, as they suggest that cooperation in one-shot interactions is not automatic, but appears only at later stages of reasoning. PMID:27251762

  6. Rethinking spontaneous giving: Extreme time pressure and ego-depletion favor self-regarding reactions.

    PubMed

    Capraro, Valerio; Cococcioni, Giorgia

    2016-06-02

    Previous experimental studies suggest that cooperation in one-shot anonymous interactions is, on average, spontaneous, rather than calculative. To explain this finding, it has been proposed that people internalize cooperative heuristics in their everyday life and bring them as intuitive strategies in new and atypical situations. Yet, these studies have important limitations, as they promote intuitive responses using weak time pressure or conceptual priming of intuition. Since these manipulations do not deplete participants' ability to reason completely, it remains unclear whether cooperative heuristics are really automatic or they emerge after a small, but positive, amount of deliberation. Consistent with the latter hypothesis, we report two experiments demonstrating that spontaneous reactions in one-shot anonymous interactions tend to be egoistic. In doing so, our findings shed further light on the cognitive underpinnings of cooperation, as they suggest that cooperation in one-shot interactions is not automatic, but appears only at later stages of reasoning.

  7. Modulating the DNA polymerase β reaction equilibrium to dissect the reverse reaction

    PubMed Central

    Shock, David D.; Freudenthal, Bret D.; Beard, William A.; Wilson, Samuel H.

    2017-01-01

    DNA polymerases catalyze efficient and high fidelity DNA synthesis. While this reaction favors nucleotide incorporation, polymerases also catalyze a reverse reaction, pyrophosphorolysis, removing the DNA primer terminus and generating deoxynucleoside triphosphates. Since pyrophosphorolysis can influence polymerase fidelity and sensitivity to chain-terminating nucleosides, we analyzed pyrophosphorolysis with human DNA polymerase β and found the reaction to be inefficient. The lack of a thio-elemental effect indicated that it was limited by a non-chemical step. Utilizing a pyrophosphate analog, where the bridging oxygen is replaced with an imido-group (PNP), increased the rate of the reverse reaction and displayed a large thio-elemental effect indicating that chemistry was now rate determining. Time-lapse crystallography with PNP captured structures consistent with a chemical equilibrium that favored the reverse reaction. These results highlight the importance of the bridging atom between the β- and γ-phosphates of the incoming nucleotide in reaction chemistry, enzyme conformational changes, and overall reaction equilibrium. PMID:28759020

  8. Vitamin C with metabolites: additional analysis suggests favorable changes in oxalate.

    PubMed

    Moyad, Mark A; Combs, Maile A; Baisley, Joshua E; Evans, Malkanthi

    2009-01-01

    A previously published randomized trial found a significant difference in the proportion of individuals experiencing oxalate reduction with a vitamin C with metabolites product compared with ascorbic acid (vitamin C). This represented a notable finding, which argued against the possibility of a chance finding due to the design and consistency of results. However, these researchers believed it was necessary to further analyze this study to continue to garner more insight on the strength or weakness of original findings. All favorable, neutral, and non-favorable changes of 24-hour oxalate from the previous clinical trial were grouped. Oxalate was considered to "decrease" or "increase" with each intervention only if a 10% or larger change occurred in the 24-hour oxalate baseline value when taking one product compared to another. A greater proportion of subjects taking both products at different time periods experienced favorable oxalate changes with vitamin C with metabolites product compared to ascorbic acid. If this reflects the true clinical scenario, this would represent an important clinical finding on a population level because at least 20% more individuals would experience a more favorable change. Regardless, this further analysis continues to suggest that the original observations were valid and could have positive clinical implications for some patients.

  9. Exit channel dynamics in a micro-hydrated SN2 reaction of the hydroxyl anion.

    PubMed

    Otto, R; Brox, J; Trippel, S; Stei, M; Best, T; Wester, R

    2013-08-29

    We report on the reaction dynamics of the monosolvated SN2 reaction of cold OH(-)(H2O) with CH3I that have been studied using crossed beam ion imaging. Two SN2 reaction channels are possible for this reaction: Formation of unsolvated I(-) and of solvated I(-)(H2O) products. We find a strong preference for the formation of unsolvated I(-) reaction products with respect to the energetically favored reaction toward solvated I(-)(H2O). Angle differential cross section measurements reveal similar velocity and angular distributions for all solvated and parts of the unsolvated reaction products. We furthermore find that the contribution of these two products to the total product flux can be described by the same collision energy dependence. We interpret our findings in terms of a joint reaction mechanism in which a CH3OH(H2O)···I(-) complex is formed that decays into either solvated or unsolvated products. Quantum chemical calculation are used to support this assumption.

  10. Spontaneous Hedonic Reactions to Social Media Cues.

    PubMed

    van Koningsbruggen, Guido M; Hartmann, Tilo; Eden, Allison; Veling, Harm

    2017-05-01

    Why is it so difficult to resist the desire to use social media? One possibility is that frequent social media users possess strong and spontaneous hedonic reactions to social media cues, which, in turn, makes it difficult to resist social media temptations. In two studies (total N = 200), we investigated less-frequent and frequent social media users' spontaneous hedonic reactions to social media cues using the Affect Misattribution Procedure-an implicit measure of affective reactions. Results demonstrated that frequent social media users showed more favorable affective reactions in response to social media (vs. control) cues, whereas less-frequent social media users' affective reactions did not differ between social media and control cues (Studies 1 and 2). Moreover, the spontaneous hedonic reactions to social media (vs. control) cues were related to self-reported cravings to use social media and partially accounted for the link between social media use and social media cravings (Study 2). These findings suggest that frequent social media users' spontaneous hedonic reactions in response to social media cues might contribute to their difficulties in resisting desires to use social media.

  11. Molecular crowding favors reactivity of a human ribozyme under physiological ionic conditions.

    PubMed

    Strulson, Christopher A; Yennawar, Neela H; Rambo, Robert P; Bevilacqua, Philip C

    2013-11-19

    In an effort to relate RNA folding to function under cellular-like conditions, we monitored the self-cleavage reaction of the human hepatitis delta virus-like CPEB3 ribozyme in the background of physiological ionic concentrations and various crowding and cosolute agents. We found that at physiological free Mg(2+) concentrations (∼0.1-0.5 mM), both crowders and cosolutes stimulate the rate of self-cleavage, up to ∼6-fold, but that in 10 mM Mg(2+) (conditions widely used for in vitro ribozyme studies) these same additives have virtually no effect on the self-cleavage rate. We further observe a dependence of the self-cleavage rate on crowder size, wherein the level of rate stimulation is diminished for crowders larger than the size of the unfolded RNA. Monitoring effects of crowding and cosolute agents on rates in biological amounts of urea revealed additive-promoted increases at both low and high Mg(2+) concentrations, with a maximal stimulation of more than 10-fold and a rescue of the rate to its urea-free values. Small-angle X-ray scattering experiments reveal a structural basis for this stimulation in that higher-molecular weight crowding agents favor a more compact form of the ribozyme in 0.5 mM Mg(2+) that is essentially equivalent to the form under standard ribozyme conditions of 10 mM Mg(2+) without a crowder. This finding suggests that at least a portion of the rate enhancement arises from favoring the native RNA tertiary structure. We conclude that cellular-like crowding supports ribozyme reactivity by favoring a compact form of the ribozyme, but only under physiological ionic and cosolute conditions.

  12. Deformation of interface in a partially miscible system during favorable displacement

    NASA Astrophysics Data System (ADS)

    Suzuki, Ryuta; Nagatsu, Yuichiro; Mishra, Manoranjan; Ban, Takahiko

    2017-11-01

    The Saffman-Taylor instability triggers a well-known viscous fingering (VF, called unfavorable displacement), occurring when a less viscous fluid displaces a more viscous one in porous media or in a Hele-Shaw cell because the boundary of the two fluids becomes hydrodynamically unstable. In the reverse situation (called favorable displacement) in which a more viscous fluid displaces a less viscous one, no instabilities occur due to hydrodynamically stable system. It has been reported that the favorable displacements become unstable by several physicochemical effects. So far, studies of both displacements have focused on fluids that are either fully miscible or immiscible. However, little attention has been paid to displacements in partially miscible system. Here, we have discovered that a partial miscibility triggers fingering instability in a favorable displacement without any chemical reactions. The occurrence of this new instability is induced by not hydrodynamic effects but a thermodynamic effect that is so-called Korteweg effect in which convection is induced during phase separation process in a partially miscible system.

  13. Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

    NASA Technical Reports Server (NTRS)

    Liechty, Derek S.; Lewis, Mark J.

    2010-01-01

    Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

  14. GRIZZLY/FAVOR Interface Project Report

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

    Dickson, Terry L; Williams, Paul T; Yin, Shengjun

    As part of the Light Water Reactor Sustainability (LWRS) Program, the objective of the GRIZZLY/FAVOR Interface project is to create the capability to apply GRIZZLY 3-D finite element (thermal and stress) analysis results as input to FAVOR probabilistic fracture mechanics (PFM) analyses. The one benefit of FAVOR to Grizzly is the PROBABILISTIC capability. This document describes the implementation of the GRIZZLY/FAVOR Interface, the preliminary verification and tests results and a user guide that provides detailed step-by-step instructions to run the program.

  15. An automated method to find reaction mechanisms and solve the kinetics in organometallic catalysis.

    PubMed

    Varela, J A; Vázquez, S A; Martínez-Núñez, E

    2017-05-01

    A novel computational method is proposed in this work for use in discovering reaction mechanisms and solving the kinetics of transition metal-catalyzed reactions. The method does not rely on either chemical intuition or assumed a priori mechanisms, and it works in a fully automated fashion. Its core is a procedure, recently developed by one of the authors, that combines accelerated direct dynamics with an efficient geometry-based post-processing algorithm to find transition states (Martinez-Nunez, E., J. Comput. Chem. 2015 , 36 , 222-234). In the present work, several auxiliary tools have been added to deal with the specific features of transition metal catalytic reactions. As a test case, we chose the cobalt-catalyzed hydroformylation of ethylene because of its well-established mechanism, and the fact that it has already been used in previous automated computational studies. Besides the generally accepted mechanism of Heck and Breslow, several side reactions, such as hydrogenation of the alkene, emerged from our calculations. Additionally, the calculated rate law for the hydroformylation reaction agrees reasonably well with those obtained in previous experimental and theoretical studies.

  16. Bis(amino)cyclopropenylidene (BAC) catalyzed aza-benzoin reaction.

    PubMed

    Wilde, Myron M D; Gravel, Michel

    2014-10-17

    A bis(amino)cyclopropenylidene (BAC) catalyzed aza-benzoin reaction between aldehydes and phosphinoyl imines has been developed. The reaction is general with a wide range of aromatic aldehydes and aromatic imines. The reaction displays excellent chemoselectivity favoring aza-benzoin products over homobenzoin products.

  17. Reactions of protective service workers towards people who stutter.

    PubMed

    Li, Jian; Arnold, Hayley S; Beste-Guldborg, Ann

    2016-12-01

    This study sought to assess whether protective service workers differ from people in non-protective services occupations in their intended reactions towards people who stutter (PWS). Analyses were based on questionnaire responses regarding intended reactions toward PWS from 171 protective services workers and 2595 non-protective services workers in the United States. A propensity score matching procedure was used to identify a comparison group of non-protective services workers for the protective services workers. The matching covariate variables included age, gender, years of education, familiarity with PWS, and beliefs about PWS. Findings indicated that protective services workers had less helpful intended behavioral reactions and more negative affective reactions towards PWS than the matched non-protective services workers. Examination of the matching covariate variables in the larger sample also indicated that protective services workers had less accurate beliefs about PWS compared to respondents not in protective services professions. Less favorable intended reactions of protective services workers toward PWS indicate a need for protective services workers to receive training in best practices when interacting with PWS. Copyright © 2016 Elsevier Inc. All rights reserved.

  18. Young and old drivers favor curbs on their own driving privileges

    DOT National Transportation Integrated Search

    2000-01-15

    Initiatives aimed at reducing car crashes among the youngest and oldest drivers are favored by most Americans, including younger and older people whose own driving might be curtailed. A national survey conducted recently finds that new safety measure...

  19. Psychological foundations of xenophilia: the role of major personality traits in predicting favorable attitudes toward cross-cultural contact and exploration.

    PubMed

    Stürmer, Stefan; Benbow, Alison E F; Siem, Birte; Barth, Markus; Bodansky, Alexander N; Lotz-Schmitt, Katharina

    2013-11-01

    Building on an integration of research findings on intergroup behavior from multiple fields of scientific inquiry (biological and cultural paleoanthropology, social psychology), as well as research on the HEXACO personality framework (e.g., Ashton & Lee, 2007), 3 independent studies (total N = 1,007) were conducted to introduce and test a fresh personality perspective on human xenophilia. Even though the studies focused on different criteria (Study 1: favorable attitudes toward contact with immigrants, Study 2: habitual cross-cultural exploration, Study 3: favorable attitudes toward contact with indigenous people) and employed different operationalizations of major personality traits (the HEXACO Personality Inventory-Revised [HEXACO-PI-R], the 10-item Big Five Inventory [BFI-10]) results were remarkably similar. First, path analyses confirmed that major personality traits were significant and direct predictors of xenophilia that were independent of the contributions of individual differences commonly predicting xenophobic reactions across studies. Second, and in line with the authors' more specific hypotheses, hierarchical regression analyses also corroborated that individual differences in the levels of endeavor-related personality traits (i.e., eXtraversion, Openness, and Conscientiousness) had a substantially greater power in predicting individual differences in xenophilia than individual differences in levels of altruism/cooperation-related traits (i.e., Honesty-Humility, Emotionality, and Agreeableness). The implications of these findings for more general psychological theorizing on human sociality are discussed. PsycINFO Database Record (c) 2013 APA, all rights reserved

  20. Why Do Enolate Anions Favor O-Alkylation over C-Alkylation in the Gas Phase? The Roles of Resonance and Inductive Effects in the Gas-Phase SN2 Reaction between the Acetaldehyde Enolate Anion and Methyl Fluoride.

    PubMed

    Seitz, Christian G; Zhang, Huaiyu; Mo, Yirong; Karty, Joel M

    2016-05-06

    Contributions by resonance and inductive effects toward the net activation barrier were determined computationally for the gas-phase SN2 reaction between the acetaldehyde enolate anion and methyl fluoride, for both O-methylation and C-methylation, in order to understand why this reaction favors O-methylation. With the use of the vinylogue extrapolation methodology, resonance effects were determined to contribute toward increasing the size of the barrier by about 9.5 kcal/mol for O-methylation and by about 21.2 kcal/mol for C-methylation. Inductive effects were determined to contribute toward increasing the size of the barrier by about 1.7 kcal/mol for O-methylation and 4.2 kcal/mol for C-methylation. Employing our block-localized wave function methodology, we determined the contributions by resonance to be 12.8 kcal/mol for O-methylation and 22.3 kcal/mol for C-methylation. Thus, whereas inductive effects have significant contributions, resonance is the dominant factor that leads to O-methylation being favored. More specifically, resonance serves to increase the size the barrier for C-methylation significantly more than it does for O-methylation.

  1. Possibility of the Nonenzymatic Browning (Maillard) Reaction in the ISM

    NASA Astrophysics Data System (ADS)

    Jalbout, Abraham F.; Shipar, M. Abul Haider

    2008-04-01

    The possibility of the occurrence of the nonenzymatic browning reaction in the gaseous phase in the interstellar medium has been investigated by using Density Functional Theory computations. Mechanisms for the reactions between formaldehyde ( Fald) + glycine ( Gly), Fald + NH 3 and Fald + methylamine ( MeAm) have been proposed, and the possibility of the formation of different compounds in the proposed mechanisms has been evaluated through calculating the Gibb's free energy changes for different steps of the reaction, by following the total mass balance. The Fald + Gly reaction under basic conditions is found as the most favorable for producing 1-methyl-amino methene or 1-methyl-amino methelene ( MAM). The reaction under acidic conditions is found to be the least favorable for producing MAM. The Fald + NH 3 reaction is found to be plausible for the production of MeAm, which can participate by reaction with Fald, resulting in the formation of MAM.

  2. Antibody-mediated cofactor-driven reactions

    DOEpatents

    Schultz, Peter G.

    1993-01-01

    Chemical reactions capable of being rate-enhanced by auxiliary species which interact with the reactants but do not become chemically bound to them in the formation of the final product are performed in the presence of antibodies which promote the reactions. The antibodies contain regions within their antigen binding sites which recognize the auxiliary species in a conformation which promotes the reaction. The antigen binding site frequently recognizes a particular transition state complex or other high energy complex along the reaction coordinate, thereby promoting the progress of the reaction along the desired route as opposed to other less favorable routes. Various classes of reaction together with appropriate antigen binding site specificities tailored for each are disclosed.

  3. Favorable prognostic role of tropomodulins in neuroblastoma.

    PubMed

    Bettinsoli, Paola; Ferrari-Toninelli, Giulia; Bonini, Sara Anna; Guarienti, Michela; Cangelosi, Davide; Varesio, Luigi; Memo, Maurizio

    2018-06-05

    Neuroblastoma is a pediatric tumor of the sympatoadrenal lineage of the neural crest characterized by high molecular and clinical heterogeneity, which are the main causes of the poor response to standard multimodal therapy. The identification of new and selective biomarkers is important to improve our knowledge on the mechanisms of neuroblastoma progression and to find the targets for innovative cancer therapies. This study identifies a positive correlation among tropomodulins (TMODs) proteins expression and neuroblastoma progression. TMODs bind the pointed end of actin filaments, regulate polymerization and depolymerization processes modifying actin cytoskeletal dynamic and influencing neuronal development processes. Expression levels of TMODs genes were analyzed in 17 datasets comprising different types of tumors, including neuroblastoma, and it was demonstrated that high levels of tropomodulin1 ( TMOD1 ) and tropomodulin 2 ( TMOD2 ) correlate positively with high survival probability and with favorable clinical and molecular characteristics. Functional studies on neuroblastoma cell lines, showed that TMOD1 knockin induced cell cycle arrest, cell proliferation arrest and a mature functional differentiation. TMOD1 overexpression was responsible for particular cell morphology and biochemical changes which directed cells towards a neuronal favorable differentiation profile. TMOD1 downregulation also induced cell proliferation arrest but caused the loss of mature cell differentiation and promoted the development of neuroendocrine cellular characteristics, delineating an aggressive and unfavorable tumor behavior. Overall, these data indicated that TMODs are favorable prognostic biomarkers in neuroblastoma and we believe that they could contribute to unravel a new pathophysiological mechanism of neuroblastoma resistance contributing to the design of personalized therapeutics opportunities.

  4. ReactionMap: an efficient atom-mapping algorithm for chemical reactions.

    PubMed

    Fooshee, David; Andronico, Alessio; Baldi, Pierre

    2013-11-25

    Large databases of chemical reactions provide new data-mining opportunities and challenges. Key challenges result from the imperfect quality of the data and the fact that many of these reactions are not properly balanced or atom-mapped. Here, we describe ReactionMap, an efficient atom-mapping algorithm. Our approach uses a combination of maximum common chemical subgraph search and minimization of an assignment cost function derived empirically from training data. We use a set of over 259,000 balanced atom-mapped reactions from the SPRESI commercial database to train the system, and we validate it on random sets of 1000 and 17,996 reactions sampled from this pool. These large test sets represent a broad range of chemical reaction types, and ReactionMap correctly maps about 99% of the atoms and about 96% of the reactions, with a mean time per mapping of 2 s. Most correctly mapped reactions are mapped with high confidence. Mapping accuracy compares favorably with ChemAxon's AutoMapper, versions 5 and 6.1, and the DREAM Web tool. These approaches correctly map 60.7%, 86.5%, and 90.3% of the reactions, respectively, on the same data set. A ReactionMap server is available on the ChemDB Web portal at http://cdb.ics.uci.edu .

  5. Insulin-sensitive obese children display a favorable metabolic profile.

    PubMed

    Vukovic, Rade; Mitrovic, Katarina; Milenkovic, Tatjana; Todorovic, Sladjana; Soldatovic, Ivan; Sipetic-Grujicic, Sandra; Zdravkovic, Dragan

    2013-02-01

    Most of what is known about the metabolically healthy obese phenomenon is derived from studies in the adult population and no standardized criteria to identify these individuals exist to date. The aim of this study was to determine if the preserved insulin sensitivity evaluated by homeostatic model assessment of insulin resistance (HOMA-IR) index is associated with favorable metabolic profile in the obese children. We studied a group of 248 children and adolescents (150 female, 98 male), aged 5.9-18.9 years with diet-induced obesity (BMI >95th percentile). The entire cohort was divided into quartiles based on levels of insulin resistance determined by HOMA-IR index. Subjects in the lower quartile of HOMA-IR were classified as insulin-sensitive group (ISG), whereas children in the upper quartile were categorized as insulin-resistant group (IRG). The ISG subjects had values of HOMA-IR ≤2.75 while the children from the IRG group had HOMA-IR ≥6.16. Subjects from ISG group had lower basal β-cell activity and were less likely to have impaired fasting glucose or impaired glucose tolerance. Concentrations of LDL and total cholesterol, triglycerides, and transaminases were lower and HDL cholesterol levels were higher in ISG subjects. Findings obtained by the use of Matsuda index correlated well with the findings obtained by the use of HOMA-IR. Lower HOMA-IR values were significantly associated with favorable metabolic profile in studied children, which correlates with findings in the adult population and emphasizes the need for further, longitudinal studies of insulin resistance development in childhood obesity.

  6. Are organizational justice rules gendered? Reactions to men's and women's justice violations.

    PubMed

    Caleo, Suzette

    2016-10-01

    Research has shown that gender role prescriptions can bias reactions to men's and women's work behaviors. The current work draws upon this idea and extends it to consider violations of procedural and interactional justice rules. The results of four experimental studies demonstrate that men and women receive differential performance evaluation ratings and reward recommendations when they violate those organizational justice rules that coincide with the content of prescriptive gender stereotypes. Specifically, women were rated less favorably than men when they exhibited interactional injustice (Study 1 and Study 4), but not when they engaged in procedural injustice (Study 2). Findings also indicate that interactional justice violations (e.g., being impolite, not caring about the well-being of subordinates), but not procedural justice violations, are deemed less acceptable for female managers than male managers (Study 3). Overall, the findings suggest that reactions to injustice can be influenced by expectations of how men and women should behave. (PsycINFO Database Record (c) 2016 APA, all rights reserved).

  7. Reaching the limits of reciprocity in favor exchange: The effects of generous, stingy, and matched favor giving on social status.

    PubMed

    Ouyang, Kan; Xu, Erica; Huang, Xu; Liu, Wu; Tang, Yipeng

    2018-03-08

    Group members gain social status via giving favors to others, but why and when they do so remain unclear in the literature. Building on social exchange theory and social status literature, we identify three types of favor giving among group members (generous, stingy, and matched) and propose that an affective mechanism (i.e., gratitude) and a cognitive mechanism (i.e., perceived competence) underlie the relationship between favor giving and status attainment. Specifically, generous/stingy favor giving has a linear relationship with status attainment through both gratitude and perceived competence, whereas matched favor giving has a curvilinear relationship with status attainment only through perceived competence. An experimental study and a field study lend support to our propositions. Our study complements the literature by offering a complete picture of how three types of favor giving among group members shape their social status in different ways. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

  8. Favoring the unfavored: Selective electrochemical nitrogen fixation using a reticular chemistry approach

    PubMed Central

    Lee, Hiang Kwee; Koh, Charlynn Sher Lin; Lee, Yih Hong; Liu, Chong; Phang, In Yee; Han, Xuemei; Tsung, Chia-Kuang; Ling, Xing Yi

    2018-01-01

    Electrochemical nitrogen-to-ammonia fixation is emerging as a sustainable strategy to tackle the hydrogen- and energy-intensive operations by Haber-Bosch process for ammonia production. However, current electrochemical nitrogen reduction reaction (NRR) progress is impeded by overwhelming competition from the hydrogen evolution reaction (HER) across all traditional NRR catalysts and the requirement for elevated temperature/pressure. We achieve both excellent NRR selectivity (~90%) and a significant boost to Faradic efficiency by 10 percentage points even at ambient operations by coating a superhydrophobic metal-organic framework (MOF) layer over the NRR electrocatalyst. Our reticular chemistry approach exploits MOF’s water-repelling and molecular-concentrating effects to overcome HER-imposed bottlenecks, uncovering the unprecedented electrochemical features of NRR critical for future theoretical studies. By favoring the originally unfavored NRR, we envisage our electrocatalytic design as a starting point for high-performance nitrogen-to-ammonia electroconversion directly from water vapor–abundant air to address increasing global demand of ammonia in (bio)chemical and energy industries. PMID:29536047

  9. Effects of Maternal Mental Health on Engagement in Favorable Health Practices During Pregnancy

    PubMed Central

    Alhusen, Jeanne L.; Ayres, Lauren; DePriest, Kelli

    2016-01-01

    Introduction A woman’s health practices during pregnancy are associated with maternal and neonatal outcomes. Yet limited research has examined predictors of a woman’s engagement in favorable health practices, particularly in pregnant women at greatest risk for adverse outcomes. We examined the role of mental health on engagement in favorable health practices during pregnancy in a sample of pregnant, low-income, predominantly African American women. Methods A convenience sample of pregnant women was obtained from 3 obstetric clinics within a large Mid-Atlantic academic health system. Pregnant women (N = 166) completed measures of depression, social support, and engagement in favorable health practices during their second trimester. Six domains of health practices (ie, balance of rest and exercise, safety measures, nutrition, substance use, health care access, access to pregnancy-related information) were assessed by the Health Practices in Pregnancy Questionnaire-II. Multiple linear regression was used to examine predictors of engagement in favorable health practices. Results Fifty-nine percent of the study participants experienced depressive symptomatology during pregnancy. Multivariate linear regression modeling demonstrated that increased depressive symptoms, decreased social support, young age, and prepregnancy overweight or obesity were significant predictors of nonengagement in favorable health practices during pregnancy. Discussion Findings suggest that pregnant women with poor mental health (eg, depressive symptomatology, poor social support) and specific sociodemographic characteristics (eg, young age, prepregnancy overweight or obesity) were less likely to engage in favorable health practices during pregnancy. Health care providers are uniquely positioned to assess a woman’s mental health and related indicators to optimize pregnancy and neonatal outcomes. PMID:26849176

  10. Effects of Maternal Mental Health on Engagement in Favorable Health Practices During Pregnancy.

    PubMed

    Alhusen, Jeanne L; Ayres, Lauren; DePriest, Kelli

    2016-01-01

    A woman's health practices during pregnancy are associated with maternal and neonatal outcomes. Yet limited research has examined predictors of a woman's engagement in favorable health practices, particularly in pregnant women at greatest risk for adverse outcomes. We examined the role of mental health on engagement in favorable health practices during pregnancy in a sample of pregnant, low-income, predominantly African American women. A convenience sample of pregnant women was obtained from 3 obstetric clinics within a large Mid-Atlantic academic health system. Pregnant women (N = 166) completed measures of depression, social support, and engagement in favorable health practices during their second trimester. Six domains of health practices (ie, balance of rest and exercise, safety measures, nutrition, substance use, health care access, access to pregnancy-related information) were assessed by the Health Practices in Pregnancy Questionnaire-II. Multiple linear regression was used to examine predictors of engagement in favorable health practices. Fifty-nine percent of the study participants experienced depressive symptomatology during pregnancy. Multivariate linear regression modeling demonstrated that increased depressive symptoms, decreased social support, young age, and prepregnancy overweight or obesity were significant predictors of nonengagement in favorable health practices during pregnancy. Findings suggest that pregnant women with poor mental health (eg, depressive symptomatology, poor social support) and specific sociodemographic characteristics (eg, young age, prepregnancy overweight or obesity) were less likely to engage in favorable health practices during pregnancy. Health care providers are uniquely positioned to assess a woman's mental health and related indicators to optimize pregnancy and neonatal outcomes. © 2016 by the American College of Nurse-Midwives.

  11. Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides

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

    Zhu, Z.; Espenson, J.H.

    1996-10-16

    Methylrhenium trioxide (CH{sub 3}ReO{sub 3} or MTO) catalyzes several classes of reactions of ethyl diazoacetate, EDA. It is the first high valent oxo complex for carbene transfer. Under mild conditions and in the absence of other substrates, EDA was converted to a 9:1 mixture of diethyl maleate and diethyl fumarate. In the presence of alcohols, {alpha}-alkoxy ethyl acetates were obtained in good yield. The yields dropped for the larger and more branched alcohols, the balance of material being diethyl maleate and fumarate. An electron-donating group in the para position of phenols favors the formation of {alpha}-phenoxy ethyl acetates. The usemore » of EDA to form {alpha}-thio ethyl acetates and N-substituted glycine ethyl esters, on the other hand, is hardly affected by the size or structure of the parent thiol or amine, with all of these reactions proceeding in high yield. MTO-catalyzed cycloaddition reactions occur between EDA and aromatic imines, olefins, and carbonyl compounds. Three-membered ring products are formed: aziridines, cyclopropanes, and epoxides, respectively. The reactions favor the formation of trans products, and provide a convenient route for the preparation of aziridines. Intermediate carbenoid and nitrenoid species have been proposed. In the presence of an oxygen source such as an epoxide, ethyl diazoacetate and azibenzil are converted to an oxalic acid monoethyl ester and to benzil; at the same time the epoxide was converted to an olefin. 75 refs., 1 fig., 7 tabs.« less

  12. Why Koreans are More Likely to Favor "Apology," While Americans are More Likely to Favor "Thank You"

    ERIC Educational Resources Information Center

    Lee, Hye Eun; Park, Hee Sun

    2011-01-01

    Two studies investigated whether apologies or thanks are preferred in asking favors in the United States and Korea, and how this relates to perceptions of reduction in positive and negative face threats. In the first study (n = 224), participants composed an e-mail message where a favor was asked. In the second (n = 807), participants completed…

  13. 25 CFR 700.519 - Gifts, entertainment and favors.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 25 Indians 2 2011-04-01 2011-04-01 false Gifts, entertainment and favors. 700.519 Section 700.519... Employee Responsibility and Conduct § 700.519 Gifts, entertainment and favors. (a) Acceptance of gratuities, including gifts, entertainment and favors, (no matter how innocently tendered or received) from those who...

  14. 25 CFR 700.519 - Gifts, entertainment and favors.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 25 Indians 2 2014-04-01 2014-04-01 false Gifts, entertainment and favors. 700.519 Section 700.519... Employee Responsibility and Conduct § 700.519 Gifts, entertainment and favors. (a) Acceptance of gratuities, including gifts, entertainment and favors, (no matter how innocently tendered or received) from those who...

  15. 25 CFR 700.519 - Gifts, entertainment and favors.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 25 Indians 2 2012-04-01 2012-04-01 false Gifts, entertainment and favors. 700.519 Section 700.519... Employee Responsibility and Conduct § 700.519 Gifts, entertainment and favors. (a) Acceptance of gratuities, including gifts, entertainment and favors, (no matter how innocently tendered or received) from those who...

  16. 25 CFR 700.519 - Gifts, entertainment and favors.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 25 Indians 2 2013-04-01 2013-04-01 false Gifts, entertainment and favors. 700.519 Section 700.519... Employee Responsibility and Conduct § 700.519 Gifts, entertainment and favors. (a) Acceptance of gratuities, including gifts, entertainment and favors, (no matter how innocently tendered or received) from those who...

  17. Stochastic surface walking reaction sampling for resolving heterogeneous catalytic reaction network: A revisit to the mechanism of water-gas shift reaction on Cu

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

    2017-10-01

    Heterogeneous catalytic reactions on surface and interfaces are renowned for ample intermediate adsorbates and complex reaction networks. The common practice to reveal the reaction mechanism is via theoretical computation, which locates all likely transition states based on the pre-guessed reaction mechanism. Here we develop a new theoretical method, namely, stochastic surface walking (SSW)-Cat method, to resolve the lowest energy reaction pathway of heterogeneous catalytic reactions, which combines our recently developed SSW global structure optimization and SSW reaction sampling. The SSW-Cat is automated and massively parallel, taking a rough reaction pattern as input to guide reaction search. We present the detailed algorithm, discuss the key features, and demonstrate the efficiency in a model catalytic reaction, water-gas shift reaction on Cu(111) (CO + H2O → CO2 + H2). The SSW-Cat simulation shows that water dissociation is the rate-determining step and formic acid (HCOOH) is the kinetically favorable product, instead of the observed final products, CO2 and H2. It implies that CO2 and H2 are secondary products from further decomposition of HCOOH at high temperatures. Being a general purpose tool for reaction prediction, the SSW-Cat may be utilized for rational catalyst design via large-scale computations.

  18. 11 CFR 7.20 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 11 Federal Elections 1 2011-01-01 2011-01-01 false Gifts, entertainment, and favors. 7.20 Section... of Special Commission Employees § 7.20 Gifts, entertainment, and favors. Except as provided at 11 CFR... a gift, gratuity, loan, entertainment, or favor for himself or herself, or for another person...

  19. 11 CFR 7.20 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 11 Federal Elections 1 2010-01-01 2010-01-01 false Gifts, entertainment, and favors. 7.20 Section... of Special Commission Employees § 7.20 Gifts, entertainment, and favors. Except as provided at 11 CFR... a gift, gratuity, loan, entertainment, or favor for himself or herself, or for another person...

  20. Effects of Personality Disorders on Self-Other Agreement and Favorableness in Personality Descriptions.

    PubMed

    Tandler, Nancy; Mosch, Alice; Wolf, Annegret; Borkenau, Peter

    2016-10-01

    The authors studied effects of self-reported personality disorder (PD) symptoms on interpersonal perception, particularly self-other agreement and favorableness. Using a round-robin design, 52 groups of four well-acquainted students described themselves and each other on a measure of the Five-Factor model of personality and were administered a self-report screening instrument for DSM-IV (Axis 2). Using the Social Accuracy Model, the peer reports were predicted, across items, from either (a) the target person's self-reports plus the self-report item means, or (b) the items' social desirability. This resulted in separate coefficients for each peer-target dyad, indicating either self-other agreement or favorableness. These coefficients were then predicted from the PD scores of the target and the peer, using multilevel modeling. Main findings were that persons scoring high on PD measures agreed less with their peers on their unique personality characteristics, and that such persons were described by, and described their peers, less favorably.

  1. A Networks Approach to Modeling Enzymatic Reactions.

    PubMed

    Imhof, P

    2016-01-01

    Modeling enzymatic reactions is a demanding task due to the complexity of the system, the many degrees of freedom involved and the complex, chemical, and conformational transitions associated with the reaction. Consequently, enzymatic reactions are not determined by precisely one reaction pathway. Hence, it is beneficial to obtain a comprehensive picture of possible reaction paths and competing mechanisms. By combining individually generated intermediate states and chemical transition steps a network of such pathways can be constructed. Transition networks are a discretized representation of a potential energy landscape consisting of a multitude of reaction pathways connecting the end states of the reaction. The graph structure of the network allows an easy identification of the energetically most favorable pathways as well as a number of alternative routes. © 2016 Elsevier Inc. All rights reserved.

  2. Promising reciprocity: When proposing a favor for a request increases compliance even if the favor is not accepted.

    PubMed

    Guéguen, Nicolas; Meineri, Sébastien; Ruiz, Clément; Pascual, Alexandre

    2016-01-01

    Research has reported that reciprocity is an important social norm in relationships. In previous studies on reciprocity, participants' behavior was examined after receiving a favor from someone. In a series of field studies, we examined the effect of a statement that proved that a solicitor was someone who respected this principle. Confederates solicited participants for money or a cigarette in exchange for stamps or money, respectively. It was found that the participants complied more readily with the request in the promised favor condition, but most of them refused to take the promised favor. We conclude that individuals were led to help those who respected the putative norm of reciprocity in their social interaction.

  3. Adverse drug reactions induced by valproic acid.

    PubMed

    Nanau, Radu M; Neuman, Manuela G

    2013-10-01

    Valproic acid is a widely-used first-generation antiepileptic drug, prescribed predominantly in epilepsy and psychiatric disorders. VPA has good efficacy and pharmacoeconomic profiles, as well as a relatively favorable safety profile. However, adverse drug reactions have been reported in relation with valproic acid use, either as monotherapy or polytherapy with other antiepileptic drugs or antipsychotic drugs. This systematic review discusses valproic acid adverse drug reactions, in terms of hepatotoxicity, mitochondrial toxicity, hyperammonemic encephalopathy, hypersensitivity syndrome reactions, neurological toxicity, metabolic and endocrine adverse events, and teratogenicity. Copyright © 2013 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

  4. Uricase alkaline enzymosomes with enhanced stabilities and anti-hyperuricemia effects induced by favorable microenvironmental changes

    PubMed Central

    Zhou, Yunli; Zhang, Mi; He, Dan; Hu, Xueyuan; Xiong, Huarong; Wu, Jianyong; Zhu, Biyue; Zhang, Jingqing

    2016-01-01

    Enzyme therapy is an effective strategy to treat diseases. Three strategies were pursued to provide the favorable microenvironments for uricase (UCU) to eventually improve its features: using the right type of buffer to constitute the liquid media where catalyze reactions take place; entrapping UCU inside the selectively permeable lipid vesicle membranes; and entrapping catalase together with UCU inside the membranes. The nanosized alkaline enzymosomes containing UCU/(UCU and catalase) (ESU/ESUC) in bicine buffer had better thermal, hypothermal, acid-base and proteolytic stabilities, in vitro and in vivo kinetic characteristics, and uric acid lowering effects. The favorable microenvironments were conducive to the establishment of the enzymosomes with superior properties. It was the first time that two therapeutic enzymes were simultaneously entrapped into one enzymosome having the right type of buffer to achieve added treatment efficacy. The development of ESU/ESUC in bicine buffer provides valuable tactics in hypouricemic therapy and enzymosomal application. PMID:26823332

  5. Anatomy of an Elementary Chemical Reaction

    NASA Astrophysics Data System (ADS)

    Alexander, Andrew J.; Zare, Richard N.

    1998-09-01

    The alchemists of old sought the knowledge to transform one material to another-for example, base metals into gold-as a path to the elixir of life. As chemists have concerned themselves with the transformation from compound to compound, so they have become involved in trying to uncover the structures of molecules and the pathways that reactions follow. Classically, the study of reaction mechanisms in chemistry encompasses reaction kinetics, the study of velocities or rates of reactions, and reaction dynamics, the study of the nanoscopic motion and rearrangement of atoms during a reactive event. An essential aim of this article is to bring the reader to a favorable vantage point with a brief introduction to reactive dynamics, and from there to describe some examples of recent strategies that have been employed to promote a fundamental understanding of the anatomy of elementary chemical reactions. In the final section we ponder future directions for this rapidly evolving field of research.

  6. 19 CFR 200.735-105 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 19 Customs Duties 3 2011-04-01 2011-04-01 false Gifts, entertainment, and favors. 200.735-105...-105 Gifts, entertainment, and favors. (a) Except as provided in paragraph (b) of this section, no employee may solicit or accept, directly or indirectly, any gift, gratuity, favor, entertainment, loan, or...

  7. 19 CFR 200.735-105 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 19 Customs Duties 3 2014-04-01 2014-04-01 false Gifts, entertainment, and favors. 200.735-105...-105 Gifts, entertainment, and favors. (a) Except as provided in paragraph (b) of this section, no employee may solicit or accept, directly or indirectly, any gift, gratuity, favor, entertainment, loan, or...

  8. 19 CFR 200.735-105 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 19 Customs Duties 3 2012-04-01 2012-04-01 false Gifts, entertainment, and favors. 200.735-105...-105 Gifts, entertainment, and favors. (a) Except as provided in paragraph (b) of this section, no employee may solicit or accept, directly or indirectly, any gift, gratuity, favor, entertainment, loan, or...

  9. 22 CFR 1203.735-305 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 22 Foreign Relations 2 2013-04-01 2009-04-01 true Gifts, entertainment, and favors. 1203.735-305....735-305 Gifts, entertainment, and favors. (a) Except as provided in paragraph (b) of this section, a..., gratuity, loan, entertainment, or favor for the employee or another person, particularly one with whom the...

  10. 22 CFR 1203.735-305 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 22 Foreign Relations 2 2011-04-01 2009-04-01 true Gifts, entertainment, and favors. 1203.735-305....735-305 Gifts, entertainment, and favors. (a) Except as provided in paragraph (b) of this section, a..., gratuity, loan, entertainment, or favor for the employee or another person, particularly one with whom the...

  11. 22 CFR 1203.735-305 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 22 Foreign Relations 2 2012-04-01 2009-04-01 true Gifts, entertainment, and favors. 1203.735-305....735-305 Gifts, entertainment, and favors. (a) Except as provided in paragraph (b) of this section, a..., gratuity, loan, entertainment, or favor for the employee or another person, particularly one with whom the...

  12. 22 CFR 1203.735-305 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 22 Foreign Relations 2 2014-04-01 2014-04-01 false Gifts, entertainment, and favors. 1203.735-305....735-305 Gifts, entertainment, and favors. (a) Except as provided in paragraph (b) of this section, a..., gratuity, loan, entertainment, or favor for the employee or another person, particularly one with whom the...

  13. Spatial structure favors cooperative behavior in the snowdrift game with multiple interactive dynamics

    NASA Astrophysics Data System (ADS)

    Su, Qi; Li, Aming; Wang, Long

    2017-02-01

    Spatial reciprocity is generally regarded as a positive rule facilitating the evolution of cooperation. However, a few recent studies show that, in the snowdrift game, spatial structure still could be detrimental to cooperation. Here we propose a model of multiple interactive dynamics, where each individual can cooperate and defect simultaneously against different neighbors. We realize individuals' multiple interactions simply by endowing them with strategies relevant to probabilities, and every one decides to cooperate or defect with a probability. With multiple interactive dynamics, the cooperation level in square lattices is higher than that in the well-mixed case for a wide range of cost-to-benefit ratio r, implying that spatial structure favors cooperative behavior in the snowdrift game. Moreover, in square lattices, the most favorable strategy follows a simple relation of r, which confers theoretically the average evolutionary frequency of cooperative behavior. We further extend our study to various homogeneous and heterogeneous networks, which demonstrates the robustness of our results. Here multiple interactive dynamics stabilizes the positive role of spatial structure on the evolution of cooperation and individuals' distinct reactions to different neighbors can be a new line in understanding the emergence of cooperation.

  14. Favorable Attitudes Towards Serosorting are Associated With Overall Less Frequent Condom Use Among Young Black Men Having Sex Men

    PubMed Central

    Crosby, Richard A.; Mena, Leandro; Geter, Angelica

    2018-01-01

    This study determined whether YBMSM endorsing serosorting are less likely to use condoms. A questionnaire assessed men’s attitudes towards serosorting with a three-item scale; various sexual risk behaviors were measured using a 90-day recall period. Favorable attitudes toward serosorting were associated with a greater likelihood of condomless sex as a top (P<.001) and as a bottom (P<.001), as well as a lower likelihood of using condoms with main partners (P=.003). Findings suggest that YBMSM having favorable attitudes toward serosorting may be more likely to report condomless sex than their counterparts without favorable attitudes. PMID:26433647

  15. Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions.

    PubMed

    Williams, Peggy E; Marshall, David L; Poad, Berwyck L J; Narreddula, Venkateswara R; Kirk, Benjamin B; Trevitt, Adam J; Blanksby, Stephen J

    2018-06-04

    In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions. Graphical Abstract.

  16. Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions

    NASA Astrophysics Data System (ADS)

    Williams, Peggy E.; Marshall, David L.; Poad, Berwyck L. J.; Narreddula, Venkateswara R.; Kirk, Benjamin B.; Trevitt, Adam J.; Blanksby, Stephen J.

    2018-06-01

    In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions.

  17. Evaluation of an S-system root-finding method for estimating parameters in a metabolic reaction model.

    PubMed

    Iwata, Michio; Miyawaki-Kuwakado, Atsuko; Yoshida, Erika; Komori, Soichiro; Shiraishi, Fumihide

    2018-02-02

    In a mathematical model, estimation of parameters from time-series data of metabolic concentrations in cells is a challenging task. However, it seems that a promising approach for such estimation has not yet been established. Biochemical Systems Theory (BST) is a powerful methodology to construct a power-law type model for a given metabolic reaction system and to then characterize it efficiently. In this paper, we discuss the use of an S-system root-finding method (S-system method) to estimate parameters from time-series data of metabolite concentrations. We demonstrate that the S-system method is superior to the Newton-Raphson method in terms of the convergence region and iteration number. We also investigate the usefulness of a translocation technique and a complex-step differentiation method toward the practical application of the S-system method. The results indicate that the S-system method is useful to construct mathematical models for a variety of metabolic reaction networks. Copyright © 2018 Elsevier Inc. All rights reserved.

  18. 18 CFR 706.303 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 18 Conservation of Power and Water Resources 2 2012-04-01 2012-04-01 false Gifts, entertainment....303 Gifts, entertainment, and favors. (a) Except as provided in paragraph (b) of this section a..., entertainment, or favor for himself or another person, particularly one with whom he has family, business, or...

  19. Methanol decomposition reactions over a boron-doped graphene supported Ru-Pt catalyst.

    PubMed

    Damte, Jemal Yimer; Lyu, Shang-Lin; Leggesse, Ermias Girma; Jiang, Jyh Chiang

    2018-04-04

    The decomposition of methanol is currently attracting research attention due to the potential widespread applications of its end products. In this work, density functional theory (DFT) calculations have been performed to investigate the adsorption and decomposition of methanol on a Ru-Pt/boron doped graphene surface. We find that the most favorable reaction pathway is methanol (CH3OH) decomposition through O-H bond breaking to form methoxide (CH3O) as the initial step, followed by further dehydrogenation steps which generate formaldehyde (CH2O), formyl (CHO), and carbon monoxide (CO). The calculations illustrate that CH3OH and CO groups prefer to adsorb at the Ru-top sites, while CH2OH, CH3O, CH2O, CHO, and H2 groups favor the Ru-Pt bridge sites, indicating the preference of Ru atoms to adsorb the active intermediates or species having lone-pair electrons. Based on the results, it is found that the energy barrier for CH3OH decomposition through the initial O-H bond breaking is less than its desorption energy of 0.95 eV, showing that CH3OH prefers to undergo decomposition to CH3O rather than direct desorption. The study provides in-depth theoretical insights into the potentially enhanced catalytic activity of Ru-Pt/boron doped graphene surfaces for methanol decomposition reactions, thereby contributing to the understanding and designing of an efficient catalyst under optimum conditions.

  20. Findings

    MedlinePlus

    ... Issue All Issues Explore Findings by Topic Cell Biology Cellular Structures, Functions, Processes, Imaging, Stress Response Chemistry ... Glycobiology, Synthesis, Natural Products, Chemical Reactions Computers in Biology Bioinformatics, Modeling, Systems Biology, Data Visualization Diseases Cancer, ...

  1. Most children with eosinophilic esophagitis have a favorable outcome as young adults.

    PubMed

    Bohm, M; Jacobs, J W; Gupta, A; Gupta, S; Wo, J M

    2017-01-01

    The disease progression of eosinophilic esophagitis (EoE) from childhood into adulthood is unclear. To determine the clinical outcome of patients who were diagnosed with EoE as children, and who now are young adults. Children (<18 years old) diagnosed with EoE were enrolled in a prospective registry on demographics, presenting symptoms, and endoscopic/histologic findings. Subjects who now are adults (≥18 years old) were identified, and a structured telephone interview was conducted to obtain follow-up data on symptom prevalence (dysphagia to solids and liquids, nausea/vomiting, abdominal pain, and heartburn/regurgitation), food impaction, medication usage, health-care utilization, and resolution of atopy/food allergies. A favorable outcome was defined if EoE symptoms were resolved or improved by subjects' assessment. Unfavorable outcomes was defined as symptoms same or worse. Clinical variables that predicted a favorable outcome as an adult were examined. Mayo Dysphagia Scale (MDQ-30: scored 0-100) was administered to validate the outcome assessment. Mantel-Haenszel odds ratio and unpaired t-test were used. Fifty-eight subjects (64% male) who met study criteria were enrolled. Mean age at diagnosis was 12 years (range 4-17) and mean duration of follow-up was 8.3 years (2-16). As children, the most common presenting symptoms were abdominal pain (54%), dysphagia (33%), and vomiting (24%). As young adults, 47 subjects (81%) had a favorable outcome. Total MDQ-30 scores were 4.6 (0-30) and 14.1 (0-50) in subjects with favorable outcome and unfavorable outcome, respectively (P = 0.015). Two-thirds of subjects did not use steroids or proton pump inhibitors in the preceeding 12 months. Male children with EoE were four times more likely to have a favorable outcome as young adults compared with female children. Females were more likely to report nausea/vomiting as young adults (odds ratio 3.23, CI 0.97-10.60). Of all presenting symptoms in EoE children, dysphagia

  2. Hydrogen/Chlorine exchange reactions of gaseous carbanions.

    PubMed

    Chen, Hao; Cooks, R Graham; Meurer, Eduardo C; Eberlin, Marcos N

    2005-12-01

    Gas-phase reactions of three typical carbanions CH(2)NO(2)(-), CH(2)CN(-), and CH(2)S(O)CH(3)(-) with the chloromethanes CH(2)Cl(2), CHCl(3), and CCl(4), examined by tandem mass spectrometry, show a novel hydrogen/chlorine exchange reaction. For example, reaction between the nitromethyl anion CH(2)NO(2)(-) and carbon tetrachloride CCl(4) forms the ion CHClNO(2)(-). The suggested reaction mechanism involves nucleophilic attack by CH(2)NO(2)(-) at the chlorine of CCl(4) followed by proton transfer within the resulting complex [CH(2)ClNO(2) + CCl(3)(-)] to form CHClNO(2)(-) and CHCl(3). Two other carbanions CH(2)CN(-) and CH(2)S(O)CH(3)(-) also undergo the novel hydrogen/chlorine exchange reactions with CCl(4) but to a much smaller extent, their higher nucleophilicities favoring competitive nucleophilic attack reactions. Proton abstraction is the exclusive pathway in the reactions of these carbanions with CHCl(3). While CH(2)CN(-) and CH(2)S(O)CH(3)(-) promote mainly proton abstraction and nucleophilic displacement in reactions with CH(2)Cl(2), CH(2)NO(2)(-) does not react.

  3. Metal-phthalocyanine functionalized carbon nanotubes as catalyst for the oxygen reduction reaction: A theoretical study

    NASA Astrophysics Data System (ADS)

    Orellana, Walter

    2012-07-01

    The covalent functionalization of metallic single-walled carbon nanotubes (CNTs) with transition metal phthalocyanines (MPc, with M = Mn, Fe and Co) are addressed by density functional calculations. The CNT-MPc catalytic activity toward the oxygen reduction reaction (ORR) is investigated through the O2 stretching frequency adsorbed on the phthalocyanine metal center. We find better reduction abilities when the CNT functionalization occurs through sp2-like bonds. Multiple stable-spin states for the M-O2 adduct are also found for M = Mn and Fe, suggesting higher ORR rates. The CNT-MPc complexes show metallic characteristics, suggesting favorable conditions to work as ORR cathode catalysts in fuel cells.

  4. Evaluation of the tissue reaction to a new bilayered collagen matrix in vivo and its translation to the clinic.

    PubMed

    Ghanaati, Shahram; Schlee, Markus; Webber, Matthew J; Willershausen, Ines; Barbeck, Mike; Balic, Ela; Görlach, Christoph; Stupp, Samuel I; Sader, Robert A; Kirkpatrick, C James

    2011-02-01

    This study evaluates a new collagen matrix that is designed with a bilayered structure in order to promote guided tissue regeneration and integration within the host tissue. This material induced a mild tissue reaction when assessed in a murine model and was well integrated within the host tissue, persisting in the implantation bed throughout the in vivo study. A more porous layer was rapidly infiltrated by host mesenchymal cells, while a layer designed to be a barrier allowed cell attachment and host tissue integration, but at the same time remained impermeable to invading cells for the first 30 days of the study. The tissue reaction was favorable, and unlike a typical foreign body response, did not include the presence of multinucleated giant cells, lymphocytes, or granulation tissue. In the context of translation, we show preliminary results from the clinical use of this biomaterial applied to soft tissue regeneration in the treatment of gingival tissue recession and exposed roots of human teeth. Such a condition would greatly benefit from guided tissue regeneration strategies. Our findings demonstrate that this material successfully promoted the ingrowth of gingival tissue and reversed gingival tissue recession. Of particular importance is the fact that the histological evidence from these human studies corroborates our findings in the murine model, with the barrier layer preventing unspecific tissue ingrowth, as the scaffold becomes infiltrated by mesenchymal cells from adjacent tissue into the porous layer. Also in the clinical situation no multinucleated giant cells, no granulation tissue and no evidence of a marked inflammatory response were observed. In conclusion, this bilayered matrix elicits a favorable tissue reaction, demonstrates potential as a barrier for preferential tissue ingrowth, and achieves a desirable therapeutic result when applied in humans for soft tissue regeneration.

  5. Cassini finds molecular hydrogen in the Enceladus plume: Evidence for hydrothermal processes

    NASA Astrophysics Data System (ADS)

    Waite, J. Hunter; Glein, Christopher R.; Perryman, Rebecca S.; Teolis, Ben D.; Magee, Brian A.; Miller, Greg; Grimes, Jacob; Perry, Mark E.; Miller, Kelly E.; Bouquet, Alexis; Lunine, Jonathan I.; Brockwell, Tim; Bolton, Scott J.

    2017-04-01

    Saturn’s moon Enceladus has an ice-covered ocean; a plume of material erupts from cracks in the ice. The plume contains chemical signatures of water-rock interaction between the ocean and a rocky core. We used the Ion Neutral Mass Spectrometer onboard the Cassini spacecraft to detect molecular hydrogen in the plume. By using the instrument’s open-source mode, background processes of hydrogen production in the instrument were minimized and quantified, enabling the identification of a statistically significant signal of hydrogen native to Enceladus. We find that the most plausible source of this hydrogen is ongoing hydrothermal reactions of rock containing reduced minerals and organic materials. The relatively high hydrogen abundance in the plume signals thermodynamic disequilibrium that favors the formation of methane from CO2 in Enceladus’ ocean.

  6. 36 CFR 905.735-202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 36 Parks, Forests, and Public Property 3 2012-07-01 2012-07-01 false Gifts, entertainment, and favors. 905.735-202 Section 905.735-202 Parks, Forests, and Public Property PENNSYLVANIA AVENUE..., entertainment, and favors. Pursuant to paragraph (b) of 5 CFR 735.202, the following exceptions to the...

  7. 36 CFR 905.735-202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 36 Parks, Forests, and Public Property 3 2011-07-01 2011-07-01 false Gifts, entertainment, and favors. 905.735-202 Section 905.735-202 Parks, Forests, and Public Property PENNSYLVANIA AVENUE..., entertainment, and favors. Pursuant to paragraph (b) of 5 CFR 735.202, the following exceptions to the...

  8. 36 CFR 905.735-202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 36 Parks, Forests, and Public Property 3 2014-07-01 2014-07-01 false Gifts, entertainment, and favors. 905.735-202 Section 905.735-202 Parks, Forests, and Public Property PENNSYLVANIA AVENUE..., entertainment, and favors. Pursuant to paragraph (b) of 5 CFR 735.202, the following exceptions to the...

  9. Employee reactions to managed care.

    PubMed

    Proenca, E J

    1999-01-01

    Employee reactions to managed care get less managerial and research attention than organizational reactions to it. This article examines the manner in which health services employees react to managed care and finds that their reaction affects perceived job insecurity, organizational commitment, and job satisfaction. Organization-based self-esteem, role conflict, and supervisory support moderate these relationships. The managerial implications of these findings are discussed.

  10. A study of ethanol reactions on O2-treated Au/TiO2. Effect of support and metal loading on reaction selectivity

    NASA Astrophysics Data System (ADS)

    Nadeem, M. A.; Waterhouse, G. I. N.; Idriss, H.

    2016-08-01

    The reactions of ethanol have been studied on bare and Au supported TiO2 polymorphs (anatase and rutile) in order to understand the effect of Au loading and prior O2 treatment on the reaction selectivity and conversion using temperature programmed desorption (TPD). Although O2 treatment has negligible effect on the reaction selectivity of ethanol on TiO2 alone it considerably affects the reaction on Au/TiO2. Au/TiO2 had three main effects on the reaction when compared to TiO2 alone. First, it switches the reaction selectivity of the dehydration (to ethylene) in favor of dehydrogenation (to acetaldehyde) on both polymorphs. Second, it decreases the desorption temperature of the main reaction products. Third, it increases secondary reaction products (mainly C4 (crotonaldehyde, butene, furan) reaching ca. 78% of the overall carbon selectivity for the 8 wt.% Au/TiO2 anatase. These effects are more pronounced on the anatase phase when compared to that on the rutile phase. Reasons for these are discussed.

  11. 22 CFR 1203.735-202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 22 Foreign Relations 2 2011-04-01 2009-04-01 true Gifts, entertainment, and favors. 1203.735-202..., entertainment, and favors. (a) Acceptance prohibited. Except as provided in paragraphs (b), (c), and (d) of this..., entertainment, loan, or any other thing of monetary value, from a person who: (1) Has, or is seeking to obtain...

  12. 22 CFR 1203.735-202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 22 Foreign Relations 2 2013-04-01 2009-04-01 true Gifts, entertainment, and favors. 1203.735-202..., entertainment, and favors. (a) Acceptance prohibited. Except as provided in paragraphs (b), (c), and (d) of this..., entertainment, loan, or any other thing of monetary value, from a person who: (1) Has, or is seeking to obtain...

  13. 22 CFR 1203.735-202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 22 Foreign Relations 2 2012-04-01 2009-04-01 true Gifts, entertainment, and favors. 1203.735-202..., entertainment, and favors. (a) Acceptance prohibited. Except as provided in paragraphs (b), (c), and (d) of this..., entertainment, loan, or any other thing of monetary value, from a person who: (1) Has, or is seeking to obtain...

  14. 22 CFR 1203.735-202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 22 Foreign Relations 2 2014-04-01 2014-04-01 false Gifts, entertainment, and favors. 1203.735-202..., entertainment, and favors. (a) Acceptance prohibited. Except as provided in paragraphs (b), (c), and (d) of this..., entertainment, loan, or any other thing of monetary value, from a person who: (1) Has, or is seeking to obtain...

  15. AZALEP a randomized controlled trial of azathioprine to treat leprosy nerve damage and Type 1 reactions in India: Main findings

    PubMed Central

    Darlong, Joydeepa; Govindharaj, Pitchaimani; Kurian, Royce; Sundarrao, Pamidipani; John, Annamma S.

    2017-01-01

    Background Leprosy Type 1 reactions are difficult to treat and only 70% of patients respond to steroid treatment. Azathioprine has been used as an immune-suppressant and we tested its efficacy in treating leprosy T1R. Methodology Randomised controlled trial adding azathioprine to steroid treatment for leprosy reactions. This trial was conducted in four leprosy hospitals in India. Patients with a new leprosy Type 1 reaction affecting either skin or nerve were recruited. They were given a 20 week course of oral prednisolone either with placebo or azathioprine 50mg for 24, 36 or 48 weeks. Outcomes were measured using a verified combined clinical reaction severity score (CCS) and the score difference between baseline and end of study calculated. An intention to treat analysis was done on the 279 patients who had an outcome. Principal findings 345 patients were recruited, 145 were lost due to adverse events, loss to follow up or death. 36% needed extra steroids due to a recurrence of their skin and/or nerve reaction. 76% of patients had improvements in their CCS the end of the study, 22% had no change and 1.1% deteriorated. Adding azathioprine to steroid treatment did not improve CCS. So the improvements were attributable to treatment with steroids. We analysed the skin, sensory and motor scores separately and found that skin improvement contributed most with 78.9% of patients having skin improvement, azathioprine treatment for 48 weeks improved sensory scores it also improved motor scores but so did treatment with prednisolone alone. We identified significant adverse effects attributable to steroid treatment. When azathioprine and Dapsone were given together significant numbers of patients developed significant anaemia. Conclusions Azathioprine is not recommended for the treatment of leprosy reactions and does not improve steroid treatment. Recurrent reactions are a major challenge. We have also identified that 65% of patients with sensory and 50% with motor nerve

  16. Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

    NASA Astrophysics Data System (ADS)

    Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

    2018-06-01

    Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

  17. Regiochemistry in cobalt-mediated intermolecular Pauson-Khand reactions of unsymmetrical internal heteroaromatic alkynes with norbornene.

    PubMed

    Moulton, Benjamin E; Whitwood, Adrian C; Duhme-Klair, Anne K; Lynam, Jason M; Fairlamb, Ian J S

    2011-07-01

    The intermolecular Pauson-Khand (PK) reactions of sterically comparable (2-phenylethynyl)heteroaromatic compounds with norbornene, mediated by Co(2)(CO)(8) to give cyclopentenone products, were examined in this study. A synthetic protocol utilizing focused-microwave dielectric heating proved indispensable in the efficient synthesis of the PK cyclopentenone products. "π-Deficient" heteroaromatic substrates, e.g., 2-pyrones, and some "π-excessive" heteroaromatics such as 2- and 3-thiophene and 2-furan favor the β-position in the newly formed cyclopentenone ring. Other π-excessive heteroaromatics such as 2-pyrrole or 2-indole favor the α-position. A π-excessive 3-indole derivative gave a nearly equal mixture of regioisomers. The position of the nitrogen in pyridyl-containing alkyne substrates also affects the regiochemical outcome of the PK reaction. A 2-pyridyl alkyne, possessing a proximal nitrogen, influences the regioselectivity relative to a 4-pyridyl variant quite dramatically, favoring the β-position in the newly formed cyclopentenone ring. A 2-pyrimidylalkyne exhibits similar behavior to the 2-pyridylalkyne. Compounds that do not participate in PK reactions with norbornene include (2-phenylethynyl)imidazoles and the related benzimidazoles, which promote rapid decomposition of the in situ generated (μ(2)-alkyne)Co(2)(CO)(6) complexes. This stands in contrast with other nitrogen-containing heteroaromatics, e.g., pyrrole-, indole-, and pyrimidine-derived compounds, which effectively undergo PK reactions. Overall, the type of heteroaromatic group dramatically influences PK regioselectivity, which can in part be explained by rationalization of the current reaction mechanism, but not fully.

  18. Organic radicals for the enhancement of oxygen reduction reaction in Li-O2 batteries.

    PubMed

    Tesio, A Y; Blasi, D; Olivares-Marín, M; Ratera, I; Tonti, D; Veciana, J

    2015-12-25

    We examine for the first time the ability of inert carbon free-radicals as soluble redox mediators to catalyze and enhance the oxygen reduction reaction in a (TEGDME)-based electrolyte. We demonstrate that the tris(2,4,6-trichlorophenyl)methyl (TTM) radical is capable of chemically favoring the oxygen reduction reaction improving significantly the Li-O2 battery performance.

  19. Cassini finds molecular hydrogen in the Enceladus plume: Evidence for hydrothermal processes.

    PubMed

    Waite, J Hunter; Glein, Christopher R; Perryman, Rebecca S; Teolis, Ben D; Magee, Brian A; Miller, Greg; Grimes, Jacob; Perry, Mark E; Miller, Kelly E; Bouquet, Alexis; Lunine, Jonathan I; Brockwell, Tim; Bolton, Scott J

    2017-04-14

    Saturn's moon Enceladus has an ice-covered ocean; a plume of material erupts from cracks in the ice. The plume contains chemical signatures of water-rock interaction between the ocean and a rocky core. We used the Ion Neutral Mass Spectrometer onboard the Cassini spacecraft to detect molecular hydrogen in the plume. By using the instrument's open-source mode, background processes of hydrogen production in the instrument were minimized and quantified, enabling the identification of a statistically significant signal of hydrogen native to Enceladus. We find that the most plausible source of this hydrogen is ongoing hydrothermal reactions of rock containing reduced minerals and organic materials. The relatively high hydrogen abundance in the plume signals thermodynamic disequilibrium that favors the formation of methane from CO 2 in Enceladus' ocean. Copyright © 2017, American Association for the Advancement of Science.

  20. The unexpected product of Diels-Alder reaction between "indanocyclon" and maleimide

    NASA Astrophysics Data System (ADS)

    Dobrowolski, Michał A.; Roszkowski, Piotr; Struga, Marta; Szulczyk, Daniel

    2017-02-01

    A heterocyclic compound commonly known as "indanocyclon" undergoes an unexpected Diels-Alder addition with maleimide. The resulting product has been isolated and characterized in order to get an information about its structure and possible mechanism of the reaction. Extensive comparison of single crystal properties of 3-(2,8-dioxo-1,3-diphenyl-2,8-dihydrocyclopenta[a]inden-8a(1H)-yl)pyrrolidine-2,5-dione and favorable product of the reaction has been also performed.

  1. Quantum Chemistry Study of Cycloaddition Pathways for the Reaction of o-Benzyne with Fullerenes and Carbon Nanotubes

    NASA Technical Reports Server (NTRS)

    Jaffe, Richard; Han, Jie; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    Functionalization of fullerenes via the [2+2] cycloaddition reaction with o-benzyne has been demonstrated in the laboratory. In contrast, [2+4) cycloaddition products are formed when benzyne reacts with planar polycyclic aromatic hydrocarbons. Using density functional theory (DFT) calculations with Becke's hybrid functional and small contracted gaussian basis sets, we are able to reproduce these product preferences. The objective of this work is to explore the functionalization of carbon nanotubes. We have studied o-benzyne cycloaddition products with a [14,0] single-walled nanotube. We find both the [2+2] and [2+4] adducts to be stable, with the latter product being somewhat favored.

  2. Kinetic Studies on the Reaction of Chlorosulfonyl Isocyanate with Monofluoralkenes: Experimental Evidence for Both Stepwise and Concerted Mechanisms, and a Pre-equilibrium Complex on the Reaction Pathway

    DTIC Science & Technology

    2012-12-14

    lactams that are readily reduced to β-lactams. Substitution of a vinyl hydrogen for a vinyl fluorine changes the dynamics for reaction with CSI so...hydrogen for a vinyl fluorine changes the dynamics for reaction with CSI so that a concerted pathway is favored. Rate constants were measured for...step pathway has not been demonstrated experimentally.3c In a recent paper, we found that substituting a hydrogen for a fluorine on the π-bond of an

  3. Patient-shared TCRβ-CDR3 clonotypes correlate with favorable prognosis in chronic hepatitis B.

    PubMed

    Jiang, Qiong; Zhao, Tingting; Zheng, Wenhong; Zhou, Jijun; Wang, Haoliang; Dong, Hui; Chen, Yongwen; Tang, Xiaoqin; Liu, Cong; Ye, Lilin; Mao, Qing; Wang, Chunlin; Han, Jian; Shang, Xiaoyun; Wu, Yuzhang

    2018-06-01

    The presence of shared T cell clonotypes was found in several different diseases, but its relationship with the progression of disease remains unclear. By sequencing the complementary determining region 3 of T cell receptor (TCR) β chains from the purified antigen-experienced CD8 + T cells, we characterized the T cell repertoire in a prospective cohort study among 75 patients with chronic hepatitis B in China, as well as a healthy control and a validation cohort. We found that most T cell clones from patients harbored the 'patient-specific' TCR sequences. However, 'patient-shared' TCR clonotypes were also widely found, which correlated with the favorable turnover of disease. Interestingly, the frequency of the 'patient-shared' clonotypes can serve as a biomarker for favorable prognosis. Based on the clonotypes in those patients with favorable outcomes, we created a database including several clusters of protective anti-HBV CD8 + T cell clonotypes that might be a reasonable target for therapeutic vaccine development or adoptive cell transfer therapy. These findings were validated in an additional independent cohort of patients. These results suggest that the 'patient-shared' TCR clonotypes may serve as a valuable prognostic tool in the treatment of chronic hepatitis B and possibly other chronic viral diseases. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  4. 45 CFR 73.735-502 - Permissible acceptance of gifts, entertainment, and favors.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 45 Public Welfare 1 2014-10-01 2014-10-01 false Permissible acceptance of gifts, entertainment... GENERAL ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-502 Permissible acceptance of gifts, entertainment, and favors. (a) An employee may accept a gift, gratuity, favor...

  5. 45 CFR 73.735-502 - Permissible acceptance of gifts, entertainment, and favors.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 45 Public Welfare 1 2011-10-01 2011-10-01 false Permissible acceptance of gifts, entertainment... GENERAL ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-502 Permissible acceptance of gifts, entertainment, and favors. (a) An employee may accept a gift, gratuity, favor...

  6. 45 CFR 73.735-502 - Permissible acceptance of gifts, entertainment, and favors.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 45 Public Welfare 1 2012-10-01 2012-10-01 false Permissible acceptance of gifts, entertainment... GENERAL ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-502 Permissible acceptance of gifts, entertainment, and favors. (a) An employee may accept a gift, gratuity, favor...

  7. 45 CFR 73.735-502 - Permissible acceptance of gifts, entertainment, and favors.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 45 Public Welfare 1 2013-10-01 2013-10-01 false Permissible acceptance of gifts, entertainment... GENERAL ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-502 Permissible acceptance of gifts, entertainment, and favors. (a) An employee may accept a gift, gratuity, favor...

  8. The effects of an intervention to increase liberal arts mathematics and science majors' knowledge of and attitudinal favorability toward the teaching profession

    NASA Astrophysics Data System (ADS)

    Klemballa, Carolyn

    In light of the persistent shortage of qualified mathematics and science teachers and the new teacher qualification provisions of the recently passed No Child Left Behind Act, This study tested the impact of an educational intervention designed to enhance interest in public school teaching careers among undergraduate students who were declared/intended majors in mathematics and/or natural science. Besides salary, research reveals content fear as the biggest roadblock to attracting mathematics and science teachers. Because of this, liberal arts majors in mathematics and science are a target pool of individuals to recruit into teaching. The researcher hypothesized that knowledge and attitudinal favorability would both increase after an intervention about teaching careers and that an increase in one variable would be associated with the other. Also, knowledge and attitudinal favorability would have a greater increase after a more intensive intervention than a less intensive intervention or no intervention. The researcher also hypothesized that if undergraduates were less decided in their career, lower classmen, and female, their attitudes toward the teaching profession would increase the most. One hundred eighty-nine college students, 73 males and 116 females, including 85 freshmen, 67 sophomores, 18 juniors and 19 seniors, at University A and University B were randomly assigned to a workshop, reading, or control group. The workshop group attended a workshop about the teaching profession. The reading group read articles with the same information presented in the workshop. The control group read unrelated articles. The findings from this study indicate that an intervention about teaching does significantly increase both knowledge and attitudinal favorability toward teaching (p < .01). A low significant correlation was found between knowledge and attitudinal favorability (p < .05). Findings also suggested that a more intensive intervention yields a higher increase in

  9. Shoulder and Lower Back Joint Reaction Forces in Seated Double Poling.

    PubMed

    Lund Ohlsson, Marie; Danvind, Jonas; Holmberg, L Joakim

    2018-04-13

    Overuse injuries in the shoulders and lower back are hypothesized to be common in cross-country sit-skiing. Athletes with reduced trunk muscle control mainly sits with their knees higher than hips (KH). To reduce spinal flexion, a position with the knees below the hips (KL) was enabled for these athletes using a frontal trunk support. The aim of the study was to compare the shoulder joint (glenohumeral joint) and L4-L5 joint reactions between the sitting positions KL and KH. Five able-bodied female athletes performed submaximal and maximal exercise tests in the sitting positions KL and KH on a ski-ergometer. Measured pole forces and 3-dimensional kinematics served as input for inverse-dynamics simulations to compute the muscle forces and joint reactions in the shoulder and L4-L5 joint. This was the first musculoskeletal simulation study of seated double poling. The results showed that the KH position was favorable for higher performance and decreased values of the shoulder joint reactions for female able-bodied athletes with full trunk control. The KL position was favorable for lower L4-L5 joint reactions and might therefore reduce the risk of lower back injuries. These results indicate that it is hard to optimize both performance and safety in the same sit-ski.

  10. Efficient Constant-Time Complexity Algorithm for Stochastic Simulation of Large Reaction Networks.

    PubMed

    Thanh, Vo Hong; Zunino, Roberto; Priami, Corrado

    2017-01-01

    Exact stochastic simulation is an indispensable tool for a quantitative study of biochemical reaction networks. The simulation realizes the time evolution of the model by randomly choosing a reaction to fire and update the system state according to a probability that is proportional to the reaction propensity. Two computationally expensive tasks in simulating large biochemical networks are the selection of next reaction firings and the update of reaction propensities due to state changes. We present in this work a new exact algorithm to optimize both of these simulation bottlenecks. Our algorithm employs the composition-rejection on the propensity bounds of reactions to select the next reaction firing. The selection of next reaction firings is independent of the number reactions while the update of propensities is skipped and performed only when necessary. It therefore provides a favorable scaling for the computational complexity in simulating large reaction networks. We benchmark our new algorithm with the state of the art algorithms available in literature to demonstrate its applicability and efficiency.

  11. ENHANCING THE STABILITY OF POROUS CATALYSTS WITH SUPERCRITICAL REACTION MEDIA. (R826034)

    EPA Science Inventory

    Adsorption/desorption and pore-transport are key parameters influencing the activity and product selectivity in porous catalysts. With conventional reaction media (gas or liquid phase), one of these parameters is generally favorable while the other is not. For instance, while ...

  12. Head-to-head randomized trials are mostly industry sponsored and almost always favor the industry sponsor.

    PubMed

    Flacco, Maria Elena; Manzoli, Lamberto; Boccia, Stefania; Capasso, Lorenzo; Aleksovska, Katina; Rosso, Annalisa; Scaioli, Giacomo; De Vito, Corrado; Siliquini, Roberta; Villari, Paolo; Ioannidis, John P A

    2015-07-01

    To map the current status of head-to-head comparative randomized evidence and to assess whether funding may impact on trial design and results. From a 50% random sample of the randomized controlled trials (RCTs) published in journals indexed in PubMed during 2011, we selected the trials with ≥ 100 participants, evaluating the efficacy and safety of drugs, biologics, and medical devices through a head-to-head comparison. We analyzed 319 trials. Overall, 238,386 of the 289,718 randomized subjects (82.3%) were included in the 182 trials funded by companies. Of the 182 industry-sponsored trials, only 23 had two industry sponsors and only three involved truly antagonistic comparisons. Industry-sponsored trials were larger, more commonly registered, used more frequently noninferiority/equivalence designs, had higher citation impact, and were more likely to have "favorable" results (superiority or noninferiority/equivalence for the experimental treatment) than nonindustry-sponsored trials. Industry funding [odds ratio (OR) 2.8; 95% confidence interval (CI): 1.6, 4.7] and noninferiority/equivalence designs (OR 3.2; 95% CI: 1.5, 6.6), but not sample size, were strongly associated with "favorable" findings. Fifty-five of the 57 (96.5%) industry-funded noninferiority/equivalence trials got desirable "favorable" results. The literature of head-to-head RCTs is dominated by the industry. Industry-sponsored comparative assessments systematically yield favorable results for the sponsors, even more so when noninferiority designs are involved. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  13. A favorable course of palliative sedation: searching for indicators using caregivers' perspectives.

    PubMed

    Brinkkemper, Tijn; Rietjens, Judith A C; Deliens, Luc; Ribbe, Miel W; Swart, Siebe J; Loer, Stephan A; Zuurmond, Wouter W A; Perez, Roberto S G M

    2015-03-01

    Comparing characteristics of a favorable sedation course during palliative sedation to a less favorable course based on the reports Dutch physicians and nurses. Cases identified as having a favorable sedation course less often concerned a male patient (P = .019 nurses' cases), reached the intended sedation depth significantly quicker (P < .05 both nurses and physicians' cases), reached a deeper level of sedation (P = .015 physicians' cases), and had a shorter total duration of sedation compared (P < .001 physicians' cases) to patients with a less favorable sedation course. A favorable course during palliative sedation seems more probable when health care professionals report on a (relatively) shorter time to reach the required depth of sedation and when a deeper level of sedation can be obtained. © The Author(s) 2013.

  14. 36 CFR § 905.735-202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 36 Parks, Forests, and Public Property 3 2013-07-01 2012-07-01 true Gifts, entertainment, and favors. § 905.735-202 Section § 905.735-202 Parks, Forests, and Public Property PENNSYLVANIA AVENUE..., entertainment, and favors. Pursuant to paragraph (b) of 5 CFR 735.202, the following exceptions to the...

  15. Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

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

    Liu, Cong; Evans, Tabitha J.; Cheng, Lei

    2015-10-02

    These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Majormore » products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.« less

  16. Reaction Gradients Viewed Inside Single Photoactive Particles

    NASA Astrophysics Data System (ADS)

    Alpert, P.; Corral Arroyo, P.; Dou, J.; Kreiger, U.; Luo, B.; Peter, T.; Ammann, M.

    2017-12-01

    In terms of chemical selectivity and spatial resolution, a technique known as scanning transmission X-ray microscopy coupled to near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) is unmatched and will remain so for years into the future. We present a recent development coupling STXM/NEXAFS to a custom-built photochemical environmental reactor in which aerosol particles reside allowing for in situ chemical imaging. A laboratory investigation of metal-organic complex photochemistry was conducted. Transition metals are of great importance to atmospheric chemistry and aerosol photochemical aging due to their ability to catalyze oxidation reactions. Aerosol particles composed of mixtures of citric acid and iron citrate were probed for their organic carbon composition and iron oxidation state under atmospherically relevant conditions. At 40% relative humidity, oxygen diffusion and reaction was severely limited. Fe was reoxidized in the first 200 nm of the particle surface leaving reduced iron in the core. Similar gradients were observed at 60% RH, however waiting approximately 2 hours in the dark resulted in a recovery of the initial Fe(III) concentration. We draw two main conclusions from our findings. Frist, the oxidation gradients must have been the result of anoxic conditions at the interior of aerosol particles. This was predicted using a newly developed model for molecular diffusion through multiple layers with a reaction framework describing the photochemical processing of the metal organic matrix. Second, the lifetime of organic radicals in an anoxic diffusion limited organic matrix must be considerably long ( hours) to completely reoxidize iron as they wait for molecular oxygen. Long radical lifetimes in viscous organic aerosol in turn, could create high radical concentrations or favor radical-radical reactions in particles typically not considered when oxygen is plentiful. Our results impact predictions of aerosol physiochemical properties, e

  17. Musical FAVORS: Reintroducing music to adult cochlear implant users.

    PubMed

    Plant, Geoff

    2015-09-01

    Music represents a considerable challenge for many adult users of cochlear implants (CIs). Around half of adult CI users report that they do not find music enjoyable, and, in some cases, despite enhanced speech perception skills, this leads to considerable frustration and disappointment for the CI user. This paper presents suggestions to improve the musical experiences of deafened adults with CIs. Interviews with a number of adult CI users revealed that there were a number of factors which could lead to enhanced music experiences. The acronym FAVORS (familiar music, auditory-visual access, open-mindedness, and simple arrangements) summarizes the factors that have been identified, which can help CI users in their early music listening experiences. Each of these factors is discussed in detail, along with suggestions for how they can be used in therapy sessions. The use of a group approach (music focus groups) is also discussed and an overview of the approach and exercises used is presented. The importance of live music experiences is also discussed.

  18. Finding the optimal dose of vitamin K1 to treat vitamin K deficiency and to avoid anaphylactoid reactions.

    PubMed

    Mi, Yan-Ni; Ping, Na-Na; Li, Bo; Xiao, Xue; Zhu, Yan-Bing; Cao, Lei; Ren, Jian-Kang; Cao, Yong-Xiao

    2017-10-01

    Vitamin K1 injection induces severe dose-related anaphylactoid reactions and overdose for the treatment of vitamin K deficiency. We aimed to find an optimal and small dose of vitamin K1 injection to treat vitamin K deficiency and avoid anaphylactoid reactions in animal. Rats were administered a vitamin K-deficient diet and gentamicin to establish vitamin K deficiency model. Behaviour tests were performed in beagle dogs to observe anaphylactoid reactions. The results showed an increased protein induced by vitamin K absence or antagonist II (PIVKA-II) levels, a prolonging of prothrombin time (PT) and activated partial thromboplastin time (APTT) and a decrease in vitamin K-dependent coagulation factor (F) II, VII, IX and X activities in the model group. In vitamin K1 0.01 mg/kg group, the liver vitamin K1 levels increased fivefold and the liver vitamin K2 levels increased to the normal amount. Coagulation markers PT, APTT, FVII and FIX activities returned to normal. Both in the 0.1 and 1.0 mg/kg vitamin K1 groups, coagulation functions completely returned to normal. Moreover, the amount of liver vitamin K1 was 40 (0.1 mg/kg) or 100 (1.0 mg/kg) times as in normal. Vitamin K2 was about 4 (0.1 mg/kg) or 5 (1.0 mg/kg) times as the normal amount. There was no obvious anaphylactoid symptom in dogs with the dose of 0.03 mg/kg, which is equivalent to the dose of 0.01 mg/kg in rats. These results demonstrated that a small dose of vitamin K1 is effective to improve vitamin K deficiency and to prevent anaphylactoid reactions, simultaneously. © 2017 Société Française de Pharmacologie et de Thérapeutique.

  19. New Study Says CAI May Favor Introverts.

    ERIC Educational Resources Information Center

    Hopmeier, George

    1981-01-01

    A personality research study using the Myers-Briggs Type Indicator indicates that computer-assisted instruction programs favor introverts, i.e., those learners who can concentrate on details, memorize facts, and stay with a task until it is completed. (JJD)

  20. Roles of different initial Maillard intermediates and pathways in meat flavor formation for cysteine-xylose-glycine model reaction systems.

    PubMed

    Hou, Li; Xie, Jianchun; Zhao, Jian; Zhao, Mengyao; Fan, Mengdie; Xiao, Qunfei; Liang, Jingjing; Chen, Feng

    2017-10-01

    To explore initial Maillard reaction pathways and mechanisms for maximal formation of meaty flavors in heated cysteine-xylose-glycine systems, model reactions with synthesized initial Maillard intermediates, Gly-Amadori, TTCA (2-threityl-thiazolidine-4-carboxylic acids) and Cys-Amadori, were investigated. Relative relativities were characterized by spectrophotometrically monitoring the development of colorless degradation intermediates and browning reaction products. Aroma compounds formed were determined by solid-phase microextraction combined with GC-MS and GC-olfactometry. Gly-Amadori showed the fastest reaction followed by Cys-Amadori then TTCA. Free glycine accelerated reaction of TTCA, whereas cysteine inhibited that of Gly-Amadori due to association forming relatively stable thiazolidines. Cys-Amadori/Gly had the highest reactivity in development of both meaty flavors and brown products. TTCA/Gly favored yielding meaty flavors, whereas Gly-Amadori/Cys favored generation of brown products. Conclusively, initial formation of TTCA and pathway involving TTCA with glycine were more applicable to efficiently produce processed-meat flavorings in a cysteine-xylose-glycine system. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Trimolecular reactions of uranium hexafluoride with water.

    PubMed

    Lind, Maria C; Garrison, Stephen L; Becnel, James M

    2010-04-08

    The hydrolysis reaction of uranium hexafluoride (UF(6)) is a key step in the synthesis of uranium dioxide (UO(2)) powder for nuclear fuels. Mechanisms for the hydrolysis reactions are studied here with density functional theory and the Stuttgart small-core scalar relativistic pseudopotential and associated basis set for uranium. The reaction of a single UF(6) molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizable barrier of 78.2 kJ x mol(-1), indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO(2) product coupled with the observations of rapid, spontaneous hydrolysis at ambient conditions, an alternate reaction pathway must exist. In the present work, two trimolecular hydrolysis mechanisms are studied with density functional theory: (1) the reaction between two UF(6) molecules and one water molecule, and (2) the reaction of two water molecules with a single UF(6) molecule. The predicted reaction of two UF(6) molecules with one water molecule displays an interesting "fluorine-shuttle" mechanism, a significant energy barrier of 69.0 kJ x mol(-1) to the formation of UF(5)OH, and an enthalpy of reaction (DeltaH(298)) of +17.9 kJ x mol(-1). The reaction of a single UF(6) molecule with two water molecules displays a "proton-shuttle" mechanism, and is more favorable, having a slightly lower computed energy barrier of 58.9 kJ x mol(-1) and an exothermic enthalpy of reaction (DeltaH(298)) of -13.9 kJ x mol(-1). The exothermic nature of the overall UF(6) + 2H(2)O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging.

  2. RRKM and master equation kinetic analysis of parallel addition reactions of isomeric radical intermediates in hydrocarbon flames

    NASA Astrophysics Data System (ADS)

    Winter, Pierre M.; Rheaume, Michael; Cooksy, Andrew L.

    2017-08-01

    We have calculated the temperature-dependent rate coefficients of the addition reactions of butadien-2-yl (C4H5) and acroylyl (C3H3O) radicals with ethene (C2H4), carbon monoxide (CO), formaldehyde (H2CO), hydrogen cyanide (HCN), and ketene (H2CCO), in order to explore the balance between kinetic and thermodynamic control in these combustion-related reactions. For the C4H5 radical, the 1,3-diene form of the addition products is more stable than the 1,2-diene, but the 1,2-diene form of the radical intermediate is stabilized by an allylic delocalization, which may influence the relative activation energies. For the reactions combining C3H3O with C2H4, CO, and HCN, the opposite is true: the 1,2-enone form of the addition products is more stable than the 1,3-enone, whereas the 1,3-enone is the slightly more stable radical species. Optimized geometries and vibrational modes were computed with the QCISD/aug-cc-pVDZ level and basis, followed by single-point CCSD(T)-F12a/cc-pVDZ-F12 energy calculations. Our findings indicate that the kinetics in all cases favor reaction along the 1,3 pathway for both the C4H5 and C3H3O systems. The Rice-Ramsperger-Kassel-Marcus (RRKM) microcanonical rate coefficients and subsequent solution of the chemical master equation were used to predict the time-evolution of our system under conditions from 500 K to 2000 K and from 10-5 bar to 10 bars. Despite the 1,3 reaction pathway being more favorable for the C4H5 system, our results predict branching ratios of the 1,2 to 1,3 product as high as 0.48 at 1 bar. Similar results hold for the acroylyl system under these combustion conditions, suggesting that under kinetic control the branching of these reactions may be much more significant than the thermodynamics would suggest. This effect may be partly attributed to the low energy difference between 1,2 and 1,3 forms of the radical intermediate. No substantial pressure-dependence is found for the overall forward reaction rates until pressures

  3. 45 CFR 73.735-503 - Criminal provisions relating to gifts, entertainment, and favors.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ..., entertainment, and favors. 73.735-503 Section 73.735-503 Public Welfare DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-503 Criminal provisions relating to gifts, entertainment, and favors. (a) The law provides criminal penalties for whoever...

  4. 45 CFR 73.735-503 - Criminal provisions relating to gifts, entertainment, and favors.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ..., entertainment, and favors. 73.735-503 Section 73.735-503 Public Welfare DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-503 Criminal provisions relating to gifts, entertainment, and favors. (a) The law provides criminal penalties for whoever...

  5. 45 CFR 73.735-503 - Criminal provisions relating to gifts, entertainment, and favors.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ..., entertainment, and favors. 73.735-503 Section 73.735-503 Public Welfare DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-503 Criminal provisions relating to gifts, entertainment, and favors. (a) The law provides criminal penalties for whoever...

  6. 45 CFR 73.735-503 - Criminal provisions relating to gifts, entertainment, and favors.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ..., entertainment, and favors. 73.735-503 Section 73.735-503 Public Welfare Department of Health and Human Services GENERAL ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-503 Criminal provisions relating to gifts, entertainment, and favors. (a) The law provides criminal penalties for whoever...

  7. Age differences in feedback reactions: The roles of employee feedback orientation on social awareness and utility.

    PubMed

    Wang, Mo; Burlacu, Gabriela; Truxillo, Donald; James, Keith; Yao, Xiang

    2015-07-01

    Organizations worldwide are currently experiencing shifts in the age composition of their workforces. The workforce is aging and becoming increasingly age-diverse, suggesting that organizational researchers and practitioners need to better understand how age differences may manifest in the workplace and the implications for human resource practice. Integrating socioemotional selectivity theory with the performance feedback literature and using a time-lagged design, the current study examined age differences in moderating the relationships between the characteristics of performance feedback and employee reactions to the feedback event. The results suggest that older workers had higher levels of feedback orientation on social awareness, but lower levels of feedback orientation on utility than younger workers. Furthermore, the positive associations between favorability of feedback and feedback delivery and feedback reactions were stronger for older workers than for younger workers, whereas the positive association between feedback quality and feedback reactions was stronger for younger workers than for older workers. Finally, the current study revealed that age-related differences in employee feedback orientation could explain the different patterns of relationships between feedback characteristics and feedback reactions across older and younger workers. These findings have both theoretical and practical implications for building theory about workplace aging and improving ways that performance feedback is managed across employees from diverse age groups. (c) 2015 APA, all rights reserved).

  8. Reaction pathways of propene pyrolysis.

    PubMed

    Qu, Yena; Su, Kehe; Wang, Xin; Liu, Yan; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong

    2010-05-01

    The gas-phase reaction pathways in preparing pyrolytic carbon with propene pyrolysis have been investigated in detail with a total number of 110 transition states and 50 intermediates. The structure of the species was determined with density functional theory at B3PW91/6-311G(d,p) level. The transition states and their linked intermediates were confirmed with frequency and the intrinsic reaction coordinates analyses. The elementary reactions were explored in the pathways of both direct and the radical attacking decompositions. The energy barriers and the reaction energies were determined with accurate model chemistry method at G3(MP2) level after an examination of the nondynamic electronic correlations. The heat capacities and entropies were obtained with statistical thermodynamics. The Gibbs free energies at 298.15 K for all the reaction steps were reported. Those at any temperature can be developed with classical thermodynamics by using the fitted (as a function of temperature) heat capacities. It was found that the most favorable paths are mainly in the radical attacking chain reactions. The chain was proposed with 26 reaction steps including two steps of the initialization of the chain to produce H and CH(3) radicals. For a typical temperature (1200 K) adopted in the experiments, the highest energy barriers were found in the production of C(3) to be 203.4 and 193.7 kJ/mol. The highest energy barriers for the production of C(2) and C were found 174.1 and 181.4 kJ/mol, respectively. These results are comparable with the most recent experimental observation of the apparent activation energy 201.9 +/- 0.6 or 137 +/- 25 kJ/mol. Copyright 2010 Wiley Periodicals, Inc.

  9. Nitropyrroles, Diels-Alder reactions assisted by microwave irradiation and solvent effect. An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Mancini, Pedro M. E.; Kneeteman, María N.; Cainelli, Mauro; Ormachea, Carla M.; Domingo, Luis R.

    2017-11-01

    The behaviors of N-tosylnitropyrroles acting as electrophilic dienophiles in polar Diels-Alder reactions joint to different dienes of increeased nucleophilicity are analyzed. The reactions were developed under microwave irradiation using toluene or protic ionic liquids (PILs) as solvents and in free solvent conditions. In all the cases explored we observed good yields in short reaction times. For these reactions, the free solvent condition and the use of protic ionic liquids as solvents offer similar results. However, the free solvent conditions favor environmental sustainability. The role of PILs in these polar Diels-Alder reactions has been theoretically studied within the Molecular Electron Density Theory.

  10. Communication: State-to-state dynamics of the Cl + H2O → HCl + OH reaction: Energy flow into reaction coordinate and transition-state control of product energy disposal.

    PubMed

    Zhao, Bin; Sun, Zhigang; Guo, Hua

    2015-06-28

    Quantum state-to-state dynamics of a prototypical four-atom reaction, namely, Cl + H2O → HCl + OH, is investigated for the first time in full dimensionality using a transition-state wave packet method. The state-to-state reactivity and its dependence on the reactant internal excitations are analyzed and found to share many similarities both energetically and dynamically with the H + H2O → H2 + OH reaction. The strong enhancement of reactivity by the H2O stretching vibrational excitations in both reactions is attributed to the favorable energy flow into the reaction coordinate near the transition state. On the other hand, the insensitivity of the product state distributions with regard to reactant internal excitation stems apparently from the transition-state control of product energy disposal.

  11. Accelerated isothermal nucleic acid amplification in betaine-free reaction.

    PubMed

    Ma, Cuiping; Wang, Yifan; Zhang, Pansong; Shi, Chao

    2017-08-01

    Betaine was used as a common additive to isothermal nucleic acid amplification reactions because of lowering the melting temperature (Tm) of DNA. Herein, we reported a novel finding that betaine was inhibiting the reaction efficiency of isothermal amplification reactions. In this work, we have verified this finding by classical loop-mediated isothermal amplification that the addition of 0.8 M betaine inhibited the efficiency of reaction dropping to approximately 1%. Additionally, we clarified the mechanism of betaine hindering isothermal amplification reactions with a molecular barrier to lower associate rate constant K1 for intermolecular hybridization. This finding would be very significant for studies on the interaction between small molecule substance and DNA, and the development of point-of-care testing because of simplifying reaction system and increasing reaction efficiency. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Perceptions of Chinese cancer patients of the favorable and unfavorable words conveyed by their social support providers.

    PubMed

    Liu, Jun-E; Mok, Esther; Wong, Thomas

    2005-01-01

    The aim of this study is to describe the experience and expectations of Chinese cancer patients with regard to the favorable and unfavorable words conveyed by their social support providers. In-depth interviews were conducted with 20 patients with cancer using a qualitative approach, and the data obtained were analyzed using content analysis. The findings indicated that favorable words inspired patients with cancer and raised their hopes. Such words included words expressing positive confirmation of patients' physical condition and mental status, words of encouragement and consolation, discussions of successful cases, information about advanced medical techniques and developments, practical instructions, emotional support from close relatives, confirmation about previous achievements for the family and about one's career, as well as small talk to distract the patient. Unfavorable words were those that weakened the patients' hopes and self-esteem. They included words expressing negative information and pessimistic attitudes, those indicating an overprotective attitude on the part of close relatives, as well as words expressing commiseration, advice, and an underestimation of the patients' suffering without empathy. The findings provide guidelines for nurses to communicate with patients with cancer verbally in a Chinese cultural context, and outline strategies for communication to meet psychologic needs of patients.

  13. Development of intelligent model to determine favorable wheelchair tilt and recline angles for people with spinal cord injury.

    PubMed

    Fu, Jicheng; Jan, Yih-Kuen; Jones, Maria

    2011-01-01

    Machine-learning techniques have found widespread applications in bioinformatics. Such techniques provide invaluable insight on understanding the complex biomedical mechanisms and predicting the optimal individualized intervention for patients. In our case, we are particularly interested in developing an individualized clinical guideline on wheelchair tilt and recline usage for people with spinal cord injury (SCI). The current clinical practice suggests uniform settings to all patients. However, our previous study revealed that the response of skin blood flow to wheelchair tilt and recline settings varied largely among patients. Our finding suggests that an individualized setting is needed for people with SCI to maximally utilize the residual neurological function to reduce pressure ulcer risk. In order to achieve this goal, we intend to develop an intelligent model to determine the favorable wheelchair usage to reduce pressure ulcers risk for wheelchair users with SCI. In this study, we use artificial neural networks (ANNs) to construct an intelligent model that can predict whether a given tilt and recline setting will be favorable to people with SCI based on neurological functions and SCI injury history. Our results indicate that the intelligent model significantly outperforms the traditional statistical approach in accurately classifying favorable wheelchair tilt and recline settings. To the best of our knowledge, this is the first study using intelligent models to predict the favorable wheelchair tilt and recline angles. Our methods demonstrate the feasibility of using ANN to develop individualized wheelchair tilt and recline guidance for people with SCI.

  14. Children in Foster Care and the Development of Favorable Outcomes

    PubMed Central

    Fisher, Philip A.

    2011-01-01

    Young foster children have invariably faced a variety of risks that are strongly linked to long-term deficits in functioning across multiple developmental domains. Despite these risks, however, some children demonstrate more favorable outcomes and exhibit adaptation and the development of assets. In the present study, the relationship of early childhood factors (e.g., maltreatment history, placement history, parenting practices, environmental stress, developmental status, and attachment behavior) to the development of favorable outcomes in middle childhood were examined in a sample of foster children who had been in foster care in preschool (N = 35). Favorable outcomes were defined as demonstrations of emotion regulation and school adjustment in during middle childhood. Developmental status (particularly attention and executive functioning) and a lack of environmental stress during early childhood foster care experiences had a significant positive relationship with the development of emotion regulation and school adjustment in middle childhood. PMID:21987598

  15. Unimolecular reaction of acetone oxide and its reaction with water in the atmosphere.

    PubMed

    Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G

    2018-05-29

    Criegee intermediates (i.e., carbonyl oxides with two radical sites) are known to be important atmospheric reagents; however, our knowledge of their reaction kinetics is still limited. Although experimental methods have been developed to directly measure the reaction rate constants of stabilized Criegee intermediates, the experimental results cover limited temperature ranges and do not completely agree well with one another. Here we investigate the unimolecular reaction of acetone oxide [(CH 3 ) 2 COO] and its bimolecular reaction with H 2 O to obtain rate constants with quantitative accuracy comparable to experimental accuracy. We do this by using CCSDT(Q)/CBS//CCSD(T)-F12a/DZ-F12 benchmark results to select and validate exchange-correlation functionals, which are then used for direct dynamics calculations by variational transition state theory with small-curvature tunneling and torsional and high-frequency anharmonicity. We find that tunneling is very significant in the unimolecular reaction of (CH 3 ) 2 COO and its bimolecular reaction with H 2 O. We show that the atmospheric lifetimes of (CH 3 ) 2 COO depend on temperature and that the unimolecular reaction of (CH 3 ) 2 COO is the dominant decay mode above 240 K, while the (CH 3 ) 2 COO + SO 2 reaction can compete with the corresponding unimolecular reaction below 240 K when the SO 2 concentration is 9 × 10 10 molecules per cubic centimeter. We also find that experimental results may not be sufficiently accurate for the unimolecular reaction of (CH 3 ) 2 COO above 310 K. Not only does the present investigation provide insights into the decay of (CH 3 ) 2 COO in the atmosphere, but it also provides an illustration of how to use theoretical methods to predict quantitative rate constants of medium-sized Criegee intermediates.

  16. Same behavior, different consequences: reactions to men's and women's altruistic citizenship behavior.

    PubMed

    Heilman, Madeline E; Chen, Julie J

    2005-05-01

    In 2 experimental studies, the authors hypothesized that the performance of altruistic citizenship behavior in a work setting would enhance the favorability of men's (but not women's) evaluations and recommendations, whereas the withholding of altruistic citizenship behavior would diminish the favorability of women's (but not men's) evaluations and recommendations. Results supported the authors' predictions. Together with the results of a 3rd study demonstrating that work-related altruism is thought to be less optional for women than for men, these results suggest that gender-stereotypic prescriptions regarding how men and women should behave result in different evaluative reactions to the same altruistic behavior, depending on the performer's sex.

  17. [Biological and social correlates of favorable and unfavorable neurosis course].

    PubMed

    Sarsembaev, K T

    2003-01-01

    Four hundred ninety seven patients with neurosis of Astana (Kazakhstan) community, 116 men and 381 women, have been studied. The patients were traced in 5-year follow up study. Favorable and unfavorable types of the disorder were established, the latter being characterized by transforming into neurotic personality development. The influence of endogenous and environmental factors on neurosis prognosis was examined. To elaborate adequate measures for preventing neurotic personality development, criteria for favorable and unfavorable prognosis of neurotic disorders were suggested.

  18. Organocatalytic aza-Michael/retro-aza-Michael reaction: pronounced chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction.

    PubMed

    Cai, Yong-Feng; Li, Li; Luo, Meng-Xian; Yang, Ke-Fang; Lai, Guo-Qiao; Jiang, Jian-Xiong; Xu, Li-Wen

    2011-05-01

    A detailed experimental investigation of an aza-Michael reaction of aniline and chalcone is presented. A series of Cinchona alkaloid-derived organocatalysts with different functional groups were prepared and used in the aza-Michael and retro-aza-Michael reaction. There was an interesting finding that a complete reversal of stereoselectivity when a benzoyl group was introduced to the cinchonine and cinchonidine. The chirality amplification vs. time proceeds in the quinine-derived organocatalyst containing silicon-based bulky group, QN-TBS, -catalyzed aza-Michael reaction under solvent-free conditions. In addition, we have demonstrated for the first time that racemization was occurred in suitable solvents under mild conditions due to retro-aza-Michael reaction of the Michael adduct of aniline with chalcone. These indicate the equilibrium of retro-aza-Michael reaction and aza-Michael reaction produce the happening of chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction under different conditions, which would be beneficial to the development of novel chiral catalysts for the aza-Michael reactions. Copyright © 2011 Wiley-Liss, Inc.

  19. Theoretical study on the identity ion pair SN2 reactions of LiX with CH3SX (X=Cl, Br, and I): structure, mechanism, and potential energy surface.

    PubMed

    Ren, Yi; Gai, Jing-Gang; Xiong, Yan; Lee, Kuo-Hsing; Chu, San-Yan

    2007-07-26

    Three archetypal ion pair nucleophilic substitution reactions at the methylsulfenyl sulfur atom LiX+CH3SX-->XSCH3+LiX (X=Cl, Br, and I) are investigated by the modified Gaussian-2 theory. Including lithium cation in the anionic models makes the ion pair reactions proceed along an SN2 mechanism, contrary to the addition-elimination pathway occurring in the corresponding anionic nucleophilic substitution reactions X-+CH3SX-->XSCH3+X-. Two reaction pathways for the ion pair SN2 reactions at sulfur, inversion and retention, are proposed. Results indicate the inversion pathway is favorable for all the halogens. Comparison of the transition structures and energetics for the ion pair SN2 at sulfur with the potential competition ion pair SN2 reactions at carbon LiX+CH3SX-->XCH3+LiXS shows that the SN2 reactions at carbon are not favorable from the viewpoints of kinetics and thermodynamics.

  20. Direct Monte Carlo simulation of chemical reaction systems: Simple bimolecular reactions

    NASA Astrophysics Data System (ADS)

    Piersall, Shannon D.; Anderson, James B.

    1991-07-01

    In applications to several simple reaction systems we have explored a ``direct simulation'' method for predicting and understanding the behavior of gas phase chemical reaction systems. This Monte Carlo method, originated by Bird, has been found remarkably successful in treating a number of difficult problems in rarefied dynamics. Extension to chemical reactions offers a powerful tool for treating reaction systems with nonthermal distributions, with coupled gas-dynamic and reaction effects, with emission and adsorption of radiation, and with many other effects difficult to treat in any other way. The usual differential equations of chemical kinetics are eliminated. For a bimolecular reaction of the type A+B→C+D with a rate sufficiently low to allow a continued thermal equilibrium of reactants we find that direct simulation reproduces the expected second order kinetics. Simulations for a range of temperatures yield the activation energies expected for the reaction models specified. For faster reactions under conditions leading to a depletion of energetic reactant species, the expected slowing of reaction rates and departures from equilibrium distributions are observed. The minimum sample sizes required for adequate simulations are as low as 1000 molecules for these cases. The calculations are found to be simple and straightforward for the homogeneous systems considered. Although computation requirements may be excessively high for very slow reactions, they are reasonably low for fast reactions, for which nonequilibrium effects are most important.

  1. Uranium favorability of the San Rafael Swell area, east-central Utah

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

    Mickle, D G; Jones, C A; Gallagher, G L

    1977-10-01

    The San Rafael Swell project area in east-central Utah is approximately 3,000 sq mi and includes the San Rafael Swell anticline and the northern part of the Waterpocket Fold monocline at Capitol Reef. Rocks in the area are predominantly sedimentary rocks of Pennsylvanian through Cretaceous age. Important deposits of uranium in the project area are restricted to two formations, the Chinle (Triassic) and Morrison (Jurassic) Formations. A third formation, the White Rim Sandstone (Permian), was also studied because of reported exploration activity. The White Rim Sandstone is considered generally unfavorable on the basis of lithologic characteristics, distance from a possiblemore » source of uranium, lack of apparent mineralization, and the scarcity of anomalies on gamma-ray logs or in rock, water, and stream-sediment samples. The lower Chinle from the Moss Back Member down to the base of the formation is favorable because it is a known producer. New areas for exploration are all subsurface. Both Salt Wash and Brushy Basin Members of the Morrison Formation are favorable. The Salt Wash Member is favorable because it is a known producer. The Brushy Basin Member is favorable as a low-grade resource.« less

  2. Monetary favors and their influence on neural responses and revealed preference

    PubMed Central

    Harvey, Ann H.; Kirk, Ulrich; Denfield, George H.; Montague, P. Read

    2010-01-01

    Favors from a sender to a receiver are known to bias decisions made by the recipient, especially when the decision relates to the sender – a feature of social exchange known as reciprocity. Using an art-viewing paradigm possessing no objectively correct answer for preferring one piece of art over another, we show that sponsorship of the experiment by a company endows the company’s logo with the capacity to bias revealed preference for art displayed next to the logo. Merely offering to sponsor the experiment similarly endowed the gesturing company’s logo with the capacity to bias revealed preferences. These effects do not depend upon the size of the displayed art or the proximity of the sponsoring logo to the piece of art. We used fMRI to show that such monetary favors do not modulate a special collection of brain responses, but instead modulate responses in neural networks normally activated by a wide range of preference judgments. The results raise the important possibility that monetary favors bias judgments in domains seemingly unrelated to the favor, but nevertheless act in an implicit way through neural networks that underlie normal, ongoing preference judgments. PMID:20631188

  3. Decay analysis of compound nuclei with masses A ≈30 - 200 formed in reactions involving loosely bound projectiles

    NASA Astrophysics Data System (ADS)

    Kaur, Mandeep; Singh, BirBikram; Sharma, Manoj K.; Gupta, Raj K.

    2015-08-01

    The dynamics of compound nuclei formed in the reactions using loosely bound projectiles are analyzed within the framework of the dynamical cluster-decay model (DCM) of Gupta and Collaborators. We have considered the reactions with neutron-rich and neutron-deficient projectiles, respectively, as 7Li , 9Be , and 7Be , on various targets at three different Elab energies, forming compound nuclei in the mass region A ˜30 - 200. For these reactions, the contributions of light-particle (LP, A ≤4 ) cross sections σLP, energetically favored intermediate-mass-fragment (IMF, 5 ≤A2≤20 ) cross sections σIMF, as well as the fusion-fission ff cross sections σff constitute the σfus(=σLP+σIMF+σff ), i.e., the contributions of the emitted LPs, IMFs, and ff fragments are added for all the angular momenta up to the ℓmax value for the respective reactions. Interestingly, we find that the empirically fitted neck-length parameter Δ Remp , the only parameter of the DCM, is uniquely fixed to address σfus for all the reactions having the same loosely bound projectile at a chosen incident laboratory energy. It may be noted that, in DCM, the dynamical collective mass motion of preformed LPs, IMFs, and ff fragments or clusters, through the modified interaction potential barrier, are treated on parallel footing. The modification of the barrier is due to nonzero Δ Remp , and the values of corresponding modified interaction-barrier heights Δ VBemp for such reactions are almost of the same order, specifically at the respective ℓmax value.

  4. Diels–Alder Reactions of Allene with Benzene and Butadiene: Concerted, Stepwise, and Ambimodal Transition States

    PubMed Central

    2015-01-01

    Multiconfigurational complete active space methods (CASSCF and CASPT2) have been used to investigate the (4 + 2) cycloadditions of allene with butadiene and with benzene. Both concerted and stepwise radical pathways were examined to determine the mechanism of the Diels–Alder reactions with an allene dienophile. Reaction with butadiene occurs via a single ambimodal transition state that can lead to either the concerted or stepwise trajectories along the potential energy surface, while reaction with benzene involves two separate transition states and favors the concerted mechanism relative to the stepwise mechanism via a diradical intermediate. PMID:25216056

  5. The amalgamation stage of fusion reactions

    NASA Astrophysics Data System (ADS)

    Mouze, Genevieve

    2005-04-01

    There is no need of a repulsive potential in the amalgamation stage for explaining the small fusion cross sections. The repulsive potential proposed by A. Adamian et al.(1) can advantageously be replaced by the affinity of the reaction of re-dissociation of the compound nucleus into its entrance-channel configuration. This reaction, which occurs after the penetration of the Coulomb barrier, is an equilibrium between dual and compact form of the compound nucleus, and the energy Q released in the dissociation is equal to the energy required for amalgamating. The total energy of the confined system being equal to the height B of the Coulomb barrier, the intrinsic excitation energy of the compact nucleus is equal to (B - Q). In the reaction 82Se+ 138Ba (2), the dissociation of 220Th releases 180.524 MeV, and B= 196.08 MeV. With an intrinsic excitation energy of 15.56 MeV, the confined compact 220Th has enough energy for emitting two neutrons ( S(2n) = 13.85 MeV). Thus the favored xn channel of fusion reactions can be precisely predicted. This new, mass-data-based model of fusion is completely parameter-free. 1 G.G. Adamian et al., PRC 69 (2004) 044601. 2 K. Satou et al. PRC C 65(2002) 054602.

  6. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells

    PubMed Central

    Sawant, Sandesh Y.; Han, Thi Hiep; Cho, Moo Hwan

    2016-01-01

    Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored. PMID:28029116

  7. Distinguishing and quantifying the torquoselectivity in competitive ring-opening reactions using the stress tensor and QTAIM.

    PubMed

    Guo, Huan; Morales-Bayuelo, Alejandro; Xu, Tianlv; Momen, Roya; Wang, Lingling; Yang, Ping; Kirk, Steven R; Jenkins, Samantha

    2016-12-05

    Currently the theories to explain and predict the classification of the electronic reorganization due to the torquoselectivity of a ring-opening reaction cannot accommodate the directional character of the reaction pathway; the torquoselectivity is a type of stereoselectivity and therefore is dependent on the pathway. Therefore, in this investigation we introduced new measures from quantum theory of atoms in molecules and the stress tensor to clearly distinguish and quantify the transition states of the inward (TSIC) and outward (TSOC) conrotations of competitive ring-opening reactions of 3-(trifluoromethyl)cyclobut-1-ene and 1-cyano-1-methylcyclobutene. We find the metallicity ξ(r b ) of the ring-opening bond does not occur exactly at the transition state in agreement with transition state theory. The vector-based stress tensor response β σ was used to distinguish the effect of the CN, CH 3 , and CF 3 groups on the TSIC and TSOC paths that was consistent with the ellipticity ε, the total local energy density H(r b ) and the stress tensor stiffness S σ . We determine the directional properties of the TSIC and TSOC ring-opening reactions by constructing a stress tensor UσTS space with trajectories TσTS (s) with length l in real space, longer l correlated with the lowest density functional theory-evaluated total energy barrier and hence will be more thermodynamically favored. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  8. 45 CFR 73.735-501 - Prohibited acceptance of gifts, entertainment, and favors.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 45 Public Welfare 1 2010-10-01 2010-10-01 false Prohibited acceptance of gifts, entertainment, and... ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-501 Prohibited acceptance of gifts... directly or indirectly solicit or accept anything of monetary value, including gifts, gratuities, favors...

  9. To Form a Favorable Idea of Chemistry

    ERIC Educational Resources Information Center

    Heikkinen, Henry W.

    2010-01-01

    "To confess the truth, Mrs. B., I am not disposed to form a very favorable idea of chemistry, nor do I expect to derive much entertainment from it." That 200-year-old statement by Caroline to Mrs. Bryan, her teacher, appeared on the first page of Jane Marcet's pioneering secondary school textbook, "Conversations on Chemistry". It was published 17…

  10. AZALEP a randomized controlled trial of azathioprine to treat leprosy nerve damage and Type 1 reactions in India: Main findings.

    PubMed

    Lockwood, Diana N J; Darlong, Joydeepa; Govindharaj, Pitchaimani; Kurian, Royce; Sundarrao, Pamidipani; John, Annamma S

    2017-03-01

    azathioprine in the treatment of nerve damage and giving a higher dose for 48 weeks to patients. These findings highlight the difficulty in switching off leprosy inflammation and the need for better treatments for reactions and nerve damage. There is also a research need to identify patients who have recurrences and optimize treatments for them. Patients with recurrences may benefit from combined treatment with steroids and azathioprine. We have also shown that significant numbers of patients treated with steroids develop adverse effects and this needs to be highlighted in leprosy programmes. Research is needed to identify patients who do not respond to steroid treatment and develop alternative treatments for them. ClinicalTrials.gov This trial was registered with the Indian Council of Medical research clinical Trial register as a clinical trial Number-REFCTRI/2016/12/007558.

  11. CO2 hydrogenation to methanol on supported Au catalysts under moderate reaction conditions: support and particle size effects.

    PubMed

    Hartadi, Yeusy; Widmann, Daniel; Behm, R Jürgen

    2015-02-01

    The potential of metal oxide supported Au catalysts for the formation of methanol from CO2 and H2 under conditions favorable for decentralized and local conversion, which could be concepts for chemical energy storage, was investigated. Significant differences in the catalytic activity and selectivity of Au/Al2 O3 , Au/TiO2 , AuZnO, and Au/ZrO2 catalysts for methanol formation under moderate reaction conditions at a pressure of 5 bar and temperatures between 220 and 240 °C demonstrate pronounced support effects. A high selectivity (>50 %) for methanol formation was obtained only for Au/ZnO. Furthermore, measurements on Au/ZnO samples with different Au particle sizes reveal distinct Au particle size effects: although the activity increases strongly with the decreasing particle size, the selectivity decreases. The consequences of these findings for the reaction mechanism and for the potential of Au/ZnO catalysts for chemical energy storage and a "green" methanol technology are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Supervisors' attitudes and skills for active listening with regard to working conditions and psychological stress reactions among subordinate workers.

    PubMed

    Mineyama, Sachiko; Tsutsumi, Akizumi; Takao, Soshi; Nishiuchi, Kyoko; Kawakami, Norito

    2007-03-01

    We investigated whether supervisors' listening attitudes and skills were related to working conditions and psychological stress reactions among their subordinates. The subjects included 41 male supervisors and their immediate subordinates (n=203). The supervisors completed a short version of the Active Listening Attitude Scale (ALAS) consisting of two subscales: Listening Attitude and Listening Skill for Active Listening. The subordinates rated working conditions and their psychological stress reactions using selected scales of the Job Content Questionnaire and the Brief Job Stress Questionnaire. Those subordinates who worked under supervisors with a higher score of Listening Attitude and Listening Skill reported a more favorable psychological stress reaction than those who worked under supervisors with a lower score of Listening Attitude and Listening Skill. Those subordinates who worked under supervisors with a higher score of Listening Skill reported higher worksite support than those who worked under supervisors with a lower score of Listening Skill. Those subordinates who worked under supervisors with a higher score of Listening Attitude reported higher job control than those who worked under supervisors with a lower score of Listening Attitude. A supervisor's listening attitude and skill appeared to affect psychological stress reactions predominantly among male subordinates than among female subordinates. Psychological stress reactions were lower among younger subordinates who worked under supervisors with high listening skill, while no statistically difference was observed among older subordinates. These findings suggest that a supervisor's listening attitude and skill have an effect on working conditions and psychological stress reactions among subordinates and that the effects vary according to the subordinates' sex and age.

  13. Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

    PubMed

    Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

    2017-12-21

    Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

  14. 18 CFR 706.303 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 18 Conservation of Power and Water Resources 2 2011-04-01 2011-04-01 false Gifts, entertainment, and favors. 706.303 Section 706.303 Conservation of Power and Water Resources WATER RESOURCES COUNCIL EMPLOYEE RESPONSIBILITIES AND CONDUCT Conduct and Responsibilities of Special Government Employees § 706...

  15. 18 CFR 706.303 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 18 Conservation of Power and Water Resources 2 2010-04-01 2010-04-01 false Gifts, entertainment, and favors. 706.303 Section 706.303 Conservation of Power and Water Resources WATER RESOURCES COUNCIL EMPLOYEE RESPONSIBILITIES AND CONDUCT Conduct and Responsibilities of Special Government Employees § 706...

  16. 18 CFR 706.303 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 18 Conservation of Power and Water Resources 2 2013-04-01 2012-04-01 true Gifts, entertainment, and favors. 706.303 Section 706.303 Conservation of Power and Water Resources WATER RESOURCES COUNCIL EMPLOYEE RESPONSIBILITIES AND CONDUCT Conduct and Responsibilities of Special Government Employees § 706...

  17. 18 CFR 706.202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 18 Conservation of Power and Water Resources 2 2013-04-01 2012-04-01 true Gifts, entertainment, and favors. 706.202 Section 706.202 Conservation of Power and Water Resources WATER RESOURCES COUNCIL EMPLOYEE RESPONSIBILITIES AND CONDUCT Conduct and Responsibilities of Employees § 706.202 Gifts...

  18. 18 CFR 706.202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 18 Conservation of Power and Water Resources 2 2010-04-01 2010-04-01 false Gifts, entertainment, and favors. 706.202 Section 706.202 Conservation of Power and Water Resources WATER RESOURCES COUNCIL EMPLOYEE RESPONSIBILITIES AND CONDUCT Conduct and Responsibilities of Employees § 706.202 Gifts...

  19. 18 CFR 706.202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 18 Conservation of Power and Water Resources 2 2014-04-01 2014-04-01 false Gifts, entertainment, and favors. 706.202 Section 706.202 Conservation of Power and Water Resources WATER RESOURCES COUNCIL EMPLOYEE RESPONSIBILITIES AND CONDUCT Conduct and Responsibilities of Employees § 706.202 Gifts...

  20. 18 CFR 706.202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 18 Conservation of Power and Water Resources 2 2012-04-01 2012-04-01 false Gifts, entertainment, and favors. 706.202 Section 706.202 Conservation of Power and Water Resources WATER RESOURCES COUNCIL EMPLOYEE RESPONSIBILITIES AND CONDUCT Conduct and Responsibilities of Employees § 706.202 Gifts...

  1. 18 CFR 706.303 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 18 Conservation of Power and Water Resources 2 2014-04-01 2014-04-01 false Gifts, entertainment, and favors. 706.303 Section 706.303 Conservation of Power and Water Resources WATER RESOURCES COUNCIL EMPLOYEE RESPONSIBILITIES AND CONDUCT Conduct and Responsibilities of Special Government Employees § 706...

  2. 18 CFR 706.202 - Gifts, entertainment, and favors.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 18 Conservation of Power and Water Resources 2 2011-04-01 2011-04-01 false Gifts, entertainment, and favors. 706.202 Section 706.202 Conservation of Power and Water Resources WATER RESOURCES COUNCIL EMPLOYEE RESPONSIBILITIES AND CONDUCT Conduct and Responsibilities of Employees § 706.202 Gifts...

  3. Drug reaction with eosinophilia and systemic symptoms (DRESS): A histopathology based analysis.

    PubMed

    Sasidharanpillai, Sarita; Govindan, Aparna; Riyaz, Najeeba; Binitha, Manikoth P; Muhammed, Kunnummal; Khader, Anza; Reena Mariyath, Olasseri K; Simin, Muhammedkutty; Subin, Kunnari

    2016-01-01

    The data on the histology of cutaneous lesions of drug reaction with eosinophilia and systemic symptoms (DRESS) is limited. To study the histopathology of cutaneous lesions of drug reaction with eosinophilia and systemic symptoms (DRESS) and to identify any features with diagnostic or prognostic significance. All patients admitted to the dermatology ward of government medical college, Kozhikode from January 1, 2014 to December 31, 2014 with probable or definite DRESS as per the RegiSCAR scoring system and who were willing to undergo skin biopsy were included in this prospective study. The study population comprised of nine patients. The consistent histological finding documented was the predominantly lymphocytic dermal inflammatory infiltrate. Four of the five patients whose histology revealed focal interface dermatitis and keratinocyte vacuolation with or without apoptotic keratinocytes, had elevated liver transaminases. Tissue eosinophilia was associated with disease flares. The presence of atypical lymphocytes in peripheral smear and histological evidence of dense dermal inflammatory infiltrate showed an association with hepatic involvement. The main limitations of our study were the small sample size and our inability to carry out a detailed immunohistochemistry work-up. In the appropriate setting, varying combinations of epidermal hyperplasia, spongiosis, parakeratosis and individually necrotic keratinocytes in the background of lymphocyte predominant dermal infiltrate (with some atypia) favor a diagnosis of drug reaction with eosinophilia and systemic symptoms. Female sex, the presence of atypical lymphocytes in peripheral smear, dense dermal inflammatory infiltrate, tissue eosinophilia and interface dermatitis with or without keratinocyte necrosis was associated with a poor prognosis.

  4. Feasibility Study of Venus Surfuce Cooling Using Chemical Reactions with the Atmosphere

    NASA Technical Reports Server (NTRS)

    Evans, Christopher

    2013-01-01

    A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options

  5. Feasibility Study of Venus Surface Cooling Using Chemical Reactions with the Atmosphere

    NASA Technical Reports Server (NTRS)

    Evans, Christopher

    2013-01-01

    A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options.

  6. Reaction Event Counting Statistics of Biopolymer Reaction Systems with Dynamic Heterogeneity.

    PubMed

    Lim, Yu Rim; Park, Seong Jun; Park, Bo Jung; Cao, Jianshu; Silbey, Robert J; Sung, Jaeyoung

    2012-04-10

    We investigate the reaction event counting statistics (RECS) of an elementary biopolymer reaction in which the rate coefficient is dependent on states of the biopolymer and the surrounding environment and discover a universal kinetic phase transition in the RECS of the reaction system with dynamic heterogeneity. From an exact analysis for a general model of elementary biopolymer reactions, we find that the variance in the number of reaction events is dependent on the square of the mean number of the reaction events when the size of measurement time is small on the relaxation time scale of rate coefficient fluctuations, which does not conform to renewal statistics. On the other hand, when the size of the measurement time interval is much greater than the relaxation time of rate coefficient fluctuations, the variance becomes linearly proportional to the mean reaction number in accordance with renewal statistics. Gillespie's stochastic simulation method is generalized for the reaction system with a rate coefficient fluctuation. The simulation results confirm the correctness of the analytic results for the time dependent mean and variance of the reaction event number distribution. On the basis of the obtained results, we propose a method of quantitative analysis for the reaction event counting statistics of reaction systems with rate coefficient fluctuations, which enables one to extract information about the magnitude and the relaxation times of the fluctuating reaction rate coefficient, without a bias that can be introduced by assuming a particular kinetic model of conformational dynamics and the conformation dependent reactivity. An exact relationship is established between a higher moment of the reaction event number distribution and the multitime correlation of the reaction rate for the reaction system with a nonequilibrium initial state distribution as well as for the system with the equilibrium initial state distribution.

  7. 45 CFR 73.735-501 - Prohibited acceptance of gifts, entertainment, and favors.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 45 Public Welfare 1 2012-10-01 2012-10-01 false Prohibited acceptance of gifts, entertainment, and... ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-501 Prohibited acceptance of gifts, entertainment, and favors. (a) Except as provided in §§ 73.735-502 and 73.735-506, an employee shall not...

  8. 45 CFR 73.735-501 - Prohibited acceptance of gifts, entertainment, and favors.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 45 Public Welfare 1 2013-10-01 2013-10-01 false Prohibited acceptance of gifts, entertainment, and... ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-501 Prohibited acceptance of gifts, entertainment, and favors. (a) Except as provided in §§ 73.735-502 and 73.735-506, an employee shall not...

  9. 45 CFR 73.735-501 - Prohibited acceptance of gifts, entertainment, and favors.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 45 Public Welfare 1 2014-10-01 2014-10-01 false Prohibited acceptance of gifts, entertainment, and... ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-501 Prohibited acceptance of gifts, entertainment, and favors. (a) Except as provided in §§ 73.735-502 and 73.735-506, an employee shall not...

  10. 45 CFR 73.735-501 - Prohibited acceptance of gifts, entertainment, and favors.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 45 Public Welfare 1 2011-10-01 2011-10-01 false Prohibited acceptance of gifts, entertainment, and... ADMINISTRATION STANDARDS OF CONDUCT Gifts, Entertainment, and Favors § 73.735-501 Prohibited acceptance of gifts, entertainment, and favors. (a) Except as provided in §§ 73.735-502 and 73.735-506, an employee shall not...

  11. Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

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

    Elder, Thomas; Berstis, Laura; Beckham, Gregg T.

    The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of themore » $$\\alpha$$-O cleavage reaction is lower than that of the $$\\beta$$-O reaction. In conclusion, the catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.« less

  12. Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

    DOE PAGES

    Elder, Thomas; Berstis, Laura; Beckham, Gregg T.; ...

    2016-05-28

    The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of themore » $$\\alpha$$-O cleavage reaction is lower than that of the $$\\beta$$-O reaction. In conclusion, the catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.« less

  13. Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation.

    PubMed

    Elder, Thomas; Berstis, Laura; Beckham, Gregg T; Crowley, Michael F

    2016-06-15

    The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of the α-O cleavage reaction is lower than that of the β-O reaction. The catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.

  14. Allergic-like reactions to asparaginase: Atypical allergies without asparaginase inactivation.

    PubMed

    Kloos, Robin Q H; Pieters, Rob; Escherich, Gabriele; van der Sluis, Inge M

    2016-11-01

    Asparaginase is an important component of pediatric acute lymphoblastic leukemia (ALL) therapy. Unfortunately, this treatment is hampered by hypersensitivity reactions. In general, allergies - regardless of severity - cause complete inactivation of the drug. However, we report atypical allergic reactions without inactivation of asparaginase, here called allergic-like reactions. Patients with an allergic-like reaction, who were treated according to the Dutch Childhood Oncology Group ALL-11 or the CoALL 08-09 protocol, were described. The reactions were identified by continual measurement of asparaginase activity levels. Characteristics, including timing of occurrence, symptoms, grade, and the presence of antiasparaginase antibodies, were compared to those of real allergies. Fourteen allergic-like reactions occurred in nine patients. Five reactions were to PEGasparaginase and nine to Erwinia asparaginase. Allergic-like reactions occurred relatively late after the start of infusion compared to real allergies. Antibodies were absent in all but one patient with an allergic-like reaction, while they were detected in all patients with a real allergy. Symptoms and grade did not differ between the groups. Asparaginase was continued with the same formulation in six patients of whom four finished treatment with adequate activity levels. In conclusion, allergic-like reactions occur relatively late after the start of infusion and without antibodies. Despite these clinical differences, allergic-like reactions can only be distinguished from real allergies by continually measuring asparaginase activity levels. If clinically tolerated, formulations should not be switched in case of allergic-like reactions. Moreover, failure to recognize these reactions may lead to a less favorable prognosis if asparaginase therapy is terminated unnecessarily. © 2016 Wiley Periodicals, Inc.

  15. The formation of urea in space. I. Ion-molecule, neutral-neutral, and radical gas-phase reactions

    NASA Astrophysics Data System (ADS)

    Brigiano, Flavio Siro; Jeanvoine, Yannick; Largo, Antonio; Spezia, Riccardo

    2018-02-01

    Context. Many organic molecules have been observed in the interstellar medium thanks to advances in radioastronomy, and very recently the presence of urea was also suggested. While those molecules were observed, it is not clear what the mechanisms responsible to their formation are. In fact, if gas-phase reactions are responsible, they should occur through barrierless mechanisms (or with very low barriers). In the past, mechanisms for the formation of different organic molecules were studied, providing only in a few cases energetic conditions favorable to a synthesis at very low temperature. A particularly intriguing class of such molecules are those containing one N-C-O peptide bond, which could be a building block for the formation of biological molecules. Urea is a particular case because two nitrogen atoms are linked to the C-O moiety. Thus, motivated also by the recent tentative observation of urea, we have considered the synthetic pathways responsible to its formation. Aims: We have studied the possibility of forming urea in the gas phase via different kinds of bi-molecular reactions: ion-molecule, neutral, and radical. In particular we have focused on the activation energy of these reactions in order to find possible reactants that could be responsible for to barrierless (or very low energy) pathways. Methods: We have used very accurate, highly correlated quantum chemistry calculations to locate and characterize the reaction pathways in terms of minima and transition states connecting reactants to products. Results: Most of the reactions considered have an activation energy that is too high; but the ion-molecule reaction between NH2OHNH2OH2+ and formamide is not too high. These reactants could be responsible not only for the formation of urea but also of isocyanic acid, which is an organic molecule also observed in the interstellar medium.

  16. Li7(BH)5(+): a new thermodynamically favored star-shaped molecule.

    PubMed

    Torres-Vega, Juan J; Vásquez-Espinal, Alejandro; Beltran, Maria J; Ruiz, Lina; Islas, Rafael; Tiznado, William

    2015-07-15

    The potential energy surfaces (PESs) of Lin(BH)5(n-6) systems (where n = 5, 6, and 7) were explored using the gradient embedded genetic algorithm (GEGA) program, in order to find their global minima conformations. This search predicts that the lowest-energy isomers of Li6(BH)5 and Li7(BH)5(+) contain a (BH)5(6-) pentagonal fragment, which is isoelectronic and structurally analogous to the prototypical aromatic hydrocarbon anion C5H5(-). Li7(BH)5(+), along with Li7C5(+), Li7Si5(+) and Li7Ge5(+), joins a select group of clusters that adopt a seven-peak star-shape geometry, which is favored by aromaticity in the central five-membered ring, and by the preference of Li atoms for bridging positions. The theoretical analysis of chemical bonding, based on magnetic criteria, supports the notion that electronic delocalization is an important stabilization factor in all these star-shaped clusters.

  17. Electrode Reaction Mechanism of Ag 2VO 2PO 4 Cathode

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

    Zhang, Ruibo; Abtew, Tesfaye A.; Quackenbush, Nicholas F.

    In this study, the high capacity of primary lithium-ion cathode Ag 2VO 2PO 4 is facilitated by both displacement and insertion reaction mechanisms. Whether the Ag extrusion (specifically, Ag reduction with Ag metal displaced from the host crystal) and V reduction are sequential or concurrent remains unclear. A microscopic description of the reaction mechanism is required for developing design rules for new multimechanism cathodes, combining both displacement and insertion reactions. However, the amorphization of Ag 2VO 2PO 4 during lithiation makes the investigation of the electrode reaction mechanism difficult with conventional characterization tools. For addressing this issue, a combination ofmore » local probes of pair-distribution function and X-ray spectroscopy were used to obtain a description of the discharge reaction. We determine that the initial reaction is dominated by silver extrusion with vanadium playing a supporting role. In addition, once sufficient Ag has been displaced, the residual Ag + in the host can no longer stabilize the host structure and V–O environment (i.e., onset of amorphization). After amorphization, silver extrusion continues but the vanadium reduction dominates the reaction. As a result, the crossover from primarily silver reduction displacement to vanadium reduction is facilitated by the amorphization that makes vanadium reduction increasingly more favorable.« less

  18. Electrode Reaction Mechanism of Ag 2VO 2PO 4 Cathode

    DOE PAGES

    Zhang, Ruibo; Abtew, Tesfaye A.; Quackenbush, Nicholas F.; ...

    2016-05-09

    In this study, the high capacity of primary lithium-ion cathode Ag 2VO 2PO 4 is facilitated by both displacement and insertion reaction mechanisms. Whether the Ag extrusion (specifically, Ag reduction with Ag metal displaced from the host crystal) and V reduction are sequential or concurrent remains unclear. A microscopic description of the reaction mechanism is required for developing design rules for new multimechanism cathodes, combining both displacement and insertion reactions. However, the amorphization of Ag 2VO 2PO 4 during lithiation makes the investigation of the electrode reaction mechanism difficult with conventional characterization tools. For addressing this issue, a combination ofmore » local probes of pair-distribution function and X-ray spectroscopy were used to obtain a description of the discharge reaction. We determine that the initial reaction is dominated by silver extrusion with vanadium playing a supporting role. In addition, once sufficient Ag has been displaced, the residual Ag + in the host can no longer stabilize the host structure and V–O environment (i.e., onset of amorphization). After amorphization, silver extrusion continues but the vanadium reduction dominates the reaction. As a result, the crossover from primarily silver reduction displacement to vanadium reduction is facilitated by the amorphization that makes vanadium reduction increasingly more favorable.« less

  19. APPLYING RESEARCH FINDINGS IN COMPREHENSION TO CLASSROOM PRACTICE.

    ERIC Educational Resources Information Center

    WILLIAMS, RICHARD P.

    RESEARCH SHOWS THAT, IN SPITE OF THE FAVORABLE ATTITUDE TOWARD SCIENTIFIC RESEARCH, A GAP EXISTS BETWEEN THE INITIATION OF AN INNOVATION AND ITS WIDE ACCEPTANCE. TO HELP CLOSE THE GAP, TEACHERS ARE ENCOURAGED TO APPLY RESEARCH FINDINGS TO CLASSROOM PRACTICE AND TO DETERMINE THEIR FEASIBILITY. SIXTEEN STUDIES ON COMPREHENSION CITED IN THIS ARTICLE…

  20. 49 CFR 805.735-5 - Receipt of gifts, entertainment, and favors by Members or employees.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 7 2011-10-01 2011-10-01 false Receipt of gifts, entertainment, and favors by... Receipt of gifts, entertainment, and favors by Members or employees. (a) Except as provided in paragraphs..., any gift, gratuity, favor, entertainment, loan, or any other thing of monetary value, from a person...

  1. Quantum and quasiclassical dynamics of the multi-channel H + H2S reaction.

    PubMed

    Qi, Ji; Lu, Dandan; Song, Hongwei; Li, Jun; Yang, Minghui

    2017-03-28

    The prototypical multi-channel reaction H + H 2 S → H 2 + SH/H + H 2 S has been investigated using the full-dimensional quantum scattering and quasi-classical trajectory methods to unveil the underlying competition mechanism between different product channels and the mode specificity. This reaction favors the abstraction channel over the exchange channel. For both channels, excitations in the two stretching modes promote the reaction with nearly equal efficiency and are more efficient than the bending mode excitation. However, they are all less efficient than the translational energy. In addition, the experimentally observed non-Arrhenius temperature dependence of the thermal rate constants is reasonably reproduced by the quantum dynamics calculations, confirming that the non-Arrhenius behavior is caused by the pronounced quantum tunneling.

  2. Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

    DOE PAGES

    Alfonso, Dominic R.; Kauffman, Douglas R.

    2017-08-14

    Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

  3. Assessment of trends in the electrochemical CO 2 reduction and H 2 evolution reactions on metal nanoparticles

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

    Alfonso, Dominic R.; Kauffman, Douglas R.

    Here, we used density functional theory to investigate the electrochemical CO 2 reduction and competing hydrogen evolution reaction on model Au, Ag, Cu, Ir, Ni, Pd, Pt, and Rh nanoparticles. On the coinage metal, the free energy of adsorbed COOH, CO, and H intermediates generally becomes more favorable with decreasing particle size. This pattern was also observed on all transition metals with the binding of the intermediates observed to be stronger on almost all of these metals. Comparative studies of the reaction profile reveal that H 2 evolution is the first reaction to be energetically allowed at zero applied bias

  4. Science Curriculum Components Favored by Taiwanese Biology Teachers

    NASA Astrophysics Data System (ADS)

    Lin, Chen-Yung; Hu, Reping; Changlai, Miao-Li

    2005-09-01

    The new 1-9 curriculum framework in Taiwan provides a remarkable change from previous frameworks in terms of the coverage of content and the powers of teachers. This study employs a modified repertory grid technique to investigate biology teachers' preferences with regard to six curriculum components. One hundred and eighty-five in-service and pre-service biology teachers were asked to determine which science curriculum components they liked and disliked most of all to include in their biology classes. The data show that the rank order of these science curriculum components, from top to bottom, was as follows: application of science, manipulation skills, scientific concepts, social/ethical issues, problem-solving skills, and the history of science. They also showed that pre-service biology teachers, as compared with in-service biology teachers, favored problem-solving skills significantly more than manipulative skills, while in-service biology teachers, as compared with pre-service biology teachers, favored manipulative skills significantly more than problem-solving skills. Some recommendations for ensuring the successful implementation of the Taiwanese 1-9 curriculum framework are also proposed.

  5. B, N co-doped carbon from cross-linking induced self-organization of boronate polymer for supercapacitor and oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Chang, Ying; Yuan, Conghui; Liu, Cheng; Mao, Jie; Li, Yuntong; Wu, Haiyang; Wu, Yuzhe; Xu, Yiting; Zeng, Birong; Dai, Lizong

    2017-10-01

    A novel strategy has been developed to generate B, N co-doped carbon materials (CNBs) through the pyrolysis of boronate polymer nanoparticles (BPNs) derived from the condensation reaction between catechol and boronic monomers. The morphology, surface area and heteroatom (viz. B and N) content of the CNBs can be easily adjusted by altering the molar ratio between catechol and boronic monomers. The supercapacitor and oxygen reduction reaction (ORR) performance of the CNBs are optimized. CNBs derived from equal molar ratio of catechol and boronic monomers exhibit favorable performance for supercapacitor, featuring a specific capacitance of up to 299.4 F/g at 0.2 A/g, an improved rate capability and excellent cycle stability. Notably, CNBs prepared using 1/2 molar ratio of catechol to boronic monomers show excellent ORR performance, as they demonstrate good electrocatalytic activity, high tolerance for methanol and long durability. Our findings may be of interest in the design of carbon materials with optimized electrochemical properties through the control over surface area and the content of heteroatom.

  6. Preschoolers Reduce Inequality While Favoring Individuals with More

    ERIC Educational Resources Information Center

    Li, Vivian; Spitzer, Brian; Olson, Kristina R.

    2014-01-01

    Inequalities are everywhere, yet little is known about how children respond to people affected by inequalities. This article explores two responses--minimizing inequalities and favoring those who are advantaged by them. In Studies 1a (N = 37) and 1b (N = 38), 4- and 5-year-olds allocated a resource to a disadvantaged recipient, but judged…

  7. High-rise buildings and neurologically favorable outcome after out-of-hospital cardiac arrest.

    PubMed

    Kobayashi, Daisuke; Kitamura, Tetsuhisa; Kiyohara, Kosuke; Nishiyama, Chika; Hayashida, Sumito; Fujii, Tomoko; Izawa, Junichi; Shimamoto, Tomonari; Matsuyama, Tasuku; Hatakeyama, Toshihiro; Katayama, Yusuke; Kiguchi, Takeyuki; Kawamura, Takashi; Iwami, Taku

    2016-12-01

    The number of people living in high-rise buildings has recently been increasing in Japan, and delayed transport time by emergency-medical-service (EMS) personnel from higher floors could lead to lower survival after out-of-hospital cardiac arrest (OHCA). However, there are no clinical studies assessing the association between the floor where patients reside and neurologically favorable outcome after OHCA. This was a prospective, population-based study conducted in Osaka City, Japan that enrolled adults aged >=18years suffering an OHCA of cardiac origin before EMS arrival between 2013 and 2014. The primary outcome measure was one-month survival with neurologically favorable outcome. We divided OHCA patients into the following groups: those residing on >=3 floors (the high floor group) and <3 floors (the low floor group). Multiple logistic regression analysis was used to assess factors associated with neurologically favorable outcome. A total of 2979 patients were eligible for analysis. Of them, 1885 (62.3%) occurred below the third floor and 1094 (37.4%) occurred at or above the third floor. The proportion of neurologically favorable outcome after OHCA was significantly lower in the high floor group than in the low floor group (2.7% [30/1094] versus 4.8% [91/1885], P=0.005). In a multivariate analysis, neurologically favorable outcome after OHCA was significantly lower in the high floor group than in the low floor group (adjusted odds ratio, 0.59 [95% confidence interval, 0.37-0.96]). In this population, one-month survival with neurologically favorable outcome from OHCA was lower in the high floor group than in the low floor group. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  8. Theoretical study of the mechanism of CH2CO + CN reaction

    NASA Astrophysics Data System (ADS)

    Sun, Hao; He, Hong-Qing; Hong, Bo; Chang, Ying-Fei; An, Zhe; Wang, Rong-Shun

    The potential energy surface information of the CH2CO + CN reaction is obtained at the B3LYP/6-311+G(d,p) level. To gain further mechanistic knowledge, higher-level single-point calculations for the stationary points are performed at the QCISD(T)/6-311++G(d,p) level. The CH2CO + CN reaction proceeds through four possible mechanisms: direct hydrogen abstraction, olefinic carbon addition-elimination, carbonyl carbon addition-elimination, and side oxygen addition-elimination. Our calculations demonstrate that R?IM1?TS3?P3: CH2CN + CO is the energetically favorable channel; however, channel R?IM2?TS4?P4: CH2NC + CO is considerably competitive, especially as the temperature increases (R, IM, TS, and P represent reactant, intermediate, transition state, and product, respectively). The present study may be helpful in probing the mechanism of the CH2CO + CN reaction.

  9. Alternative mechanistic explanation for ligand-dependent selectivities in copper-catalyzed N- and O-arylation reactions.

    PubMed

    Yu, Hai-Zhu; Jiang, Yuan-Ye; Fu, Yao; Liu, Lei

    2010-12-29

    The ligand-dependent selectivities in Ullmann-type reactions of amino alcohols with iodobenzene by β-diketone- and 1,10-phenanthroline-ligated Cu(I) complexes were recently explained by the single-electron transfer and iodine atom transfer mechanisms (Jones, G. O., Liu, P., Houk, K. N., and Buchwald, S. L. J. Am. Chem. Soc. 2010, 132, 6205.). The present study shows that an alternative, oxidative addition/reductive elimination mechanism may also explain the selectivities. Calculations indicate that a Cu(I) complex with a negatively charged β-diketone ligand is electronically neutral, so that oxidative addition of ArI to a β-diketone-ligated Cu(I) prefers to occur (and occur readily) in the absence of the amino alcohol. Thus, coordination of the amino alcohol in its neutral form can only occur at the Cu(III) stage where N-coordination is favored over O-coordination. The coordination step is the rate-limiting step and the outcome is that N-arylation is favored with the β-diketone ligand. On the other hand, a Cu(I) complex with a neutral 1,10-phenanthroline ligand is positively charged, so that oxidative addition of ArI to a 1,10-phenanthroline-ligated Cu(I) has to get assistance from a deprotonated amino alcohol substrate. This causes oxidative addition to become the rate-limiting step in the 1,10-phenanthroline-mediated reaction. The immediate product of the oxidative addition step is found to undergo facile reductive elimination to provide the arylation product. Because O-coordination of a deprotonated amino alcohol is favored over N-coordination in the oxidative addition transition state, O-arylation is favored with the 1,10-phenanthroline ligand.

  10. Water Assisted Reaction Mechanism of OH- with CCl4 in Aqueous Solution - Hybrid Quantum Mechanical and Molecular Mechanics Investigation

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

    Chen, Jie; Yin, Hongyun; Wang, Dunyou

    2013-02-20

    The OH- (H2O) + CCl4 reaction in aqueous solution was investigated using the combined quantum mechanical and molecular mechanics approach. The reaction mechanism of OH- (H2O) + CCl4 consists of two concerted steps - formation of OH- in the favorable attack conformation via the proton transfer process, and the nucleophilic substitution process in which the newly formed OH- attacks the CCl4. The free energy activation barrier is 38.2 kcal/mol at CCSD(T)/MM level of theory for this reaction, which is about 10.3 kcal/mol higher than that of the direct nucleophilic substitution mechanism of the OH- + CCl4 reaction in aqueous solution.

  11. Ab initio Quantum Chemical Studies of Reactions in Astrophysical Ices. Reactions Involving CH3OH, CO2, CO, HNCO in H2CO/NH3/H2O Ices

    NASA Technical Reports Server (NTRS)

    Woon, David E.

    2006-01-01

    While reactions between closed shell molecules generally involve prohibitive barriers in the gas phase, prior experimental and theoretical studies have demonstrated that some of these reactions are significantly enhanced when confined within an icy grain mantle and can occur efficiently at temperatures below 100 K with no additional energy processing. The archetypal case is the reaction of formaldehyde (H2CO) and ammonia (NH3) to yield hydroxymethylamine (NH2CH2OH). In the present work we have characterized reactions involving methanol (CH3OH), carbon dioxide (CO2), carbon monoxide (CO), and isocyanic acid (HNCO) in search of other favorable cases. Most of the emphasis is on CH3OH, which was investigated in the two-body reaction with one H2CO and the three-body reaction with two H2CO molecules. The addition of a second H2CO to the product of the reaction between CH3OH and H2CO was also considered as an alternative route to longer polyoxymethylene polymers of the -CH2O- form. The reaction between HNCO and NH3 was studied to determine if it can compete against the barrierless charge transfer process that yields OCN(-) and NH4(+). Finally, the H2CO + NH3 reaction was revisited with additional benchmark calculations that confirm that little or no barrier is present when it occurs in ice.

  12. Autoinjectors Preferred for Intramuscular Epinephrine in Anaphylaxis and Allergic Reactions

    PubMed Central

    Campbell, Ronna L.; Bellolio, M. Fernanda; Motosue, Megan S.; Sunga, Kharmene L.; Lohse, Christine M.; Rudis, Maria I.

    2016-01-01

    Introduction Epinephrine is the treatment of choice for anaphylaxis. We surveyed emergency department (ED) healthcare providers regarding two methods of intramuscular (IM) epinephrine administration (autoinjector and manual injection) for the management of anaphylaxis and allergic reactions and identified provider perceptions and preferred method of medication delivery. Methods This observational study adhered to survey reporting guidelines. It was performed through a Web-based survey completed by healthcare providers at an academic ED. The primary outcomes were assessment of provider perceptions and identification of the preferred IM epinephrine administration method by ED healthcare providers. Results Of 217 ED healthcare providers invited to participate, 172 (79%) completed the survey. Overall, 82% of respondents preferred the autoinjector method of epinephrine administration. Providers rated the autoinjector method more favorably for time required for training, ease of use, convenience, satisfaction with weight-based dosing, risk of dosing errors, and speed of administration (p<0.001 for all comparisons). However, manual injection use was rated more favorably for risk of provider self-injury and patient cost (p<0.001 for both comparisons). Three participants (2%) reported a finger stick injury from an epinephrine autoinjector. Conclusion ED healthcare providers preferred the autoinjector method of IM epinephrine administration for the management of anaphylaxis or allergic reactions. Epinephrine autoinjector use may reduce barriers to epinephrine administration for the management of anaphylaxis in the ED. PMID:27833688

  13. KOH-activated multi-walled carbon nanotubes as platinum supports for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    He, Chaoxiong; Song, Shuqin; Liu, Jinchao; Maragou, Vasiliki; Tsiakaras, Panagiotis

    In the present investigation, multi-walled carbon nanotubes (MWCNTs) thermally treated by KOH were adopted as the platinum supporting material for the oxygen reduction reaction electrocatalysts. FTIR and Raman spectra were used to investigate the surface state of MWCNTs treated by KOH at different temperatures (700, 800, and 900 °C) and showed MWCNTs can be successfully functionalized. The structural properties of KOH-activated MWCNTs supported Pt were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by the aid of cyclic voltammetry (CV) and rotating disk electrode (RDE) voltammetry. According to the experimental findings of the present work, the surrface of MWCNTs can be successfully functionalized with oxygen-containing groups after activation by KOH, favoring the good dispersion of Pt nanoparticles with narrow size distribution. The as-prepared Pt catalysts supported on KOH treated MWCNTs at higher temperature, possess higher electrochemical surface area and exhibit desirable activity towards oxygen reduction reaction (ORR). More precisely, it has been found that the electrochemical active area of Pt/MWCNTs-900 is approximately two times higher than that of Pt/MWCNTs. It can be concluded that KOH activation is an effective way to decorate MWCNTs' surface with oxygen-containing groups and bigger surface area, which makes them more suitable as electrocatalyst support materials.

  14. Basic distinctions between cold- and hot-fusion reactions in the synthesis of superheavy elements

    NASA Astrophysics Data System (ADS)

    Nasirov, A. K.; Muminov, A. I.; Giardina, G.; Mandaglio, G.

    2014-07-01

    Superheavy elements (SHE) of charge number in the range of Z = 106-112 were synthesized in so-called cold-fusion reactions. The smallness of the excitation energy of compound nuclei is the main advantage of cold-fusion reactions. However, the synthesis of SHEs of charge number in the region of Z ≥ 112 is strongly complicated in cold-fusion reactions by a sharp decrease in the cross section of a compound nucleus formation in the entrance channel because of superiority of quasifission in the competition with complete fusion. Two favorable circumstances contributed to the success of the experiments aimed at the synthesis of the Z = 113-118 elements and performed at the Laboratory of Nuclear Reactions at the Joint Institute for Nuclear Research: large cross sections for the production of a compound nucleus, which are characteristic of hot-fusion reactions, and an increase in the fission barrier for nuclei toward the stability island. The factor that complicates the formation of a compound nucleus in cold-fusion reactions is discussed.

  15. Predictors of favorable soft tissue profile outcomes following Class II Twin-block treatment

    PubMed Central

    Kim, Ji-Eun; Mah, Su-Jung; Kim, Tae-Woo; Kim, Su-Jung; Park, Ki-Ho

    2018-01-01

    Objective The aim of this study was to determine cephalometric factors that help predict favorable soft-tissue profile outcomes following treatment with the Class II Twin-block appliance. Methods Pre- and post-treatment lateral cephalograms of 45 patients treated with the Class II Twin-block appliance were retrospectively analyzed. Profile silhouettes were drawn from the cephalograms and evaluated by three orthodontists in order to determine the extent of improvement. Samples were divided into a favorable group (upper 30% of visual analogue scale [VAS] scores, n = 14) and an unfavorable group (lower 30% of VAS scores, n = 14). Skeletal and soft-tissue measurements were performed on the cephalograms and an intergroup comparison was conducted. Results An independent t-test revealed that the following pre-treatment values were lower in the favorable group compared to the unfavorable group: lower incisor to mandibular plane angle, lower incisor to pogonion distance, point A-nasion-point B angle, sella-nasion line (SN) to maxillary plane angle, SN to mandibular plane angle, gonial angle, and symphysis inclination. The favorable group had a larger incisor inclination to occlusal plane. Moreover, the favorable group showed larger post-treatment changes in gonial angle, B point projection, and pogonion projection than did the unfavorable group. Conclusions Class II malocclusion patients with a low divergent skeletal pattern and reduced lower incisor protrusions are likely to show more improvement in soft-tissue profile outcomes following Class II Twin-block treatment. PMID:29291184

  16. Predictors of favorable soft tissue profile outcomes following Class II Twin-block treatment.

    PubMed

    Kim, Ji-Eun; Mah, Su-Jung; Kim, Tae-Woo; Kim, Su-Jung; Park, Ki-Ho; Kang, Yoon-Goo

    2018-01-01

    The aim of this study was to determine cephalometric factors that help predict favorable soft-tissue profile outcomes following treatment with the Class II Twin-block appliance. Pre- and post-treatment lateral cephalograms of 45 patients treated with the Class II Twin-block appliance were retrospectively analyzed. Profile silhouettes were drawn from the cephalograms and evaluated by three orthodontists in order to determine the extent of improvement. Samples were divided into a favorable group (upper 30% of visual analogue scale [VAS] scores, n = 14) and an unfavorable group (lower 30% of VAS scores, n = 14). Skeletal and soft-tissue measurements were performed on the cephalograms and an intergroup comparison was conducted. An independent t -test revealed that the following pre-treatment values were lower in the favorable group compared to the unfavorable group: lower incisor to mandibular plane angle, lower incisor to pogonion distance, point A-nasion-point B angle, sella-nasion line (SN) to maxillary plane angle, SN to mandibular plane angle, gonial angle, and symphysis inclination. The favorable group had a larger incisor inclination to occlusal plane. Moreover, the favorable group showed larger post-treatment changes in gonial angle, B point projection, and pogonion projection than did the unfavorable group. Class II malocclusion patients with a low divergent skeletal pattern and reduced lower incisor protrusions are likely to show more improvement in soft-tissue profile outcomes following Class II Twin-block treatment.

  17. Addition and hydrogen abstraction reactions of an OH radical with 8-oxoguanine

    NASA Astrophysics Data System (ADS)

    Jena, N. R.; Mishra, P. C.

    2006-05-01

    Addition reaction of an OH radical at the C2, C4, C5 or C8 position of 8-oxoguanine (8OG) and abstraction of its H9 atom by an OH radical were studied using density functional theory (B3LYP) employing 6-31G ∗∗, 6-311++G ∗∗ and AUG-cc-pVDZ basis sets. Solvent effects of aqueous media were treated using the PCM model. It is found that the addition of an OH radical at the C4 position of 8OG would be most favored in both gas phase and aqueous media. These addition and abstraction reactions in aqueous media are both found to be barrierless.

  18. Energy Dependent Stereodynamics of the Ne (3P2)+Ar Reaction

    NASA Astrophysics Data System (ADS)

    Gordon, Sean D. S.; Zou, Junwen; Tanteri, Silvia; Jankunas, Justin; Osterwalder, Andreas

    2017-08-01

    The stereodynamics of the Ne (P2 3 )+Ar Penning and associative ionization reactions have been studied using a crossed molecular beam apparatus. The experiment uses a curved magnetic hexapole to polarize the Ne (P2 3 ) , which is then oriented with a shaped magnetic field in the region where it intersects with a beam of Ar (S 1 ) . The ratios of Penning to associative ionization were recorded over a range of collision energies from 320 to 500 cm-1 and the data were used to obtain Ω state dependent reactivities for the two reaction channels. These reactivities were found to compare favorably to those predicted in the theoretical work of Brumer et al.

  19. HOW MUCH FAVORABLE SELECTION IS LEFT IN MEDICARE ADVANTAGE?

    PubMed Central

    PRICE, MARY; MCWILLIAMS, J. MICHAEL; HSU, JOHN; MCGUIRE, THOMAS G.

    2015-01-01

    The health economics literature contains two models of selection, one with endogenous plan characteristics to attract good risks and one with fixed plan characteristics; neither model contains a regulator. Medicare Advantage, a principal example of selection in the literature, is, however, subject to anti-selection regulations. Because selection causes economic inefficiency and because the historically favorable selection into Medicare Advantage plans increased government cost, the effectiveness of the anti-selection regulations is an important policy question, especially since the Medicare Advantage program has grown to comprise 30 percent of Medicare beneficiaries. Moreover, similar anti-selection regulations are being used in health insurance exchanges for those under 65. Contrary to earlier work, we show that the strengthened anti-selection regulations that Medicare introduced starting in 2004 markedly reduced government overpayment attributable to favorable selection in Medicare Advantage. At least some of the remaining selection is plausibly related to fixed plan characteristics of Traditional Medicare versus Medicare Advantage rather than changed selection strategies by Medicare Advantage plans. PMID:26389127

  20. Poleward displacement of coastal upwelling-favorable winds through the 21st century

    NASA Astrophysics Data System (ADS)

    Rykaczewski, R. R.; Dunne, J. P.; Sydeman, W. J.; Garcia-Reyes, M.; Black, B.; Bograd, S. J.

    2016-02-01

    Coastal upwelling is a critical factor influencing the biological production, acidification, and deoxygenation of the ocean's major eastern boundary current ecosystems. A leading conceptual hypothesis projects that the winds that induce coastal upwelling will intensify in response to increased land-sea temperature differences associated with anthropogenic global warming. We examine this hypothesis using an ensemble of coupled, ocean-atmosphere models and find limited evidence for intensification of upwelling-favorable winds or atmospheric pressure gradients in response to increasing land-sea temperature differences. However, our analyses reveal consistent latitudinal and seasonal dependencies of projected changes in wind intensity associated with poleward migration of major atmospheric high-pressure cells. Summertime winds near poleward boundaries of climatological upwelling zones are projected to intensify, while winds near equatorward boundaries are projected to weaken. Developing a better understanding of future changes in upwelling winds is essential to identifying portions of the oceans susceptible to increased hypoxia, ocean acidification, and eutrophication under climate change.

  1. 12 CFR 560.110 - Most favored lender usury preemption.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... Section 560.110 Banks and Banking OFFICE OF THRIFT SUPERVISION, DEPARTMENT OF THE TREASURY LENDING AND INVESTMENT Lending and Investment Provisions Applicable to all Savings Associations § 560.110 Most favored... lending institution by the law of that state. If state law permits different interest charges on specified...

  2. Over 20 years of reaction access systems from MDL: a novel reaction substructure search algorithm.

    PubMed

    Chen, Lingran; Nourse, James G; Christie, Bradley D; Leland, Burton A; Grier, David L

    2002-01-01

    From REACCS, to MDL ISIS/Host Reaction Gateway, and most recently to MDL Relational Chemistry Server, a new product based on Oracle data cartridge technology, MDL's reaction database management and retrieval systems have undergone great changes. The evolution of the system architecture is briefly discussed. The evolution of MDL reaction substructure search (RSS) algorithms is detailed. This article mainly describes a novel RSS algorithm. This algorithm is based on a depth-first search approach and is able to fully and prospectively use reaction specific information, such as reacting center and atom-atom mapping (AAM) information. The new algorithm has been used in the recently released MDL Relational Chemistry Server and allows the user to precisely find reaction instances in databases while minimizing unrelated hits. Finally, the existing and new RSS algorithms are compared with several examples.

  3. Do Halogen–Hydrogen Bond Donor Interactions Dominate the Favorable Contribution of Halogens to Ligand–Protein Binding?

    PubMed Central

    2017-01-01

    Halogens are present in a significant number of drugs, contributing favorably to ligand–protein binding. Currently, the contribution of halogens, most notably chlorine and bromine, is largely attributed to halogen bonds involving favorable interactions with hydrogen bond acceptors. However, we show that halogens acting as hydrogen bond acceptors potentially make a more favorable contribution to ligand binding than halogen bonds based on quantum mechanical calculations. In addition, bioinformatics analysis of ligand–protein crystal structures shows the presence of significant numbers of such interactions. It is shown that interactions between halogens and hydrogen bond donors (HBDs) are dominated by perpendicular C–X···HBD orientations. Notably, the orientation dependence of the halogen–HBD (X–HBD) interactions is minimal over greater than 100° with favorable interaction energies ranging from −2 to −14 kcal/mol. This contrasts halogen bonds in that X–HBD interactions are substantially more favorable, being comparable to canonical hydrogen bonds, with a smaller orientation dependence, such that they make significant, favorable contributions to ligand–protein binding and, therefore, should be actively considered during rational ligand design. PMID:28657759

  4. Thermal energy storage. [by means of chemical reactions

    NASA Technical Reports Server (NTRS)

    Grodzka, P. G.

    1975-01-01

    The principles involved in thermal energy storage by sensible heat, chemical potential energy, and latent heat of fusion are examined for the purpose of evolving selection criteria for material candidates in the low ( 0 C) and high ( 100 C) temperature ranges. The examination identifies some unresolved theoretical considerations and permits a preliminary formulation of an energy storage theory. A number of candidates in the low and high temperature ranges are presented along with a rating of candidates or potential candidates. A few interesting candidates in the 0 to 100 C region are also included. It is concluded that storage by means of reactions whose reversibility can be controlled either by product removal or by catalytic means appear to offer appreciable advantages over storage with reactions whose reversability cannot be controlled. Among such advantages are listed higher heat storage capacities and more favorable options regarding temperatures of collection, storage, and delivery. Among the disadvantages are lower storage efficiencies.

  5. Transduction of Redox Signaling by Electrophile-Protein Reactions

    PubMed Central

    Rudolph, Tanja K.; Freeman, Bruce A.

    2014-01-01

    Over the last 50 years, the posttranslational modification (PTM) of proteins has emerged as a central mechanism for cells to regulate metabolism, growth, differentiation, cell-cell interactions, and immune responses. By influencing protein structure and function, PTM leads to a multiplication of proteome diversity. Redox-dependent PTMs, mediated by environmental and endogenously generated reactive species, induce cell signaling responses and can have toxic effects in organisms. PTMs induced by the electrophilic by-products of redox reactions most frequently occur at protein thiols; other nucleophilic amino acids serve as less favorable targets. Advances in mass spectrometry and affinity-chemistry strategies have improved the detection of electrophile-induced protein modifications both in vitro and in vivo and have revealed a high degree of amino acid and protein selectivity of electrophilic PTM. The identification of biological targets of electrophiles has motivated further study of the functional impact of various PTM reactions on specific signaling pathways and how this might affect organisms. PMID:19797270

  6. Aligning Metabolic Pathways Exploiting Binary Relation of Reactions.

    PubMed

    Huang, Yiran; Zhong, Cheng; Lin, Hai Xiang; Huang, Jing

    2016-01-01

    Metabolic pathway alignment has been widely used to find one-to-one and/or one-to-many reaction mappings to identify the alternative pathways that have similar functions through different sets of reactions, which has important applications in reconstructing phylogeny and understanding metabolic functions. The existing alignment methods exhaustively search reaction sets, which may become infeasible for large pathways. To address this problem, we present an effective alignment method for accurately extracting reaction mappings between two metabolic pathways. We show that connected relation between reactions can be formalized as binary relation of reactions in metabolic pathways, and the multiplications of zero-one matrices for binary relations of reactions can be accomplished in finite steps. By utilizing the multiplications of zero-one matrices for binary relation of reactions, we efficiently obtain reaction sets in a small number of steps without exhaustive search, and accurately uncover biologically relevant reaction mappings. Furthermore, we introduce a measure of topological similarity of nodes (reactions) by comparing the structural similarity of the k-neighborhood subgraphs of the nodes in aligning metabolic pathways. We employ this similarity metric to improve the accuracy of the alignments. The experimental results on the KEGG database show that when compared with other state-of-the-art methods, in most cases, our method obtains better performance in the node correctness and edge correctness, and the number of the edges of the largest common connected subgraph for one-to-one reaction mappings, and the number of correct one-to-many reaction mappings. Our method is scalable in finding more reaction mappings with better biological relevance in large metabolic pathways.

  7. Breakout reactions from the CNO-cycle

    NASA Astrophysics Data System (ADS)

    Jisonna, Louis Joseph, Jr.

    Breakout reactions from the CNO cycles leading into the rp -process in explosive stellar hydrogen burning environments have been studied using the Argonne Tandem Linac Accelerator System (ATLAS). Earlier work is reported and summarized with an introduction to the beam, target and detector development in the nuclear astrophysics group at Argonne National Laboratory. The 18 Ne(a,p) 21 Na reaction has been studied via the time inverse reaction p( 21 Na,a) 18 Ne. A 5 × 10^-5 particle nanoamp 21 Na beam was produced at the ATLAS in-flight facility via the p( 21 Ne,n) 21 Na reaction. Cross sections were obtained at five energies covering the region between 9.4 <= E x <= 9.9 MeV in the compound nucleus 22 Mg, and compared with previous measurements. The 19 Ne(p,g) 20 Na reaction was also studied by populating proton unbound states via the 3 He(20 Ne,t) 20 Na* reaction. We have observed for the first time evidence for the g- decay of the astrophysically important 2.645 MeV state in 20 Na. Branching ratios obtained for the first two proton unbound states in 20 Na were G p /G g (2.645 MeV) = [Special characters omitted.] and a lower limit of G p /G g (2.849 MeV) >= 26.0 (1-s CL). The experimental branching ratios were compared with theoretical predictions based on shell-model calculations and on the properties of mirror states in 20 F. Our results favor a J p = 1 + assignment for the 2.645 MeV state and a J p = 3 + for the 2.849 MeV at the 1-s confidence level. Our result also suggests that the resonance strength for radiative capture through the 2.645 MeV state is close to the value og[approximate] 6 meV, in agreement with the value calculated assuming it to be the mirror of the 3.172 MeV intruder state in 20 F with a 6 p2h configuration.

  8. Higher Natriuretic Peptide Levels Associate with a Favorable Adipose Tissue Distribution Profile

    PubMed Central

    Neeland, Ian J.; Winders, Benjamin R.; Ayers, Colby R.; Das, Sandeep R.; Chang, Alice Y.; Berry, Jarett D.; Khera, Amit; McGuire, Darren K.; Vega, Gloria L.; de Lemos, James A.; Turer, Aslan T.

    2013-01-01

    Objectives To investigate the association between natriuretic peptides and body fat distribution in a multiethnic cohort. Background Natriuretic peptides stimulate lipolysis, reduce weight gain, and promote adipocyte browning in animal models but data are lacking in humans. Methods 2619 participants without heart failure in the Dallas Heart Study underwent measurements of 1) B-type natriuretic peptide (BNP) and NT-proBNP and 2) body fat distribution by dual energy x-ray absorptiometry and magnetic resonance imaging. Cross-sectional associations of natriuretic peptides with adiposity phenotypes were examined after adjustment for age, sex, race, comorbidities, and body mass index. Results Median BNP and NT-proBNP levels in the study cohort (mean age 44 years, 56% women, 48% African-Americans, 32% obese) were 3.0 and 28.1 pg/mL, respectively. Natriuretic peptide levels above the median were associated with a more favorable body fat profile and less insulin resistance including lower visceral fat, liver fat, and HOMA-IR; and more lower body fat and higher adiponectin (p<0.05 for each). In multivariable analyses, NT-proBNP remained inversely associated with visceral (β= −0.08, p<0.0001) and liver fat (β= −0.14, p<0.0001) and positively associated with lower body fat (β= 0.07, p<0.0001) independent of age, sex, race, and obesity-status; findings were similar with BNP. Adjustment for body composition, HOMA-IR, circulating androgens, and adipocytokines did not attenuate the associations. Conclusions Higher natriuretic peptide levels were independently associated with a favorable adiposity profile, characterized by decreased visceral and liver fat and increased lower body fat, suggesting a link between the heart and adipose tissue distribution mediated through natriuretic peptides. PMID:23602771

  9. Reaction mechanism and kinetics of the degradation of terbacil initiated by OH radical - A theoretical study

    NASA Astrophysics Data System (ADS)

    Ponnusamy, S.; Sandhiya, L.; Senthilkumar, K.

    2018-02-01

    The reaction of terbacil with OH radical is studied by using electronic structure calculations. The reaction of terbacil with OH radical is found to proceed by H-atom abstraction, Cl-atom abstraction and OH addition reactions. The initially formed alkyl radical will undergo atmospheric transformation in the presence of molecular oxygen leading to the formation of peroxy radical. The reaction of peroxy radical with other atmospheric oxidants, such as HO2 and NO radicals is studied. The rate constant is calculated for the H-atom abstraction reactions over the temperature range of 200-1000 K. The results obtained from electronic structure calculations and kinetic study show that the H-atom abstraction reaction is more favorable. The calculated lifetime of terbacil is 24 h in normal atmospheric OH concentration. The rate constant calculated for H-atom abstraction reactions is 6 × 10-12, 4.4 × 10-12 and 3.2 × 10-12 cm3molecule-1s-1, respectively which is in agreement with the previous literature value of 1.9 × 10-12 cm3molecule-1s-1.

  10. Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons

    NASA Astrophysics Data System (ADS)

    Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.

    2017-09-01

    The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

  11. Cerebral Toxoplasmosis Diagnosed by Nested-polymerase Chain Reaction in a Patient with Rheumatoid Arthritis.

    PubMed

    Matsuura, Jun; Fujii, Akihiro; Mizuta, Ikuko; Norose, Kazumi; Mizuno, Toshiki

    2018-05-15

    A 65-year-old woman with rheumatoid arthritis (RA) visited our hospital because of right facial sensory hypoesthesia. Cerebral toxoplasmosis was suspected on brain magnetic resonance imaging. We discontinued methotrexate for RA and started a sulfamethoxazole/trimethoprim (ST) mixture. Although ST treatment was interrupted because of adverse reactions, her prognosis was favorable. The Toxoplasma 18S rDNA gene was detected by nested-polymerase chain reaction (PCR) from blood and cerebrospinal fluid. Detecting the Toxoplasma 18S rDNA gene by nested-PCR is useful for the diagnosis and safer than a brain biopsy. In addition, the discontinuation of immunosuppressants may be recommended in patients compromised by those immunosuppressants.

  12. Positive Surgical Margins in Favorable-Stage Differentiated Thyroid Cancer.

    PubMed

    Mercado, Catherine E; Drew, Peter A; Morris, Christopher G; Dziegielewski, Peter T; Mendenhall, William M; Amdur, Robert J

    2018-04-16

    The significance of positive margin in favorable-stage well-differentiated thyroid cancer is controversial. We report outcomes of positive-margin patients with a matched-pair comparison to a negative-margin group. A total of 25 patients with classic-histology papillary or follicular carcinoma, total thyroidectomy +/- node dissection, stage T1-3N0-1bM0, positive surgical margin at primary site, adjuvant radioactive iodine (I-131), and age older than 18 years were treated between 2003 and 2013. Endpoints were clinical and biochemical (thyroglobulin-only) recurrence-free survival. Matched-pair analysis involved a 1:1 match with negative-margin cases matched for overall stage and I-131 dose. Recurrence-free survival in positive-margin patients was 71% at 10 years. No patient was successfully salvaged with additional treatment. Only 1 patient died of thyroid cancer. Recurrence-free survival at 10 years was worse with a positive (71%) versus negative (90%) margin (P=0.140). Cure with a microscopically positive margin was suboptimal (71%) despite patients having classic-histology papillary and follicular carcinoma, favorable stage, and moderate-dose I-131 therapy.

  13. Computed Regioselectivity and Conjectured Biological Activity of Ene Reactions of Singlet Oxygen with the Natural Product Hyperforin.

    PubMed

    Abramova, Inna; Rudshteyn, Benjamin; Liebman, Joel F; Greer, Alexander

    2017-03-01

    Hyperforin is a constituent of St. John's wort and coexists with the singlet oxygen sensitizer hypericin. Density functional theory, molecular mechanics and Connolly surface calculations show that accessibility in the singlet oxygen "ene" reaction favors the hyperforin "southwest" and "southeast" prenyl (2-methyl-2-butenyl) groups over the northern prenyl groups. While the southern part of hyperforin is initially more susceptible to oxidation, up to 4 "ene" reactions of singlet oxygen can take place. Computational results assist in predicting the fate of adjacent hydroperoxides in hyperforin, where the loss of hydrogen atoms may lead to the formation of a hydrotrioxide and a carbonyl instead of a Russell reaction. © 2017 The American Society of Photobiology.

  14. Do Author-Suggested Reviewers Rate Submissions More Favorably than Editor-Suggested Reviewers? A Study on Atmospheric Chemistry and Physics

    PubMed Central

    Bornmann, Lutz; Daniel, Hans-Dieter

    2010-01-01

    Background Ratings in journal peer review can be affected by sources of bias. The bias variable investigated here was the information on whether authors had suggested a possible reviewer for their manuscript, and whether the editor had taken up that suggestion or had chosen a reviewer that had not been suggested by the authors. Studies have shown that author-suggested reviewers rate manuscripts more favorably than editor-suggested reviewers do. Methodology/Principal Findings Reviewers' ratings on three evaluation criteria and the reviewers' final publication recommendations were available for 552 manuscripts (in total 1145 reviews) that were submitted to Atmospheric Chemistry and Physics, an interactive open access journal using public peer review (authors' and reviewers' comments are publicly exchanged). Public peer review is supposed to bring a new openness to the reviewing process that will enhance its objectivity. In the statistical analysis the quality of a manuscript was controlled for to prevent favorable reviewers' ratings from being attributable to quality instead of to the bias variable. Conclusions/Significance Our results agree with those from other studies that editor-suggested reviewers rated manuscripts between 30% and 42% less favorably than author-suggested reviewers. Against this backdrop journal editors should consider either doing without the use of author-suggested reviewers or, if they are used, bringing in more than one editor-suggested reviewer for the review process (so that the review by author-suggested reviewers can be put in perspective). PMID:20976226

  15. Atomic alignment effect in the dissociative energy transfer reaction of metal carbonyls (Fe(CO)5, Ni(CO)4) with oriented Ar (3P2, M(J) = 2).

    PubMed

    Ohoyama, H; Matsuura, Y

    2011-10-13

    The atomic alignment effect has been studied for the dissociative energy transfer reaction of metal carbonyls (Fe(CO)(5), Ni(CO)(4)) with the oriented Ar ((3)P(2), M(J) = 2). The emission intensity from the excited metal products (Fe*, Ni*) has been measured as a function of the atomic alignment in the collision frame. The selectivity of the atomic orbital alignment of Ar ((3)P(2), M(J) = 2) (rank 2 moment, a(2)) is found to be opposite for the two reaction systems; the Fe(CO)(5) reaction is favorable at the Π configuration (positive a(2)), while the Ni(CO)(4) reaction is favorable at the Σ configuration (negative a(2)). Moreover, a significant spin alignment effect (rank 4 moment, a(4)) is recognized only in the Ni(CO)(4) reaction. The atomic alignment effect turns out to be essentially different between the two reaction systems; the Fe(CO)(5) reaction is controlled by the configuration of the half-filled 3p atomic orbital of Ar ((3)P(2)) in the collision frame (L dependence), whereas the Ni(CO)(4) reaction is controlled by the configuration of the total angular moment J (including spin) of Ar ((3)P(2)) in the collision frame (J dependence). As the origin of J dependence observed only in the Ni(CO)(4) reaction, the correlation (and/or the interference) between two electron exchange processes via the electron rearrangements is proposed.

  16. Enhancing treatment for school-age children who stutter I. Reducing negative reactions through desensitization and cognitive restructuring.

    PubMed

    Murphy, William P; Yaruss, J Scott; Quesal, Robert W

    2007-01-01

    This paper describes several treatment strategies that clinicians can use to address negative affective, behavioral, and cognitive reactions that school-age children who stutter may experience as part of their disorder. Specific strategies include desensitization to stuttering, cognitive restructuring, self-acceptance, purposeful self-disclosure, and a combination of both fluency enhancing and stuttering modification approaches. To facilitate clinicians' application of these techniques, the strategies are presented in the context of a case study involving a 9-year-old boy who participated in a comprehensive treatment program for stuttering. Following treatment, the child exhibited improved communication attitudes and a reduced frequency and severity of stuttering, combined with reduced concern about stuttering, as indicated through formal and informal assessments. Findings suggest that clinicians can help children overcome the negative reactions associated with stuttering through a number of treatment strategies that can be applied in a variety of clinical settings. After reading this article, participants will be able to: (1) define desensitization and cognitive restructuring and provide two arguments in favor of using these strategies in treatment for school-age children who stutter; (2) describe two treatment strategies for helping school-age children achieve desensitization through stuttering therapy; (3) describe two treatment strategies for helping school-age children engage in cognitive restructuring in the context of therapy.

  17. Kinetic and mechanisms of methanimine reactions with singlet and triplet molecular oxygen: Substituent and catalyst effects

    NASA Astrophysics Data System (ADS)

    Asgharzadeh, Somaie; Vahedpour, Morteza

    2018-06-01

    Methanimine reaction with O2 on singlet and triplet potential energy surfaces are investigated using B3PW91, M06-2X, MP2 and CCSD(T) methods. Thermodynamic and kinetic parameters are calculated at M06-2X method. The most favorable channel involves H-abstraction of CH2NH+O2 to the formation of HCN + H2O2 products via low level energy barrier. The catalytic effect of water molecule on HCN + H2O2 products pathway are investigated. Result shows that contribution of water molecule using complex formation with methanimine can decreases barrier energy of transition state and the reaction rate increases. Also, substituent effect of fluorine atom as deactivating group are investigated on the main reaction pathway.

  18. Cytoskeleton-centric protein transportation by exosomes transforms tumor-favorable macrophages.

    PubMed

    Chen, Zhipeng; Yang, Lijuan; Cui, Yizhi; Zhou, Yanlong; Yin, Xingfeng; Guo, Jiahui; Zhang, Gong; Wang, Tong; He, Qing-Yu

    2016-10-11

    The exosome is a key initiator of pre-metastatic niche in numerous cancers, where macrophages serve as primary inducers of tumor microenvironment. However, the proteome that can be exosomally transported from cancer cells to macrophages has not been sufficiently characterized so far. Here, we used colorectal cancer (CRC) exosomes to educate tumor-favorable macrophages. With a SILAC-based mass spectrometry strategy, we successfully traced the proteome transported from CRC exosomes to macrophages. Such a proteome primarily focused on promoting cytoskeleton rearrangement, which was biologically validated with multiple cell lines. We reproduced the exosomal transportation of functional vimentin as a proof-of-concept example. In addition, we found that some CRC exosomes could be recognized by macrophages via Fc receptors. Therefore, we revealed the active and necessary role of exosomes secreted from CRC cells to transform cancer-favorable macrophages, with the cytoskeleton-centric proteins serving as the top functional unit.

  19. Detecting Two-Spirit erotics: The fiction of Carole laFavor.

    PubMed

    Tatonetti, Lisa

    2016-01-01

    This article examines the life and novels of Carole laFavor, arguing for her importance to and influence in Two-Spirit studies. Along with being a writer, laFavor was a powerful voice for social justice and Indigenous health sovereignty in Minnesota and the nation. Her two novels, Along the Journey River and Evil Dead Center, which both focus on Anishinaabe lesbian detective protagonist Renee LaRoche, are the first lesbian detective fiction published by a Native author. Renee's embrace of a specifically Two-Spirit erotics anchors her to family and brings her tribal community a powerful healing when she employs her skills to protect her people from instances of racism, abuse, and injustice. This article, then, reads these novels as the first of an emerging genre of texts that claim an overtly Two-Spirit erotic as well as vital precursors to the present embrace of sovereign erotics in Indigenous studies.

  20. Ab initio and density functional study on the mechanism of the C2H2++methanol reaction

    NASA Astrophysics Data System (ADS)

    Irle, Stephan; Morokuma, Keiji

    1999-09-01

    High level ab initio (G2MS and CASSCF) and density functional (B3LYP) calculations were carried out to study the mechanism of the ion-molecule reaction C2H2++CH3OH for four reaction channels: hydride abstraction from methanol (HA), proton transfer from acetylene cation (PT), charge transfer (CT), and covalent complex formation (CC) channel. For the CT channel, two pathways have been found: a usual nonadiabatic pathway via A'/A″ seam of crossing, and a low-energy adiabatic pathway through an initial intermediate; the latter may be the dominant process with favorable energies and a large impact parameter. The HA process involves a low-energy direct intermediate and a very low barrier to form C2H3+CH2OH+ and is also energetically favorable. The PT processes require passage over a high-energy transition state (TS) and are not important. One of the experimentally unobserved CC channels, formation of the COCC skeleton, is energetically favorable and there is no energetic reason for it not to take place; a "dynamic bottleneck" argument may have to be invoked to explain the experiment. The increase in reaction efficiency with the C-C stretch excitation may be justified by considering the TSs for two CT pathways, where the C-C distance changed substantially from that in the reactant C2H2+. Very qualitatively, the C2H2++CH3OH potential energy surface looks more like that of the C2H2++NH3 system than the C2H2++CH4 system, because of the differences in the ionization potentials: NH3˜CH3OH

  1. Parental expectations, experiences and reactions, sense of coherence and grade of anxiety related to routine ultrasound examination with normal findings during pregnancy.

    PubMed

    Ekelin, M; Crang Svalenius, E; Larsson, A-K; Nyberg, P; Marsál, K; Dykes, A-K

    2009-10-01

    To investigate parents' expectations, experiences and reactions, sense of coherence and anxiety before and after a second-trimester routine ultrasound examination, with normal findings. Before and after ultrasound questionnaires including the scales parents' expectations, experiences and reactions to routine ultrasound examination (PEER-U state of mind index), sense of coherence (SOC) and state and trait anxiety inventory (STAI), were sent to a 1-year cohort of women and their partners. Replies received were 2183. Both parents had significantly less worried state of mind (PEER-U) after the examination than before. Women had a lower grade of state anxiety after than before, but for men there was no significant change. Before the ultrasound, women had a higher degree of worried state of mind, as well as a higher grade of state and trait anxiety and a lower sense of coherence, than men. The women showed a greater reduction in worried state of mind than the men after the ultrasound examination. There were no significant differences in sense of coherence before and after ultrasound. Women and men are affected in their psychological well-being in relation to a routine ultrasound examination, but their sense of coherence remains stable.

  2. Egocentric Fairness Perception: Emotional Reactions and Individual Differences in Overt Responses

    PubMed Central

    Bediou, Benoit; Scherer, Klaus R.

    2014-01-01

    Extensive research documents the existence of egocentric biases in the perception and application of justice norms. The origin of these biases remains poorly understood. We investigated both inter- and intra-individual differences in egocentric justice biases. Participants played an ultimatum game presumably with different anonymous players (simulated by a computer) in which they contributed differentially to the joint production of the initial endowment. We examined how contributions (low vs. high) affect proposers' offers and responders' acceptance decisions, as well as their fairness judgments and their emotional reactions to different types of offers (equal, equitable, unfair, and hyperfair). An egocentric bias in proposers' offers (indicating more flexible preferences) was found only in individualists and not in prosocials, suggesting differences in the motivations (or cognitions) underlying their choice of justice norms. Responders also showed egocentric biases in their judgments of fairness and in their emotional reactions to equal and equitable offers, but not in their acceptance decisions. Such dissociation might suggest that some form of emotion regulation occurred. Responders may evaluate offers on valence dimensions (e.g., goal conduciveness/outcome favorability and norm compatibility/justice) that are multiply interacting and potentially conflicting. The individual's acceptance/rejection decision reflects the relative weight attributed to competing appraisals. For this overt behavioral decision, the (personal) appraisal of outcome favorability that drives (analytical) acceptance of goal-conducive outcome seems to be stronger than the (social) appraisal of outcome fairness, which may trigger covert (emotional) rejection of offers that are incompatible with justice norms. Our data show that the emotional reaction patterns provide a more fine-grained readout of the overall evaluation of the proposer's action, the underlying emotional dynamics of which may

  3. Esophageal cancer associated with a sarcoid-like reaction and systemic sarcoidosis in lymph nodes: supportive findings of [18F]-fluorodeoxyglucose positron emission tomography-computed tomography during neoadjuvant therapy.

    PubMed

    Kishino, Takayoshi; Okano, Keiichi; Ando, Yasuhisa; Suto, Hironobu; Asano, Eisuke; Oshima, Minoru; Fujiwara, Masao; Usuki, Hisashi; Kobara, Hideki; Masaki, Tsutomu; Ibuki, Emi; Kushida, Yoshio; Haba, Reiji; Suzuki, Yasuyuki

    2018-06-25

    In patients with esophageal cancer, differentiation between lymph node metastasis and lymphadenopathies from sarcoidosis or sarcoid-like reactions of lymph nodes is clinically important. Herein, we report two esophageal cancer cases with lymph node involvement of sarcoid-like reaction or sarcoidosis. One patient received chemotherapy and the other chemoradiotherapy as initial treatments. In both cases, [ 18 F]-fluorodeoxyglucose positron emission tomography-computed tomography (FDG-PET/CT) was performed before and after chemo(radio)therapy. After the treatment, FDG uptake was not detected in the primary tumor, but it was slightly reduced in the hilar and mediastinal lymph nodes in both cases. These non-identical responses to chemo(radio)therapy suggest the presence of sarcoid-like reaction of lymph nodes associated with squamous cell carcinoma of the esophagus. Curative surgical resection was performed as treatment. These FDG-PET/CT findings may be helpful to distinguish between metastasis and sarcoidosis-associated lymphadenopathy in esophageal cancer.

  4. Desensitizing Children's Emotional Reactions to the Mass Media.

    ERIC Educational Resources Information Center

    Wilson, Barbara J.

    1989-01-01

    Assesses effectiveness of two desensitization strategies for reducing children's emotional reactions to mass media. Examines children having passive exposure, modeled exposure, or no exposure to lizards before watching a horror movie involving lizards. Finds that modeled exposure decreases emotional reactions and negative interpretations, whereas…

  5. Favorable Vascular Actions of Angiotensin-(1-7) in Human Obesity.

    PubMed

    Schinzari, Francesca; Tesauro, Manfredi; Veneziani, Augusto; Mores, Nadia; Di Daniele, Nicola; Cardillo, Carmine

    2018-01-01

    Obese patients have vascular dysfunction related to impaired insulin-stimulated vasodilation and increased endothelin-1-mediated vasoconstriction. In contrast to the harmful vascular actions of angiotensin (Ang) II, the angiotensin-converting enzyme 2 product Ang-(1-7) has shown to exert cardiovascular and metabolic benefits in experimental models through stimulation of the Mas receptor. We, therefore, examined the effects of exogenous Ang-(1-7) on vasodilator tone and endothelin-1-dependent vasoconstriction in obese patients. Intra-arterial infusion of Ang-(1-7) (10 nmol/min) resulted in significant increase in unstimulated forearm flow ( P =0.03), an effect that was not affected by the Mas receptor antagonist A779 (10 nmol/min; P >0.05). In the absence of hyperinsulinemia, however, forearm flow responses to graded doses of acetylcholine and sodium nitroprusside were not different during Ang-(1-7) administration compared with saline (both P >0.05). During infusion of regular insulin (0.15 mU/kg per minute), by contrast, endothelium-dependent vasodilator response to acetylcholine was significantly enhanced by Ang-(1-7) ( P =0.04 versus saline), whereas endothelium-independent response to sodium nitroprusside was not modified ( P =0.91). Finally, Ang-(1-7) decreased the vasodilator response to endothelin A receptor blockade (BQ-123; 10 nmol/min) compared with saline (6±1% versus 93±17%; P <0.001); nitric oxide inhibition by l- N -monomethylarginine (4 µmol/min) during concurrent endothelin A antagonism resulted in similar vasoconstriction in the absence or presence of Ang-(1-7 Ang-(1-7) ( P =0.69). Our findings indicate that in obese patients Ang-(1-7) has favorable effects not only to improve insulin-stimulated endothelium-dependent vasodilation but also to blunt endothelin-1-dependent vasoconstrictor tone. These findings provide support for targeting Ang-(1-7) to counteract the hemodynamic abnormalities of human obesity. © 2017 American Heart Association, Inc.

  6. Expanding the histological findings in postvaccinial non-viral folliculitis

    PubMed Central

    Bunick, Christopher G.; Mariwalla, Kavita; Ibrahim, Omer; Modi, Badri; Imaeda, Suguru; McNiff, Jennifer

    2014-01-01

    Postvaccinial non-viral folliculitis has been recognized in the past decade as a new adverse cutaneous reaction to the smallpox vaccination. Contrary to more serious smallpox vaccine reactions, postvaccinial non-viral folliculitis has a benign course resolving spontaneously within approximately seven days. We describe additional histopathological findings associated with postvaccinial non-viral folliculitis, which has only been described once previously. New findings include the presence of neutrophilic or lymphohistiocytic infiltrates that concentrate around the hair follicles. We compare our findings to the follicular nature of varicella and herpes zoster infections, generating the hypothesis of deposition of vaccinia protein within folliculosebaceous units as a potential pathophysiologic mechanism behind postvaccinial non-viral folliculitis. PMID:23278890

  7. Density functional computational studies on the glucose and glycine Maillard reaction: Formation of the Amadori rearrangement products

    NASA Astrophysics Data System (ADS)

    Jalbout, Abraham F.; Roy, Amlan K.; Shipar, Abul Haider; Ahmed, M. Samsuddin

    Theoretical energy changes of various intermediates leading to the formation of the Amadori rearrangement products (ARPs) under different mechanistic assumptions have been calculated, by using open chain glucose (O-Glu)/closed chain glucose (A-Glu and B-Glu) and glycine (Gly) as a model for the Maillard reaction. Density functional theory (DFT) computations have been applied on the proposed mechanisms under different pH conditions. Thus, the possibility of the formation of different compounds and electronic energy changes for different steps in the proposed mechanisms has been evaluated. B-Glu has been found to be more efficient than A-Glu, and A-Glu has been found more efficient than O-Glu in the reaction. The reaction under basic condition is the most favorable for the formation of ARPs. Other reaction pathways have been computed and discussed in this work.0

  8. PSCA expression is associated with favorable tumor features and reduced PSA recurrence in operated prostate cancer.

    PubMed

    Heinrich, Marie-Christine; Göbel, Cosima; Kluth, Martina; Bernreuther, Christian; Sauer, Charlotte; Schroeder, Cornelia; Möller-Koop, Christina; Hube-Magg, Claudia; Lebok, Patrick; Burandt, Eike; Sauter, Guido; Simon, Ronald; Huland, Hartwig; Graefen, Markus; Heinzer, Hans; Schlomm, Thorsten; Heumann, Asmus

    2018-05-31

    Prostate Stem Cell Antigen (PSCA) is frequently expressed in prostate cancer but its exact function is unclear. To clarify contradictory findings on the prognostic role of PSCA expression, a tissue microarray containing 13,665 prostate cancers was analyzed by immunohistochemistry. PSCA staining was absent in normal epithelial and stromal cells of the prostate. Membranous and cytoplasmic PSCA staining was seen in 53.7% of 9642 interpretable tumors. Staining was weak in 22.4%, moderate in 24.5% and strong in 6.8% of tumors. PSCA expression was associated with favorable pathological and clinical tumor features: Early pathological tumor stage (p < 0.0001), low Gleason grade (p < 0.0001), absence of lymph node metastasis (p < 0.0001), low pre-operative PSA level (p = 0.0118), negative surgical margin (p < 0.0001) and reduced PSA recurrence (p < 0.0001). PSCA expression was an independent predictor of prognosis in multivariate analysis (hazard ratio 0.84, p < 0.0001). The absence of statistical relationship to TMPRSS2:ERG fusion status, chromosomal deletion or high tumor cell proliferation argues against a major role of PSCA for regulation of cell cycle or genomic integrity. PSCA expression is linked to favorable prognosis. PSCA measurement is a candidate for inclusion in multi-parametric prognostic prostate cancer tests.

  9. Groundwater favorability map using GIS multicriteria data analysis on crystalline terrain, São Paulo State, Brazil

    NASA Astrophysics Data System (ADS)

    Madrucci, Vanessa; Taioli, Fabio; de Araújo, Carlos César

    2008-08-01

    SummaryThis paper presents the groundwater favorability mapping on a fractured terrain in the eastern portion of São Paulo State, Brazil. Remote sensing, airborne geophysical data, photogeologic interpretation, geologic and geomorphologic maps and geographic information system (GIS) techniques have been used. The results of cross-tabulation between these maps and well yield data allowed groundwater prospective parameters in a fractured-bedrock aquifer. These prospective parameters are the base for the favorability analysis whose principle is based on the knowledge-driven method. The multicriteria analysis (weighted linear combination) was carried out to give a groundwater favorability map, because the prospective parameters have different weights of importance and different classes of each parameter. The groundwater favorability map was tested by cross-tabulation with new well yield data and spring occurrence. The wells with the highest values of productivity, as well as all the springs occurrence are situated in the excellent and good favorability mapped areas. It shows good coherence between the prospective parameters and the well yield and the importance of GIS techniques for definition of target areas for detail study and wells location.

  10. A label-free amplified fluorescence DNA detection based on isothermal circular strand-displacement polymerization reaction and graphene oxide.

    PubMed

    Li, Zhen; Zhu, Wenping; Zhang, Jinwen; Jiang, Jianhui; Shen, Guoli; Yu, Ruqin

    2013-07-07

    A label-free fluorescent DNA biosensor has been presented based on isothermal circular strand-displacement polymerization reaction (ICSDPR) combined with graphene oxide (GO) binding. The proposed method is simple and cost-effective with a low detection limit of 4 pM, which compares favorably with other GO-based homogenous DNA detection methods.

  11. Surface Defect Passivation and Reaction of c-Si in H2S.

    PubMed

    Liu, Hsiang-Yu; Das, Ujjwal K; Birkmire, Robert W

    2017-12-26

    A unique passivation process of Si surface dangling bonds through reaction with hydrogen sulfide (H 2 S) is demonstrated in this paper. A high-level passivation quality with an effective minority carrier lifetime (τ eff ) of >2000 μs corresponding to a surface recombination velocity of <3 cm/s is achieved at a temperature range of 550-650 °C. X-ray photoelectron spectroscopy (XPS) confirmed the bonding states of Si and S and provides insights into the reaction pathway of Si with H 2 S and other impurity elements both during and after the reaction. Quantitative analysis of XPS spectra showed that the τ eff increases with an increase in the surface S content up to ∼3.5% and stabilizes thereafter, indicative of surface passivation by monolayer coverage of S on the Si surface. However, S passivation of the Si surface is highly unstable because of thermodynamically favorable reaction with atmospheric H 2 O and O 2 . This instability can be eliminated by capping the S-passivated Si surface with a protective thin film such as low-temperature-deposited amorphous silicon nitride.

  12. [Solitary nodular sarcoidosis demonstrating reversed tuberculin skin reaction].

    PubMed

    Osoreda, Hisayuki; Kobayashi, Hideo; Kanoh, Soichiro; Motoyoshi, Kazuo

    2008-08-01

    A 29-year-old woman was admitted because of chest radiograph abnormality. She had no respiratory complaints. Chest CT demonstrated an ill-defined nodule of 20mm with the "sarcoid galaxy sign" in the right upper lobe. Transbronchial biopsy (TBB) specimens from right S2 revealed non-caseating epithelioid cell granuloma. Initial clinical findings suggested mycobacterial infection. However, while waiting for the results of mycobacterial cultures in bronchial washing fluid, the tuberculin skin reaction was found to be negative, and enlargement of nodule, mediastinal lymphadenopathy and elevated soluble IL-2R were observed. Cultures for mycobacterium were negative and repeat TBB specimens revealed granulomatous inflammation. We diagnosed with sarcoidosis based on these findings. Solitary nodular sarcoidosis is rare with only 17 cases having been reported. These cases were diagnosed with difficulty because of non-specific clinical findings and of the 17, 16 cases (94%) were diagnosed by surgical procedures. We observed the clinico-radiological course of solitary nodules and the change in tuberculin reaction. Although a negative tuberculin skin reaction was commonly recognized in sarcoidosis patients, we confirmed that initial positive tuberculin reaction changed to negative according to disease progress. To the best of our knowledge, this is the first case report in adults.

  13. Azulene-to-naphthalene rearrangement: the Car-Parrinello metadynamics method explores various reaction mechanisms.

    PubMed

    Stirling, András; Iannuzzi, Marcella; Laio, Alessandro; Parrinello, Michele

    2004-10-18

    We studied the thermal intramolecular and radical rearrangement of azulene to naphthalene by employing a novel metadynamics method based on Car-Parrinello molecular dynamics. We demonstrate that relatively short simulations can provide us with several possible reaction mechanisms for the rearrangement. We show that different choices of the collective coordinates can steer the reaction along different pathways, thus offering the possibility of choosing the most probable mechanism. We consider herein three intramolecular mechanisms and two radical pathways. We found the norcaradiene pathway to be the preferable intramolecular mechanism, whereas the spiran mechanism is the favored radical route. We obtained high activation energies for all the intramolecular pathways (81.5-98.6 kcal mol(-1)), whereas the radical routes have activation energies of 24-39 kcal mol(-1). The calculations have also resulted in elementary steps and intermediates not yet considered. A few attractive features of the metadynamics method in studying chemical reactions are pointed out.

  14. Filtering the Net in Libraries: The Case (Mostly) in Favor.

    ERIC Educational Resources Information Center

    Banks, Michael A.

    1998-01-01

    Examines issues and decision-making involved in restricting Internet access in libraries, for the most part favoring filtering devices. Questions to consider when selecting a filtering program are provided. Some of the better filtering programs are described, and Web addresses are included for each. Security risks associated with Java and…

  15. Social-and-economic mechanism of formation of favorable investment attractiveness of the region

    NASA Astrophysics Data System (ADS)

    Tereshkina, Tatiana; Mottaeva, Angela; Andreeva, Larisa; Larinina, Tatyana

    2017-10-01

    The article is devoted to the matters of investment attractiveness of regions. The factors making the regional investments possible. The authors argue, that social-and-economic development of regions is connected with the formation of the financial mechanism, representing the set of forms and methods of the organization, planning and stimulation of financial-and-economic activity in the certain social-and-economic space. The proper mechanism of formation of favorable investment attractiveness are offered. Besides, the ways of elimination of limiting factors in formation of favorable investment attractiveness are offered.

  16. Global health actors no longer in favor of user fees: a documentary study.

    PubMed

    Robert, Emilie; Ridde, Valéry

    2013-07-26

    Since the advent of health user fees in low- and middle-income countries in the 1980s, the discourse of global health actors (GHAs) has changed to the disadvantage of this type of healthcare financing mechanism. The aim of the study was to identify and analyze the stance of GHAs in the debate on user fees. We conducted documentary research using public documents published by and officially attributed to GHAs from 2005 to 2011. We categorized GHAs into four groups: intergovernmental organizations, international non-governmental organizations, government agencies, and working groups and networks. We then classified the GHAs according to their stance relative to the abolition of user fees, and conducted a thematic analysis of their discourse to understand the arguments used by each GHA to justify its stance. We identified 56 GHAs, for which we analyzed 140 documents. Among them, 55% were in favor of the abolition of user fees or in favor of free care at the point of delivery. None of the GHAs stated that they were in favor of user fees; however, 30% did not take a stand. Only the World Bank declares that it is both in favor of user fees and in favor of free care at point of service. GHAs generally circumscribe their stance to specific populations (pregnant women, children under 5 years, etc.) or to specific health services (primary, basic, essential). Three types of arguments are used by GHAs to justify their stance: economic, moral and ethical, and pragmatic. The principle of "user pays" seems to have fizzled. Production and dissemination of evidence, as well as certain advocacy networks, may have contributed to this change in discourse. However, GHAs should go a step further and translate their words into action, so that free healthcare at the point of delivery becomes a reality in low- and middle-income countries. They should provide technical and financial support to those countries that have chosen to implement user fee exemption policies, sometimes influenced

  17. Global health actors no longer in favor of user fees: a documentary study

    PubMed Central

    2013-01-01

    Background Since the advent of health user fees in low- and middle-income countries in the 1980s, the discourse of global health actors (GHAs) has changed to the disadvantage of this type of healthcare financing mechanism. The aim of the study was to identify and analyze the stance of GHAs in the debate on user fees. Methods We conducted documentary research using public documents published by and officially attributed to GHAs from 2005 to 2011. We categorized GHAs into four groups: intergovernmental organizations, international non-governmental organizations, government agencies, and working groups and networks. We then classified the GHAs according to their stance relative to the abolition of user fees, and conducted a thematic analysis of their discourse to understand the arguments used by each GHA to justify its stance. Results We identified 56 GHAs, for which we analyzed 140 documents. Among them, 55% were in favor of the abolition of user fees or in favor of free care at the point of delivery. None of the GHAs stated that they were in favor of user fees; however, 30% did not take a stand. Only the World Bank declares that it is both in favor of user fees and in favor of free care at point of service. GHAs generally circumscribe their stance to specific populations (pregnant women, children under 5 years, etc.) or to specific health services (primary, basic, essential). Three types of arguments are used by GHAs to justify their stance: economic, moral and ethical, and pragmatic. Conclusions The principle of “user pays” seems to have fizzled. Production and dissemination of evidence, as well as certain advocacy networks, may have contributed to this change in discourse. However, GHAs should go a step further and translate their words into action, so that free healthcare at the point of delivery becomes a reality in low- and middle-income countries. They should provide technical and financial support to those countries that have chosen to implement user fee

  18. Modelling Chemical Reasoning to Predict and Invent Reactions.

    PubMed

    Segler, Marwin H S; Waller, Mark P

    2017-05-02

    The ability to reason beyond established knowledge allows organic chemists to solve synthetic problems and invent novel transformations. Herein, we propose a model that mimics chemical reasoning, and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180 000 randomly selected binary reactions. The data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-)discovering novel transformations (even including transition metal-catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph and because each single reaction prediction is typically achieved in a sub-second time frame, the model can be used as a high-throughput generator of reaction hypotheses for reaction discovery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Electromagnetic Radiation Reaction in General Relativity.

    NASA Astrophysics Data System (ADS)

    O'Donnell, Nuala

    Available from UMI in association with The British Library. This thesis examines the electromagnetic radiation reaction felt by a charged body falling freely in an external gravitational field in general relativity. The original objective was to find a new derivation of the radiation reaction force F^{i} of DeWitt and DeWitt^1 which was calculated for the special case of a point charge falling in slow motion in a weak, static gravitational field: F ^{i} = {2over 3}e^2R^{i}_{0j0 }v^{j}. This may be thought of as a local expression since it involves the particle's velocity v^{j } and the local Riemann curvature tensor R ^{i}_{0j0}. Its derivation involves integrals over the whole history of the particle, covering distances of approximately the length scale on which R^{i}_{0j0 } changes. This is different from calculations of the Abraham-Lorentz force of flat space-time involving integrals over distances only a few times the size of the charge. This work was motivated by the wish to find a "local" derivation of the local reaction force. Using Schutz's^2 local initial value method to solve the problem of a charged, rigid, spherically symmetric body moving in an external gravitational field of arbitrary metric. Calculations are done in a Riemann normal coordinate system ^3 and are only valid in a normal neighbourhood of the origin, where geodesics have not begun to cross one another. We solve Maxwell's equations for the self -force by making a slow-motion approximation and keeping terms to first order only in the Riemann tensor and velocity. It is surprising that we find no local radiation reaction. Consider two particles in a static spacetime with the same initial conditions at t = 0. Particle A is that of DeWitt and DeWitt; it feels a reaction force F^{i} = {2over 3}e^2R^{i }_{0j0}v^{j}. Particle B is accelerated from rest to the same small velocity; it feels no reaction force. The two particles therefore follow different trajectories. We conclude that there is a

  20. Favorable hierarchy detection through Lempel-Ziv coding based algorithm to aid hierarchical fracturing in mask data preparation

    NASA Astrophysics Data System (ADS)

    Bhardwaj, D. S. S.; Ghosh, Nilanjan; Rao, Nageswara; Pai, Ravi R.

    2009-10-01

    Runtime of the Mask Data Preparation (MDP) tool is largely dependent on the hierarchy of the input layout data. In this paper, we present a technique where a hierarchical or flat input design layout or almost flat mask data can be converted into a favorable hierarchical data which can be directly used by MDP tools for fracturing. A favorable hierarchy is a hierarchy of cells where polygons within cells do not overlap with each other even if bounding boxes of cells might overlap with each other. This is an important characteristic which can be intelligently made use of by intra-polygonal operations like fracturing. Otherwise, a mask data preparation (MDP) tool has to take the responsibility for resolving overlaps among polygons, which slows down the processing and increases the data size. MDP on a favorable hierarchy will thus speed up the fracturing or re-fracturing steps and also minimize the output fractured data size, as shown through the experimental results in the paper. In the proposed technique, the favorable hierarchy is generated using a modified version of the Lempel-Ziv (LZ) coding algorithm, which was originally devised for compressing character strings. A hierarchical fracturing algorithm can be employed to work on the favorable hierarchy generated, which will utilize the property of a favorable hierarchy that polygons do not overlap with each other. Apart from the obvious runtime benefits, such a favorable hierarchy allows considerable reduction in fractured data size as most mask data formats allow representation of a hierarchy containing two levels.

  1. Multilayer Network Analysis of Nuclear Reactions

    NASA Astrophysics Data System (ADS)

    Zhu, Liang; Ma, Yu-Gang; Chen, Qu; Han, Ding-Ding

    2016-08-01

    The nuclear reaction network is usually studied via precise calculation of differential equation sets, and much research interest has been focused on the characteristics of nuclides, such as half-life and size limit. In this paper, however, we adopt the methods from both multilayer and reaction networks, and obtain a distinctive view by mapping all the nuclear reactions in JINA REACLIB database into a directed network with 4 layers: neutron, proton, 4He and the remainder. The layer names correspond to reaction types decided by the currency particles consumed. This combined approach reveals that, in the remainder layer, the β-stability has high correlation with node degree difference and overlapping coefficient. Moreover, when reaction rates are considered as node strength, we find that, at lower temperatures, nuclide half-life scales reciprocally with its out-strength. The connection between physical properties and topological characteristics may help to explore the boundary of the nuclide chart.

  2. Exploring reaction pathways for O-GlcNAc transferase catalysis. A string method study.

    PubMed

    Kumari, Manju; Kozmon, Stanislav; Kulhánek, Petr; Štepán, Jakub; Tvaroška, Igor; Koča, Jaroslav

    2015-03-26

    The inverting O-GlcNAc glycosyltransferase (OGT) is an important post-translation enzyme, which catalyzes the transfer of N-acetylglucosamine from UDP-N-acetylglucosamine (UDP-GlcNAc) to the hydroxyl group of the Ser/Thr of cytoplasmic, nuclear, and mitochondrial proteins. In the past, three different catalytic bases were proposed for the reaction: His498, α-phosphate, and Asp554. In this study, we used hybrid quantum mechanics/molecular mechanics (QM/MM) Car-Parrinello molecular dynamics to investigate reaction paths using α-phosphate and Asp554 as the catalytic bases. The string method was used to calculate the free-energy reaction profiles of the tested mechanisms. During the investigations, an additional mechanism was observed. In this mechanism, a proton is transferred to α-phosphate via a water molecule. Our calculations show that the mechanism with α-phosphate acting as the base is favorable. This reaction has a rate-limiting free-energy barrier of 23.5 kcal/mol, whereas reactions utilizing Asp554 and water-assisted α-phosphate have barriers of 41.7 and 40.9 kcal/mol, respectively. Our simulations provide a new insight into the catalysis of OGT and may thus guide rational drug design of transition-state analogue inhibitors with potential therapeutic use.

  3. Autism: Too eager to learn? Event related potential findings of increased dependency on intentional learning in a serial reaction time task.

    PubMed

    Zwart, Fenny S; Vissers, Constance Th W M; van der Meij, Roemer; Kessels, Roy P C; Maes, Joseph H R

    2017-09-01

    It has been suggested that people with autism spectrum disorder (ASD) have an increased tendency to use explicit (or intentional) learning strategies. This altered learning may play a role in the development of the social communication difficulties characterizing ASD. In the current study, we investigated incidental and intentional sequence learning using a Serial Reaction Time (SRT) task in an adult ASD population. Response times and event related potentials (ERP) components (N2b and P3) were assessed as indicators of learning and knowledge. Findings showed that behaviorally, sequence learning and ensuing explicit knowledge were similar in ASD and typically developing (TD) controls. However, ERP findings showed that learning in the TD group was characterized by an enhanced N2b, while learning in the ASD group was characterized by an enhanced P3. These findings suggest that learning in the TD group might be more incidental in nature, whereas learning in the ASD group is more intentional or effortful. Increased intentional learning might serve as a strategy for individuals with ASD to control an overwhelming environment. Although this led to similar behavioral performances on the SRT task, it is very plausible that this intentional learning has adverse effects in more complex social situations, and hence contributes to the social impairments found in ASD. Autism Res 2017, 10: 1533-1543. © 2017 International Society for Autism Research, Wiley Periodicals, Inc. © 2017 International Society for Autism Research, Wiley Periodicals, Inc.

  4. Ranking methodology for determining the relative favorability for commercial development of US tar-sand deposits

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

    Aamodt, P.L.; Freiwald, J.G.

    1983-03-01

    As a part of the DOE's program to stimulate petroleum production from unconventional sources, the Los Alamos National Laboratory has developed a methodology to compare and rank tar sand deposits, based on their suitability for commercial development. Major categories influencing favorability were identified and evaluated to determine their individual and collective impacts. To facilitate their evaluation, deposit characteristics, extraction technologies, environmental controls, and institutional constraints were broken down into their elements. The elements were assessed singly and in interactive groups to determine their influence on favorability for commercial development. A numerical value was assigned each element to signify its estimatedmore » importance relative to the other elements. Eight tar sand deposits were evaluated using only one major category, deposit characteristics. This initial, and only partial favorability assessment, was solely a test of the methodology, and it was considered successful. Because only one of the four major categories was used for this initial favorability ranking, and also because the available deposit characteristic data were barely adequate for the test, these first results should be used only as an example of how the methodology is to be applied when more complete data are available. The eight deposits and their relative favorability rankings for commercial development, based only on the deposit characteristics, are Sunnyside, Utah; Asphalt Ridge, Utah; Edna, California; Santa Rosa, New Mexico; Tar Sand Triangle, Utah; PR Spring, Utah; Uvalde, Texas; and circle cliffs, Utah.« less

  5. Acetylene chain reaction on hydrogenated boron nitride monolayers: a density functional theory study.

    PubMed

    Ponce-Pérez, R; Cocoletzi, Gregorio H; Takeuchi, Noboru

    2017-11-28

    Spin-polarized first-principles total-energy calculations have been performed to investigate the possible chain reaction of acetylene molecules mediated by hydrogen abstraction on hydrogenated hexagonal boron nitride monolayers. Calculations have been done within the periodic density functional theory (DFT), employing the PBE exchange correlation potential, with van der Waals corrections (vdW-DF). Reactions at two different sites have been considered: hydrogen vacancies on top of boron and on top of nitrogen atoms. As previously calculated, at the intermediate state of the reaction, when the acetylene molecule is attached to the surface, the adsorption energy is of the order of -0.82 eV and -0.20 eV (measured with respect to the energy of the non interacting molecule-substrate system) for adsorption on top of boron and nitrogen atoms, respectively. After the hydrogen abstraction takes place, the system gains additional energy, resulting in adsorption energies of -1.52 eV and -1.30 eV, respectively. These results suggest that the chain reaction is energetically favorable. The calculated minimum energy path (MEP) for hydrogen abstraction shows very small energy barriers of the order of 5 meV and 22 meV for the reaction on top of boron and nitrogen atoms, respectively. Finally, the density of states (DOS) evolution study helps to understand the chain reaction mechanism. Graphical abstract Acetylene chain reaction on hydrogenated boron nitride monolayers.

  6. How to Find the Students' Inner Geek

    ERIC Educational Resources Information Center

    Zimmer, Marc

    2005-01-01

    As a chemistry professor at a liberal-arts college, the author believes it is his job to find the youthful awe in his students and draw it out so that they will be intrigued once again by science and nature, so that they want to learn about equilibria, pH, and redox reactions. He has to go fishing inside their brains, to find, hook, and reel in…

  7. The formation of illite from nontronite by mesophilic and thermophilic bacterial reaction

    USGS Publications Warehouse

    Jaisi, Deb P.; Eberl, Dennis D.; Dong, Hailiang; Kim, Jinwook

    2011-01-01

    The formation of illite through the smectite-to-illite (S-I) reaction is considered to be one of the most important mineral reactions occurring during diagenesis. In biologically catalyzed systems, however, this transformation has been suggested to be rapid and to bypass the high temperature and long time requirements. To understand the factors that promote the S-I reaction, the present study focused on the effects of pH, temperature, solution chemistry, and aging on the S-I reaction in microbially mediated systems. Fe(III)-reduction experiments were performed in both growth and non-growth media with two types of bacteria: mesophilic (Shewanella putrefaciens CN32) and thermophilic (Thermus scotoductus SA-01). Reductive dissolution of NAu-2 was observed and the formation of illite in treatment with thermophilic SA-01 was indicated by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). A basic pH (8.4) and high temperature (65°C) were the most favorable conditions for the formation of illite. A long incubation time was also found to enhance the formation of illite. K-nontronite (non-permanent fixation of K) was also detected and differentiated from the discrete illite in the XRD profiles. These results collectively suggested that the formation of illite associated with the biologically catalyzed smectite-to-illite reaction pathway may bypass the prolonged time and high temperature required for the S-I reaction in the absence of microbial activity.

  8. Resumption of gainful employment in aphasics: preliminary findings.

    PubMed

    Carriero, M R; Faglia, L; Vignolo, L A

    1987-12-01

    We report preliminary data on aphasic patients who, in spite of their language problems, have succeeded in finding a reasonably satisfactory occupational resettlement. Patients who: (a) still had a moderate to sever aphasia, (b) had resumed a gainful employment requiring interpersonal communication, were recalled for a check-up and assessed with: (1) a comprehensive aphasia test: (2) a semistructured interview including detailed questioning about the type and reaction to aphasia, the type of work before the onset of aphasia, the type of current work with particular emphasis on the patients' compensatory mechanisms and emotional reactions. Results comprise 10 cases up to date. One case is described in detail. Findings indicate that the ability to resume a gainful occupation is often greater than could be expected on the sole basis of formal language examination. Findings are discussed from a neuropsychological, social and rehabilitation point of view.

  9. Palladium-catalyzed C-H functionalization of acyldiazomethane and tandem cross-coupling reactions.

    PubMed

    Ye, Fei; Qu, Shuanglin; Zhou, Lei; Peng, Cheng; Wang, Chengpeng; Cheng, Jiajia; Hossain, Mohammad Lokman; Liu, Yizhou; Zhang, Yan; Wang, Zhi-Xiang; Wang, Jianbo

    2015-04-08

    Palladium-catalyzed C-H functionalization of acyldiazomethanes with aryl iodides has been developed. This reaction is featured by the retention of the diazo functionality in the transformation, thus constituting a novel method for the introduction of diazo functionality to organic molecules. Consistent with the experimental results, the density functional theory (DFT) calculation indicates that the formation of Pd-carbene species in the catalytic cycle through dinitrogen extrusion from the palladium ethyl diazoacetate (Pd-EDA) complex is less favorable. The reaction instead proceeds through Ag2CO3 assisted deprotonation and subsequently reductive elimination to afford the products with diazo functionality remained. This C-H functionalization transformation can be further combined with the recently evolved palladium-catalyzed cross-coupling reaction of diazo compounds with aryl iodides to develop a tandem coupling process for the synthesis of α,α-diaryl esters. DFT calculation supports the involvement of Pd-carbene as reactive intermediate in the catalytic cycle, which goes through facile carbene migratory insertion with a low energy barrier (3.8 kcal/mol).

  10. Further links between the maximum hardness principle and the hard/soft acid/base principle: insights from hard/soft exchange reactions.

    PubMed

    Chattaraj, Pratim K; Ayers, Paul W; Melin, Junia

    2007-08-07

    Ayers, Parr, and Pearson recently showed that insight into the hard/soft acid/base (HSAB) principle could be obtained by analyzing the energy of reactions in hard/soft exchange reactions, i.e., reactions in which a soft acid replaces a hard acid or a soft base replaces a hard base [J. Chem. Phys., 2006, 124, 194107]. We show, in accord with the maximum hardness principle, that the hardness increases for favorable hard/soft exchange reactions and decreases when the HSAB principle indicates that hard/soft exchange reactions are unfavorable. This extends the previous work of the authors, which treated only the "double hard/soft exchange" reaction [P. K. Chattaraj and P. W. Ayers, J. Chem. Phys., 2005, 123, 086101]. We also discuss two different approaches to computing the hardness of molecules from the hardness of the composing fragments, and explain how the results differ. In the present context, it seems that the arithmetic mean of fragment softnesses is the preferable definition.

  11. Intermediate-energy inverse-kinematics one-proton pickup reactions on neutron-deficient fp-shell nuclei

    NASA Astrophysics Data System (ADS)

    McDaniel, S.; Gade, A.; Tostevin, J. A.; Baugher, T.; Bazin, D.; Brown, B. A.; Cook, J. M.; Glasmacher, T.; Grinyer, G. F.; Ratkiewicz, A.; Weisshaar, D.

    2012-01-01

    Background: Thick-target-induced nucleon-adding transfer reactions onto energetic rare-isotope beams are an emerging spectroscopic tool. Their sensitivity to single-particle structure complements one-nucleon removal reaction capabilities in the quest to reveal the evolution of nuclear shell structure in very exotic nuclei. Purpose: Our purpose is to add intermediate-energy, carbon-target-induced one-proton pickup reactions to the arsenal of γ-ray-tagged direct reactions applicable in the regime of low beam intensities and to apply these for the first time to fp-shell nuclei. Methods: Inclusive and partial cross sections were measured for the 12C(48Cr,49Mn+γ)X and 12C(50Fe,51Co+γ)X proton pickup reactions at 56.7 and 61.2 MeV/nucleon, respectively, using coincident particle-γ spectroscopy at the National Superconducting Cyclotron Laboratory. The results are compared to reaction theory calculations using fp-shell-model nuclear structure input. For comparison with our previous work, the same reactions were measured on 9Be targets. Results: The measured partial cross sections confirm the specific population pattern predicted by theory, with pickup into high-ℓ orbitals being strongly favored, driven by linear and angular momentum matching. Conclusion: Carbon-target-induced pickup reactions are well suited, in the regime of modest beam intensity, to study the evolution of nuclear structure, with specific sensitivities that are well described by theory.

  12. Characterization of plastic deformation and chemical reaction in titanium-polytetrafluoroethylene mixture

    NASA Astrophysics Data System (ADS)

    Davis, Jeffery Jon

    1998-09-01

    The subject of this dissertation is the deformation process of a single metal - polymer system (titanium - polytetrafluoroethylene) and how this process leads to initiation of chemical reaction. Several different kinds of experiments were performed to characterize the behavior of this material to shock and impact. These mechanical conditions induce a rapid plastic deformation of the sample. All of the samples tested had an initial porosity which increased the plastic flow condition. It is currently believed that during the deformation process two important conditions occur: removal of the oxide layer from the metal and decomposition of the polymer. These conditions allow for rapid chemical reaction. The research from this dissertation has provided insight into the complex behavior of plastic deformation and chemical reactions in titanium - polytetrafluoroethylene (PTFE, Teflon). A hydrodynamic computational code was used to model the plastic flow for correlation with the results from the experiments. The results from this work are being used to develop an ignition and growth model for metal/polymer systems. Three sets of experiments were used to examine deformation of the 80% Ti and 20% Teflon materials: drop- weight, gas gun, and split-Hopkinson pressure bar. Recovery studies included post shot analysis of the samples using x-ray diffraction. Lagrangian hydrocode DYNA2D modeling of the drop-weight tests was performed for comparison with experiments. One of the reactions know to occur is Ti + C → TiC (s) which results in an exothermic release. However, the believed initial reactions occur between Ti and fluorine which produces TixFy gases. The thermochemical code CHEETAH was used to investigate the detonation products and concentrations possible during Ti - Teflon reaction. CHEETAH shows that the Ti - fluorine reactions are thermodynamically favorable. This research represents the most comprehensive to date study of deformation induced chemical reaction in metal/polymers.

  13. 8 CFR 316.11 - Attachment to the Constitution; favorable disposition towards the good order and happiness.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... disposition towards the good order and happiness. 316.11 Section 316.11 Aliens and Nationality DEPARTMENT OF... the Constitution; favorable disposition towards the good order and happiness. (a) General. An... favorably disposed toward the good order and happiness of the United States. Attachment implies a depth of...

  14. 8 CFR 316.11 - Attachment to the Constitution; favorable disposition towards the good order and happiness.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... disposition towards the good order and happiness. 316.11 Section 316.11 Aliens and Nationality DEPARTMENT OF... the Constitution; favorable disposition towards the good order and happiness. (a) General. An... favorably disposed toward the good order and happiness of the United States. Attachment implies a depth of...

  15. 8 CFR 316.11 - Attachment to the Constitution; favorable disposition towards the good order and happiness.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... disposition towards the good order and happiness. 316.11 Section 316.11 Aliens and Nationality DEPARTMENT OF... the Constitution; favorable disposition towards the good order and happiness. (a) General. An... favorably disposed toward the good order and happiness of the United States. Attachment implies a depth of...

  16. 8 CFR 316.11 - Attachment to the Constitution; favorable disposition towards the good order and happiness.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... disposition towards the good order and happiness. 316.11 Section 316.11 Aliens and Nationality DEPARTMENT OF... the Constitution; favorable disposition towards the good order and happiness. (a) General. An... favorably disposed toward the good order and happiness of the United States. Attachment implies a depth of...

  17. 8 CFR 316.11 - Attachment to the Constitution; favorable disposition towards the good order and happiness.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... disposition towards the good order and happiness. 316.11 Section 316.11 Aliens and Nationality DEPARTMENT OF... the Constitution; favorable disposition towards the good order and happiness. (a) General. An... favorably disposed toward the good order and happiness of the United States. Attachment implies a depth of...

  18. Insertion of Isocyanides into N-Si Bonds: Multicomponent Reactions with Azines Leading to Potent Antiparasitic Compounds.

    PubMed

    Kishore, Kranti G; Ghashghaei, Ouldouz; Estarellas, Carolina; Mestre, M Mar; Monturiol, Cristina; Kielland, Nicola; Kelly, John M; Francisco, Amanda Fortes; Jayawardhana, Shiromani; Muñoz-Torrero, Diego; Pérez, Belén; Luque, F Javier; Gámez-Montaño, Rocío; Lavilla, Rodolfo

    2016-07-25

    Trimethylsilyl chloride is an efficient activating agent for azines in isocyanide-based reactions, which then proceed through a key insertion of the isocyanide into a N-Si bond. The reaction is initiated by N activation of the azine, followed by nucleophilic attack of an isocyanide in a Reissert-type process. Finally, a second equivalent of the same or a different isocyanide inserts into the N-Si bond leading to the final adduct. The use of distinct nucleophiles leads to a variety of α-substituted dihydroazines after a selective cascade process. Based on computational studies, a mechanistic hypothesis for the course of these reactions was proposed. The resulting products exhibit significant activity against Trypanosoma brucei and T. cruzi, featuring favorable drug-like properties and safety profiles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Teaching accreditation exams reveal grading biases favor women in male-dominated disciplines in France.

    PubMed

    Breda, Thomas; Hillion, Mélina

    2016-07-29

    Discrimination against women is seen as one of the possible causes behind their underrepresentation in certain STEM (science, technology, engineering, and mathematics) subjects. We show that this is not the case for the competitive exams used to recruit almost all French secondary and postsecondary teachers and professors. Comparisons of oral non-gender-blind tests with written gender-blind tests for about 100,000 individuals observed in 11 different fields over the period 2006-2013 reveal a bias in favor of women that is strongly increasing with the extent of a field's male-domination. This bias turns from 3 to 5 percentile ranks for men in literature and foreign languages to about 10 percentile ranks for women in math, physics, or philosophy. These findings have implications for the debate over what interventions are appropriate to increase the representation of women in fields in which they are currently underrepresented. Copyright © 2016, American Association for the Advancement of Science.

  20. A decentralized process for finding equilibria given by linear equations.

    PubMed Central

    Reiter, S

    1994-01-01

    I present a decentralized process for finding the equilibria of an economy characterized by a finite number of linear equilibrium conditions. The process finds all equilibria or, if there are none, reports that, in a finite number of steps at most equal to the number of equations. The communication and computational complexity compare favorably with other decentralized processes. The process may also be interpreted as an algorithm for solving a distributed system of linear equations. Comparisons with the Linpack program for LU (lower and upper triangular decomposition of the matrix of the equation system, a version of Gaussian elimination) are presented. PMID:11607486

  1. Theoretical study on the reaction mechanism of CH 4 with CaO

    NASA Astrophysics Data System (ADS)

    Yang, Hua-Qing; Hu, Chang-Wei; Qin, Song

    2006-11-01

    The reaction pathways and energetics for the reaction of methane with CaO are discussed on the singlet spin state potential energy surface at the B3LYP/6-311+G(2df,2p) and QCISD/6-311++G(3df,3pd)//B3LYP/6-311+G(2df,2p) levels of theory. The reaction of methane with CaO is proposed to proceed in the following reaction pathways: CaO + CH 4 → CaOCH 4 → [TS] → CaOH + CH 3, CaO + CH 4 → OCaCH 4 → [TS] → HOCaCH 3 → CaOH + CH 3 or [TS] → CaCH 3OH → Ca + CH 3OH, and OCaCH 4 → [TS] → HCaOCH 3 → CaOCH 3 + H or [TS] → CaCH 3OH → Ca + CH 3OH. The gas-phase methane-methanol conversion by CaO is suggested to proceed via two kinds of important reaction intermediates, HOCaCH 3 and HCaOCH 3, and the reaction pathway via the hydroxy intermediate (HOCaCH 3) is energetically more favorable than the other one via the methoxy intermediate (HCaOCH 3). The hydroxy intermediate HOCaCH 3 is predicted to be the energetically most preferred configuration in the reaction of CaO + CH 4. Meanwhile, these three product channels (CaOH + CH 3, CaOCH 3 + H and Ca + CH 3OH) are expected to compete with each other, and the formation of methyl radical is the most preferable pathway energetically. On the other hand, the intermediates HCaOCH 3 and HOCaCH 3 are predicted to be the energetically preferred configuration in the reaction of Ca + CH 3OH, which is precisely the reverse reaction of methane hydroxylation.

  2. A Method for Finding Metabolic Pathways Using Atomic Group Tracking.

    PubMed

    Huang, Yiran; Zhong, Cheng; Lin, Hai Xiang; Wang, Jianyi

    2017-01-01

    A fundamental computational problem in metabolic engineering is to find pathways between compounds. Pathfinding methods using atom tracking have been widely used to find biochemically relevant pathways. However, these methods require the user to define the atoms to be tracked. This may lead to failing to predict the pathways that do not conserve the user-defined atoms. In this work, we propose a pathfinding method called AGPathFinder to find biochemically relevant metabolic pathways between two given compounds. In AGPathFinder, we find alternative pathways by tracking the movement of atomic groups through metabolic networks and use combined information of reaction thermodynamics and compound similarity to guide the search towards more feasible pathways and better performance. The experimental results show that atomic group tracking enables our method to find pathways without the need of defining the atoms to be tracked, avoid hub metabolites, and obtain biochemically meaningful pathways. Our results also demonstrate that atomic group tracking, when incorporated with combined information of reaction thermodynamics and compound similarity, improves the quality of the found pathways. In most cases, the average compound inclusion accuracy and reaction inclusion accuracy for the top resulting pathways of our method are around 0.90 and 0.70, respectively, which are better than those of the existing methods. Additionally, AGPathFinder provides the information of thermodynamic feasibility and compound similarity for the resulting pathways.

  3. A Method for Finding Metabolic Pathways Using Atomic Group Tracking

    PubMed Central

    Zhong, Cheng; Lin, Hai Xiang; Wang, Jianyi

    2017-01-01

    A fundamental computational problem in metabolic engineering is to find pathways between compounds. Pathfinding methods using atom tracking have been widely used to find biochemically relevant pathways. However, these methods require the user to define the atoms to be tracked. This may lead to failing to predict the pathways that do not conserve the user-defined atoms. In this work, we propose a pathfinding method called AGPathFinder to find biochemically relevant metabolic pathways between two given compounds. In AGPathFinder, we find alternative pathways by tracking the movement of atomic groups through metabolic networks and use combined information of reaction thermodynamics and compound similarity to guide the search towards more feasible pathways and better performance. The experimental results show that atomic group tracking enables our method to find pathways without the need of defining the atoms to be tracked, avoid hub metabolites, and obtain biochemically meaningful pathways. Our results also demonstrate that atomic group tracking, when incorporated with combined information of reaction thermodynamics and compound similarity, improves the quality of the found pathways. In most cases, the average compound inclusion accuracy and reaction inclusion accuracy for the top resulting pathways of our method are around 0.90 and 0.70, respectively, which are better than those of the existing methods. Additionally, AGPathFinder provides the information of thermodynamic feasibility and compound similarity for the resulting pathways. PMID:28068354

  4. Development and Validation of an Empiric Tool to Predict Favorable Neurologic Outcomes Among PICU Patients.

    PubMed

    Gupta, Punkaj; Rettiganti, Mallikarjuna; Gossett, Jeffrey M; Daufeldt, Jennifer; Rice, Tom B; Wetzel, Randall C

    2018-01-01

    To create a novel tool to predict favorable neurologic outcomes during ICU stay among children with critical illness. Logistic regression models using adaptive lasso methodology were used to identify independent factors associated with favorable neurologic outcomes. A mixed effects logistic regression model was used to create the final prediction model including all predictors selected from the lasso model. Model validation was performed using a 10-fold internal cross-validation approach. Virtual Pediatric Systems (VPS, LLC, Los Angeles, CA) database. Patients less than 18 years old admitted to one of the participating ICUs in the Virtual Pediatric Systems database were included (2009-2015). None. A total of 160,570 patients from 90 hospitals qualified for inclusion. Of these, 1,675 patients (1.04%) were associated with a decline in Pediatric Cerebral Performance Category scale by at least 2 between ICU admission and ICU discharge (unfavorable neurologic outcome). The independent factors associated with unfavorable neurologic outcome included higher weight at ICU admission, higher Pediatric Index of Morality-2 score at ICU admission, cardiac arrest, stroke, seizures, head/nonhead trauma, use of conventional mechanical ventilation and high-frequency oscillatory ventilation, prolonged hospital length of ICU stay, and prolonged use of mechanical ventilation. The presence of chromosomal anomaly, cardiac surgery, and utilization of nitric oxide were associated with favorable neurologic outcome. The final online prediction tool can be accessed at https://soipredictiontool.shinyapps.io/GNOScore/. Our model predicted 139,688 patients with favorable neurologic outcomes in an internal validation sample when the observed number of patients with favorable neurologic outcomes was among 139,591 patients. The area under the receiver operating curve for the validation model was 0.90. This proposed prediction tool encompasses 20 risk factors into one probability to predict

  5. Comparison of job stress and obesity in nurses with favorable and unfavorable work schedules.

    PubMed

    Han, Kihye; Trinkoff, Alison M; Storr, Carla L; Geiger-Brown, Jeanne; Johnson, Karen L; Park, Sungae

    2012-08-01

    To compare obesity-related factors between female nurses with favorable work schedules (WSs) and unfavorable WSs. In a cross-sectional study, 1724 female nurses were stratified by WS (favorable vs unfavorable). For each schedule type, the odds of obesity were related to health behaviors, home demands, and job stress using logistic regression models. Among nurses with unfavorable WSs, healthy behaviors (exercise, sleep) were inversely associated with obesity, whereas for those with favorable WSs, obese nurses reported significantly more unhealthy behaviors (smoking, alcohol use; odds ratio [OR], 1.19; 95% confidence interval [CI], 1.02-1.38), more physical lifting of children/dependents (OR, 1.43; 95% CI, 1.06-1.93), having more nurse input into their jobs (OR, 1.21; 95% CI, 1.02-1.44), yet less boss support at work (OR, 0.83; 95% CI, 0.68-0.99). Considering impacts of WSs on obesity and potential obesity-related health outcomes, healthful scheduling should be provided to nurses.

  6. Multiple Solutions of a Problem: Find the Best Point of the Shot

    ERIC Educational Resources Information Center

    Zelenskiy, Alexander S.

    2013-01-01

    In a recent issue of "Australian Senior Mathematics Journal" there has been published an interesting article by Galbraith and Lockwood (2010). In that article the problem of finding the most favorable points for a shot at goal in Australian football is considered from different points of view. A similar problem was considered by…

  7. Quantum chemical investigation of the primary thermal pyrolysis reactions of the sodium carboxylate group in a brown coal model.

    PubMed

    Li, Jian; Zhang, Baisheng; Zhang, Zhiqiang; Yan, Kefeng; Kang, Lixun

    2014-12-01

    The primary pyrolysis mechanisms of the sodium carboxylate group in sodium benzoate-used as a model compound of brown coal-were studied by performing quantum chemical computations using B3LYP and the CBS method. Various possible reaction pathways involving reactions such as unimolecular and bimolecular decarboxylation and decarbonylation, crosslinking, and radical attack in the brown coal matrix were explored. Without the participation of reactive radicals, unimolecular decarboxylation to release CO2 was calculated to be the most energetically favorable primary reaction pathway at the B3LYP/6-311+G (d, p) level of theory, and was also found to be more energetically favorable than decarboxylation of an carboxylic acid group. When CBS-QBS results were included, crosslinking between the sodium carboxylate group and the carboxylic acid and the decarboxylation of the sodium carboxylate group (catalyzed by the phenolic hydroxyl group) were found to be possible; this pathway competes with unimolecular decarboxylation of the sodium carboxylate group. Provided that H and CH3 radicals are present in the brown coal matrix and can access the sodium carboxylate group, accelerated pyrolysis of the sodium carboxylate group becomes feasible, leading to the release of an Na atom or an NaCO2 radical at the B3LYP/6-311+G (d, p) or CBS-QB3 level of theory, respectively.

  8. 'Football is good for your sleep': favorable sleep patterns and psychological functioning of adolescent male intense football players compared to controls.

    PubMed

    Brand, Serge; Beck, Johannes; Gerber, Markus; Hatzinger, Martin; Holsboer-Trachsler, Edith

    2009-11-01

    It is commonly assumed that physical activity exerts a favorable impact on sleep, although scientific evidence is lacking. This study investigated the impact of football sports on the sleep patterns of 36 male chronic and intense football players and 34 controls. Participants completed a sleep log for seven consecutive days. Compared to controls, football players reported shorter sleep onset latency, fewer awakenings, higher scores of sleep quality and a lower variability of sleep from weekdays to weekends. The findings suggest that football sports activity is positively associated with both quantitative and qualitative dimensions of sleep.

  9. Eliminating fast reactions in stochastic simulations of biochemical networks: A bistable genetic switch

    NASA Astrophysics Data System (ADS)

    Morelli, Marco J.; Allen, Rosalind J.; Tǎnase-Nicola, Sorin; ten Wolde, Pieter Rein

    2008-01-01

    In many stochastic simulations of biochemical reaction networks, it is desirable to "coarse grain" the reaction set, removing fast reactions while retaining the correct system dynamics. Various coarse-graining methods have been proposed, but it remains unclear which methods are reliable and which reactions can safely be eliminated. We address these issues for a model gene regulatory network that is particularly sensitive to dynamical fluctuations: a bistable genetic switch. We remove protein-DNA and/or protein-protein association-dissociation reactions from the reaction set using various coarse-graining strategies. We determine the effects on the steady-state probability distribution function and on the rate of fluctuation-driven switch flipping transitions. We find that protein-protein interactions may be safely eliminated from the reaction set, but protein-DNA interactions may not. We also find that it is important to use the chemical master equation rather than macroscopic rate equations to compute effective propensity functions for the coarse-grained reactions.

  10. Sub-barrier quasifission in heavy element formation reactions with deformed actinide target nuclei

    NASA Astrophysics Data System (ADS)

    Hinde, D. J.; Jeung, D. Y.; Prasad, E.; Wakhle, A.; Dasgupta, M.; Evers, M.; Luong, D. H.; du Rietz, R.; Simenel, C.; Simpson, E. C.; Williams, E.

    2018-02-01

    Background: The formation of superheavy elements (SHEs) by fusion of two massive nuclei is severely inhibited by the competing quasifission process. Low excitation energies favor SHE survival against fusion-fission competition. In "cold" fusion with spherical target nuclei near 208Pb, SHE yields are largest at beam energies significantly below the average capture barrier. In "hot" fusion with statically deformed actinide nuclei, this is not the case. Here the elongated deformation-aligned configurations in sub-barrier capture reactions inhibits fusion (formation of a compact compound nucleus), instead favoring rapid reseparation through quasifission. Purpose: To determine the probabilities of fast and slow quasifission in reactions with prolate statically deformed actinide nuclei, through measurement and quantitative analysis of the dependence of quasifission characteristics at beam energies spanning the average capture barrier energy. Methods: The Australian National University Heavy Ion Accelerator Facility and CUBE fission spectrometer have been used to measure fission and quasifission mass and angle distributions for reactions with projectiles from C to S, bombarding Th and U target nuclei. Results: Mass-asymmetric quasifission occurring on a fast time scale, associated with collisions with the tips of the prolate actinide nuclei, shows a rapid increase in probability with increasing projectile charge, the transition being centered around projectile atomic number ZP=14 . For mass-symmetric fission events, deviations of angular anisotropies from expectations for fusion fission, indicating a component of slower quasifission, suggest a similar transition, but centered around ZP˜8 . Conclusions: Collisions with the tips of statically deformed prolate actinide nuclei show evidence for two distinct quasifission processes of different time scales. Their probabilities both increase rapidly with the projectile charge. The probability of fusion can be severely

  11. Glucagon-like peptide-1 receptor agonists favorably address all components of metabolic syndrome.

    PubMed

    Chatterjee, Sanjay; Ghosal, Samit; Chatterjee, Saurav

    2016-10-15

    Cardiovascular death is the leading cause of mortality for patients with type 2 diabetes mellitus. The etiology of cardiovascular disease in diabetes may be divided into hyperglycemia per se and factors operating through components of metabolic syndrome (MetS). Hyperglycemia causes direct injury to vascular endothelium and possibly on cardiac myocytes. MetS is a cluster of risk factors like obesity, hyperglycemia, hypertension and dyslipidemia. The incidence of this syndrome is rising globally. Glucagon-like peptide-1 receptor agonists (GLP-1RA) are a group of drugs, which address all components of this syndrome favorably. Experimental evidence suggests that they have favorable actions on myocardium as well. Several compounds belonging to GLP-1RA class are in market now and a large number awaiting their entry. Although, originally this class of drugs emerged as a treatment for type 2 diabetes mellitus, more recent data generated revealed beneficial effects on multiple metabolic parameters. We have studied literature published between 2000 and 2016 to look into effects of GLP-1RA on components of MetS. Results from recently concluded clinical trials suggest that some of the molecules in this class may have favorable effects on cardiovascular outcome.

  12. Associations between beliefs about and reactions toward people who stutter.

    PubMed

    Arnold, Hayley S; Li, Jian

    2016-03-01

    This study sought to assess whether beliefs about people who stutter (PWS) predict intended behavioral and affective reactions toward them in a large and varied sample of respondents while taking into account familiarity with PWS and the demographic variables of age, education, and gender. Analyses were based on 2206 residents of the United States of America. The seemingly unrelated regression (SUR) technique was used to test the relationship between beliefs about PWS and behavioral and affective reactions toward PWS. Variables such as familiarity with PWS and demographic data were also controlled in the statistical model. Findings indicated that, when demographic variables and familiarity were taken into account, the accuracy of participants' beliefs about PWS significantly predicted their intended behavioral and affective reactions toward PWS. The participants' gender and familiarity with PWS were also associated with these reactions toward PWS. The finding of an association between beliefs and intended reactions validates attempts to improve public treatment of PWS through improving the accuracy of beliefs about PWS. Additionally, because familiarity with PWS is a significant predictor of helpful and positive reactions toward PWS, interventions involving PWS educating others through direct interpersonal interactions may be one effective way to improve public reactions toward individuals who stutter. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. Nonimmediate hypersensitivity reactions to iodinated contrast media.

    PubMed

    Gómez, Enrique; Ariza, Adriana; Blanca-López, Natalia; Torres, Maria J

    2013-08-01

    To provide a detailed analysis of the latest findings on the mechanisms underlying the nonimmediate reactions to iodinated contrast media and comment on the recent advances in diagnosis, focusing on the roles of the skin test, drug provocation test (DPT), and lymphocyte transformation test (LTT). Several studies have reported new findings supporting an important role for T-lymphocytes in the nonimmediate reactions to iodinated contrast media. The LTT has been used as an in-vitro tool for diagnosis, but with variable results. However, the inclusion of autologous monocyte-derived dendritic cells as professional antigen-presenting cells has improved the sensitivity of this test. Regarding in-vivo diagnosis, although skin testing has been routine, it has now been shown that its sensitivity and negative predictive value are low. Recent studies have demonstrated that the DPT is a well tolerated and useful procedure that is necessary to confirm the diagnosis of nonimmediate hypersensitivity reactions to iodinated contrast media. Nonimmediate reactions to contrast media are usually T-cell mediated. Diagnosis is based on skin testing, although its sensitivity and negative predictive value are not optimal. Consequently, drug provocation testing is often needed to confirm the diagnosis and also to seek alternative contrast media that can be tolerated.

  14. Fundamental Reaction Pathway for Peptide Metabolism by Proteasome: Insights from First-principles Quantum Mechanical/Molecular Mechanical Free Energy Calculations

    PubMed Central

    Wei, Donghui; Fang, Lei; Tang, Mingsheng; Zhan, Chang-Guo

    2013-01-01

    Proteasome is the major component of the crucial nonlysosomal protein degradation pathway in the cells, but the detailed reaction pathway is unclear. In this study, first-principles quantum mechanical/molecular mechanical free energy calculations have been performed to explore, for the first time, possible reaction pathways for proteasomal proteolysis/hydrolysis of a representative peptide, succinyl-leucyl-leucyl-valyl-tyrosyl-7-amino-4-methylcoumarin (Suc-LLVY-AMC). The computational results reveal that the most favorable reaction pathway consists of six steps. The first is a water-assisted proton transfer within proteasome, activating Thr1-Oγ. The second is a nucleophilic attack on the carbonyl carbon of a Tyr residue of substrate by the negatively charged Thr1-Oγ, followed by the dissociation of the amine AMC (third step). The fourth step is a nucleophilic attack on the carbonyl carbon of the Tyr residue of substrate by a water molecule, accompanied by a proton transfer from the water molecule to Thr1-Nz. Then, Suc-LLVY is dissociated (fifth step), and Thr1 is regenerated via a direct proton transfer from Thr1-Nz to Thr1-Oγ. According to the calculated energetic results, the overall reaction energy barrier of the proteasomal hydrolysis is associated with the transition state (TS3b) for the third step involving a water-assisted proton transfer. The determined most favorable reaction pathway and the rate-determining step have provided a reasonable interpretation of the reported experimental observations concerning the substituent and isotopic effects on the kinetics. The calculated overall free energy barrier of 18.2 kcal/mol is close to the experimentally-derived activation free energy of ~18.3–19.4 kcal/mol, suggesting that the computational results are reasonable. PMID:24111489

  15. Evolution of learning in fluctuating environments: when selection favors both social and exploratory individual learning.

    PubMed

    Borenstein, Elhanan; Feldman, Marcus W; Aoki, Kenichi

    2008-03-01

    Cumulative cultural change requires organisms that are capable of both exploratory individual learning and faithful social learning. In our model, an organism's phenotype is initially determined innately (by its genotypic value) or by social learning (copying a phenotype from the parental generation), and then may or may not be modified by individual learning (exploration around the initial phenotype). The environment alternates periodically between two states, each defined as a certain range of phenotypes that can survive. These states may overlap, in which case the same phenotype can survive in both states, or they may not. We find that a joint social and exploratory individual learning strategy-the strategy that supports cumulative culture-is likely to spread when the environmental states do not overlap. In particular, when the environmental states are contiguous and mutation is allowed among the genotypic values, this strategy will spread in either moderately or highly stable environments, depending on the exact nature of the individual learning applied. On the other hand, natural selection often favors a social learning strategy without exploration when the environmental states overlap. We find only partial support for the "consensus" view, which holds that individual learning, social learning, and innate determination of behavior will evolve at short, intermediate, and long environmental periodicities, respectively.

  16. Measuring Metacognition and Reaction Time: Further Findings on the Performances of General Education, Low-Achieving, and Institutionally Raised Students

    ERIC Educational Resources Information Center

    Al-Hilawani, Yasser A.; Abdullah, Ahmad A.

    2010-01-01

    The purpose of this study was to use the picture format to examine in depth the metacognitive performances and reaction time in general education, low-achieving, and institutionally raised students. Results revealed that institutionally raised students, unlike low-achieving students, took significantly the longest reaction time to finish the test…

  17. Altered serotonin physiology in human breast cancers favors paradoxical growth and cell survival

    PubMed Central

    2009-01-01

    Introduction The breast microenvironment can either retard or accelerate the events associated with progression of latent cancers. However, the actions of local physiological mediators in the context of breast cancers are poorly understood. Serotonin (5-HT) is a critical local regulator of epithelial homeostasis in the breast and other organs. Herein, we report complex alterations in the intrinsic mammary gland serotonin system of human breast cancers. Methods Serotonin biosynthetic capacity was analyzed in human breast tumor tissue microarrays using immunohistochemistry for tryptophan hydroxylase 1 (TPH1). Serotonin receptors (5-HT1-7) were analyzed in human breast tumors using the Oncomine database. Serotonin receptor expression, signal transduction, and 5-HT effects on breast cancer cell phenotype were compared in non-transformed and transformed human breast cells. Results In the context of the normal mammary gland, 5-HT acts as a physiological regulator of lactation and involution, in part by favoring growth arrest and cell death. This tightly regulated 5-HT system is subverted in multiple ways in human breast cancers. Specifically, TPH1 expression undergoes a non-linear change during progression, with increased expression during malignant progression. Correspondingly, the tightly regulated pattern of 5-HT receptors becomes dysregulated in human breast cancer cells, resulting in both ectopic expression of some isoforms and suppression of others. The receptor expression change is accompanied by altered downstream signaling of 5-HT receptors in human breast cancer cells, resulting in resistance to 5-HT-induced apoptosis, and stimulated proliferation. Conclusions Our data constitutes the first report of direct involvement of 5-HT in human breast cancer. Increased 5-HT biosynthetic capacity accompanied by multiple changes in 5-HT receptor expression and signaling favor malignant progression of human breast cancer cells (for example, stimulated proliferation

  18. Altered serotonin physiology in human breast cancers favors paradoxical growth and cell survival.

    PubMed

    Pai, Vaibhav P; Marshall, Aaron M; Hernandez, Laura L; Buckley, Arthur R; Horseman, Nelson D

    2009-01-01

    The breast microenvironment can either retard or accelerate the events associated with progression of latent cancers. However, the actions of local physiological mediators in the context of breast cancers are poorly understood. Serotonin (5-HT) is a critical local regulator of epithelial homeostasis in the breast and other organs. Herein, we report complex alterations in the intrinsic mammary gland serotonin system of human breast cancers. Serotonin biosynthetic capacity was analyzed in human breast tumor tissue microarrays using immunohistochemistry for tryptophan hydroxylase 1 (TPH1). Serotonin receptors (5-HT1-7) were analyzed in human breast tumors using the Oncomine database. Serotonin receptor expression, signal transduction, and 5-HT effects on breast cancer cell phenotype were compared in non-transformed and transformed human breast cells. In the context of the normal mammary gland, 5-HT acts as a physiological regulator of lactation and involution, in part by favoring growth arrest and cell death. This tightly regulated 5-HT system is subverted in multiple ways in human breast cancers. Specifically, TPH1 expression undergoes a non-linear change during progression, with increased expression during malignant progression. Correspondingly, the tightly regulated pattern of 5-HT receptors becomes dysregulated in human breast cancer cells, resulting in both ectopic expression of some isoforms and suppression of others. The receptor expression change is accompanied by altered downstream signaling of 5-HT receptors in human breast cancer cells, resulting in resistance to 5-HT-induced apoptosis, and stimulated proliferation. Our data constitutes the first report of direct involvement of 5-HT in human breast cancer. Increased 5-HT biosynthetic capacity accompanied by multiple changes in 5-HT receptor expression and signaling favor malignant progression of human breast cancer cells (for example, stimulated proliferation, inappropriate cell survival). This occurs

  19. Slow slip generated by dehydration reaction coupled with slip-induced dilatancy and thermal pressurization

    NASA Astrophysics Data System (ADS)

    Yamashita, Teruo; Schubnel, Alexandre

    2016-10-01

    Sustained slow slip, which is a distinctive feature of slow slip events (SSEs), is investigated theoretically, assuming a fault embedded within a fluid-saturated 1D thermo-poro-elastic medium. The object of study is specifically SSEs occurring at the down-dip edge of seismogenic zone in hot subduction zones, where mineral dehydrations (antigorite, lawsonite, chlorite, and glaucophane) are expected to occur near locations where deep slow slip events are observed. In the modeling, we introduce dehydration reactions, coupled with slip-induced dilatancy and thermal pressurization, and slip evolution is assumed to interact with fluid pressure change through Coulomb's frictional stress. Our calculations show that sustained slow slip events occur when the dehydration reaction is coupled with slip-induced dilatancy. Specifically, slow slip is favored by a low initial stress drop, an initial temperature of the medium close to that of the dehydration reaction equilibrium temperature, a low permeability, and overall negative volume change associated with the reaction (i.e., void space created by the reaction larger than the space occupied by the fluid released). Importantly, if we do not assume slip-induced dilatancy, slip is accelerated with time soon after the slip onset even if the dehydration reaction is assumed. This suggests that slow slip is sustained for a long time at hot subduction zones because dehydration reaction is coupled with slip-induced dilatancy. Such slip-induced dilatancy may occur at the down-dip edge of seismogenic zone at hot subduction zones because of repetitive occurrence of dehydration reaction there.

  20. Theoretical and experimental consideration of the reactions between VxOy+ and ethylene.

    PubMed

    Justes, Dina R; Mitrić, Roland; Moore, Nelly A; Bonacić-Koutecký, Vlasta; Castleman, A Welford

    2003-05-21

    We present joint theoretical and experimental results which provide evidence for the selectivity of V(x)O(y)(+) clusters in reactions toward ethylene due to the charge and different oxidation states of vanadium for different cluster sizes. Density functional calculations were performed on the reactions between V(x)O(y)(+) and ethylene, allowing us to identify the structure-reactivity relationship and to corroborate the experimental results obtained by Castleman and co-workers (Zemski, K. A.; Justes, D. R.; Castleman, A. W., Jr. J. Phys. Chem. A 2001, 105, 10237). The lowest-energy structures for the V(2)O(2)(-)(6)(+) and V(4)O(8)(-)(10)(+) clusters and the V(2)O(3)(-)(6)(+)-C(2)H(4) and V(4)O(10)(+)-C(2)H(4) complexes, as well as the energetics for reactions between ethylene and V(2)O(4)(-)(6)(+) and V(4)O(10)(+) are presented here. The oxygen transfer reaction pathway was determined to be the most energetically favorable one available to V(2)O(5)(+) and V(4)O(10)(+) via a radical-cation mechanism. The association and replacement reaction pathways were found to be the optimal channels for V(2)O(4)(+) and V(2)O(6)(+), respectively. These results are in agreement with the experimental results reported previously. Experiments were also conducted for the reactions between V(2)O(5)(+) and ethylene to include an energetic analysis at increasing pressures. It was found that the addition of energy depleted the production of V(2)O(4)(+), confirming that a more involved reaction rather than a collisional process is responsible for the observed phenomenon. In this contribution we show that investigation of reactions involving gas-phase cationic vanadium oxide clusters with small hydrocarbons is suitable for the identification of reactive centers responsible for selectivity in heterogeneous catalysis.

  1. Four-step reaction for polytriazine elastomers

    NASA Technical Reports Server (NTRS)

    Rosser, R. W.; Korus, R. A.

    1980-01-01

    Four step imidoylamidine reaction sequence is used to make crosslinked polyperfluoralkyltriazines with superior elastomeric properties, greater molecular weight, and crosslinking control. Polymers can find useful application in fuel tank sealants, o-ring, wire enamels, pneumatic ducts, and many other applications.

  2. Multivariate statistical analysis to investigate the subduction zone parameters favoring the occurrence of giant megathrust earthquakes

    NASA Astrophysics Data System (ADS)

    Brizzi, S.; Sandri, L.; Funiciello, F.; Corbi, F.; Piromallo, C.; Heuret, A.

    2018-03-01

    The observed maximum magnitude of subduction megathrust earthquakes is highly variable worldwide. One key question is which conditions, if any, favor the occurrence of giant earthquakes (Mw ≥ 8.5). Here we carry out a multivariate statistical study in order to investigate the factors affecting the maximum magnitude of subduction megathrust earthquakes. We find that the trench-parallel extent of subduction zones and the thickness of trench sediments provide the largest discriminating capability between subduction zones that have experienced giant earthquakes and those having significantly lower maximum magnitude. Monte Carlo simulations show that the observed spatial distribution of giant earthquakes cannot be explained by pure chance to a statistically significant level. We suggest that the combination of a long subduction zone with thick trench sediments likely promotes a great lateral rupture propagation, characteristic of almost all giant earthquakes.

  3. Contribution of Nano- to Microscale Roughness to Heterogeneity: Closing the Gap between Unfavorable and Favorable Colloid Attachment Conditions.

    PubMed

    Rasmuson, Anna; Pazmino, Eddy; Assemi, Shoeleh; Johnson, William P

    2017-02-21

    Surface roughness has been reported to both increase as well as decrease colloid retention. In order to better understand the boundaries within which roughness operates, attachment of a range of colloid sizes to glass with three levels of roughness was examined under both favorable (energy barrier absent) and unfavorable (energy barrier present) conditions in an impinging jet system. Smooth glass was found to provide the upper and lower bounds for attachment under favorable and unfavorable conditions, respectively. Surface roughness decreased, or even eliminated, the gap between favorable and unfavorable attachment and did so by two mechanisms: (1) under favorable conditions attachment decreased via increased hydrodynamic slip length and reduced attraction and (2) under unfavorable conditions attachment increased via reduced colloid-collector repulsion (reduced radius of curvature) and increased attraction (multiple points of contact, and possibly increased surface charge heterogeneity). Absence of a gap where these forces most strongly operate for smaller (<200 nm) and larger (>2 μm) colloids was observed and discussed. These observations elucidate the role of roughness in colloid attachment under both favorable and unfavorable conditions.

  4. Student Evaluation of UTOPIA

    ERIC Educational Resources Information Center

    Pearson, M.; Carswell, D. J.

    1978-01-01

    Reports some reactions and opinions of the students to a course in nuclear and radiation chemistry using programmed instructional aids. Concludes that the findings were very favorable to the course. (GA)

  5. Synchrotron Photoionization Study of Furan and 2-Methylfuran Reactions with Methylidyne Radical (CH) at 298 K.

    PubMed

    Carrasco, Erica; Smith, Kenneth J; Meloni, Giovanni

    2018-01-11

    The reactions of furan and 2-methylfuran with methylidyne CH (X 2 Π) radical were investigated at 298 K using synchrotron radiation produced at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Reaction products were observed by multiplexed photoionization mass spectrometry and characterized based on their photoionization spectra and kinetic time traces. Primary products observed in furan + CH are 2,4-cyclopentadien-1-one (m/z = 80), 2-penten-4-ynal (m/z = 80), and vinylacetylene (m/z = 52). From 2-methylfuran + CH, 2-4-cyclopentadien-1-carbaldehyde (m/z = 94), 2,3,4-hexatrienal (m/z = 94), 1,3 cyclopentadiene (m/z = 66), 3-penten-1-yne (Z) (m/z = 66), and vinylacetylene (m/z = 52) are the primary products observed. Using potential energy surface scans, thermodynamically favorable reaction pathways are proposed. CH addition to the π-bonds in furan and 2-methylfuran rings was found to be the entrance channel that led to formation of all identified primary products. Both reactions follow patterns of H loss and CHO loss, as well as formation of cyclic and acyclic isomers.

  6. Reaction chemistry in rechargeable Li-O2 batteries.

    PubMed

    Lim, Hee-Dae; Lee, Byungju; Bae, Youngjoon; Park, Hyeokjun; Ko, Youngmin; Kim, Haegyeom; Kim, Jinsoo; Kang, Kisuk

    2017-05-22

    The seemingly simple reaction of Li-O 2 batteries involving lithium and oxygen makes this chemistry attractive for high-energy-density storage systems; however, achieving this reaction in practical rechargeable Li-O 2 batteries has proven difficult. The reaction paths leading to the final Li 2 O 2 discharge products can be greatly affected by the operating conditions or environment, which often results in major side reactions. Recent research findings have begun to reveal how the reaction paths may be affected by the surrounding conditions and to uncover the factors contributing to the difficulty in achieving the reactions of lithium and oxygen. This progress report describes the current state of understanding of the electrode reaction mechanisms in Li-O 2 batteries; the factors that affect reaction pathways; and the effect of cell components such as solvents, salts, additives, and catalysts on the discharge product and its decomposition during charging. This comprehensive review of the recent progress in understanding the reaction chemistry of the Li-O 2 system will serve as guidelines for future research and aid in the development of reliable high-energy-density rechargeable Li-O 2 batteries.

  7. 41 CFR 101-39.404 - Claims in favor of the Government.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... VEHICLES 39-INTERAGENCY FLEET MANAGEMENT SYSTEMS 39.4-Accidents and Claims § 101-39.404 Claims in favor of... Interagency Fleet Management System (IFMS) vehicle is at fault and that party can be reasonably identified... pertaining to the accident and its investigation to the servicing GSA IFMS fleet management center. The GSA...

  8. Favorable Cardiovascular Health, Compression of Morbidity, and Healthcare Costs: Forty-Year Follow-Up of the CHA Study (Chicago Heart Association Detection Project in Industry).

    PubMed

    Allen, Norrina B; Zhao, Lihui; Liu, Lei; Daviglus, Martha; Liu, Kiang; Fries, James; Shih, Ya-Chen Tina; Garside, Daniel; Vu, Thanh-Huyen; Stamler, Jeremiah; Lloyd-Jones, Donald M

    2017-05-02

    We examined the association of cardiovascular health at younger ages with the proportion of life lived free of morbidity, the cumulative burden of morbidity, and average healthcare costs at older ages. The CHA study (Chicago Heart Association Detection Project in Industry) is a longitudinal cohort of employed men and women 18 to 74 years of age at baseline examination in 1967 to 1973. Baseline measurements included blood pressure, cholesterol, diabetes mellitus, body mass index, and smoking. Individuals were classified into 1 of 4 strata of cardiovascular health: favorable levels of all factors, 0 factors high but ≥1 elevated risk factors, 1 high risk factor, and ≥2 high risk factors. Linked Medicare and National Death Index data from 1984 to 2010 were used to determine morbidity in older age. An individual's all-cause morbidity score and cardiovascular morbidity score were calculated from International Classification of Disease, Ninth Revision codes for each year of follow-up. We included 25 804 participants who became ≥65 years of age by 2010, representing 65% of all original CHA participants (43% female; 90% white; mean age, 44 years at baseline); 6% had favorable levels of all factors, 19% had ≥1 risk factors at elevated levels, 40% had 1 high risk factor, and 35% had ≥2 high risk factors. Favorable cardiovascular health at younger ages extended survival by almost 4 years and postponed the onset of all-cause and cardiovascular morbidity by 4.5 and 7 years, respectively, resulting in compression of morbidity in both absolute and relative terms. This translated to lower cumulative and annual healthcare costs for those in favorable cardiovascular health ( P <0.001) during Medicare eligibility. Individuals in favorable cardiovascular health in early middle age live a longer, healthier life free of all types of morbidity. These findings provide strong support for prevention efforts earlier in life aimed at preserving cardiovascular health and reducing

  9. Kinetics studies of the reactions of main fourth-period monocations (Ga+, Ge+, As+, and Se+) with methyl fluoride.

    PubMed

    Barrientos, Carmen; Rayón, Víctor Manuel; Largo, Antonio; Sordo, José Ángel; Redondo, Pilar

    2013-08-22

    Thermodynamics and kinetics theoretical studies on the gas-phase reactions of fluoromethane with main fourth-period monocations (Ga(+), Ge(+), As(+), and Se(+)) have been carried out. Density functional theory (in particular mPW1K functional) was employed in the description of the potential energy surfaces, and refinement of the energies were done at the CCSD(T) level. The reaction rate constants were estimated using variational/conventional microcanonical transition state theory. From a thermodynamic viewpoint, the fluorine abstraction product is predicted for Ga(+) and Ge(+), whereas for As(+) and Se(+) the elimination product, MCH2(+) (M = As, Se) + HF, is the preferred one. Nevertheless, the most favorable channel for the reactions of CH3F with Ga(+) and Se(+) cations present a net activation barrier. In the case of Ga(+), the reaction proceeds via an addition channel forming the adduct complex, CH3FGa(+), whereas for Se(+) no reaction is found, in agreement with the experiments. The predicted reaction rate constants are in reasonable good agreement with the experimental values available. Apart from the harpoon-like mechanism, our results suggest that an oxidative addition mechanism seems to play a relevant role.

  10. Finding molecular dioxygen tunnels in homoprotocatechuate 2,3-dioxygenase: implications for different reactivity of identical subunits.

    PubMed

    Xu, Liang; Zhao, Weijie; Wang, Xicheng

    2010-01-01

    Extradiol dioxygenases facilitate microbial aerobic degradation of catechol and its derivatives by activating molecular dioxygen and incorporating both oxygen atoms into their substrates. Experimental and theoretical studies have focused on the mechanism of the reaction at the active site. However, whether the catalytic rate is limited by O(2) access to the active site has not yet been explored. Here, we choose a recently solved X-ray structure of homoprotocatechuate 2,3-dioxygenase as a typical example to determine potential pathways for O(2) migration from the solvent into the enzyme center. On the basis of the trajectories of two 10-ns molecular dynamics simulations, implicit ligand sampling was used to calculate the 3D free energy map for O(2) inside the protein. The energetically optimal routes for O(2) diffusion were identified for each subunit of the homotetrameric protein structure. The O(2) tunnels formed because of thermal fluctuations were also characterized by connecting elongated cavities inside the protein. By superimposing the favorable O(2) tunnels on to the free energy map, both energetically and geometrically preferred O(2) pathways were determined, as also were the amino acids that may be critical for O(2) passage along these paths. Our results demonstrate that identical subunits possess quite distinct O(2) tunnels. The order of O(2) affinity of these tunnels is generally consistent with the order of the catalytic rate of each subunit. As a consequence, the probability of finding the reaction product is highest in the subunit containing the highest O(2) affinity pathway.

  11. Synthesis of fluorinated graphene oxide by using an easy one-pot deoxyfluorination reaction.

    PubMed

    Aguilar-Bolados, Héctor; Contreras-Cid, Ahirton; Yazdani-Pedram, Mehrdad; Acosta-Villavicencio, Gabriela; Flores, Marcos; Fuentealba, Pablo; Neira-Carrillo, Andrónico; Verdejo, Raquel; López-Manchado, Miguel A

    2018-08-15

    The fluorination of two types of graphene oxides conducted by an easy and scalable deoxyfluorination reaction is reported. This reaction was carried out using diethylaminodifluorosulfinium tetrafluoroborate, a stable compound and an efficient reagent for replacing oxygenated functional groups of graphene oxide by fluoride. The graphene oxide produced by the Hummers' method (GOH) showed lower reactivity than that produced by the Brodie's method (GOB). X-ray photoelectron spectroscopy indicated that the highest fluorination degree achieved was 4.7 at.% when GOB was used, and the CF character corresponds to semi-ionic bonds. Additionally, a partial reduction of GO was concomitant with the functionalization reaction. The deoxyfluorination reaction changed the crystalline structure of GO, favoring the reconstruction of Csp 2 structure of the graphene lattice and reducing the number of stacked layers. The fluorination led to the modification of the electronic band structure of this material, increasing the band gap from 2.05 eV for GOB to 3.88 eV for fluorinated GOB, while for GOH the low flurionation led to a slight increase of the band gap, from 3.48 eV to 3.57 eV. Copyright © 2018 Elsevier Inc. All rights reserved.

  12. A model study of the response of hypoxia to upwelling-favorable wind on the northern Gulf of Mexico shelf

    NASA Astrophysics Data System (ADS)

    Feng, Yang; Fennel, Katja; Jackson, George A.; DiMarco, Steven F.; Hetland, Robert D.

    2014-03-01

    The hypoxic region in the northern Gulf of Mexico, one of the largest man-made hypoxic zones in the world, has received extensive scientific study and management interest. A previous statistical study has concluded that in addition to anthropogenic nitrogen loading, the observed hypoxic extent is correlated to the duration of upwelling favorable (westerly) wind without elucidating the underlying mechanism. In this study, we use a three-dimensional, coupled hydrological-biogeochemical model to mechanistically examine how variations of the hypoxic area are related to the duration of upwelling-favorable wind. We performed scenario experiments with different durations of upwelling-favorable wind using realistic winds from summer 2002 (when upwelling-favorable winds were present only for about 1 month) and summer 2009 (when upwelling-favorable conditions started early and persisted for about 2 months). While the maximum simulated hypoxic area is approximately 15,000 km2 in both cases, the evolutions of the hypoxic area and the dates when its maximum extent are reached are different. With an early start of persistently upwelling-favorable wind in 2009, the hypoxic area reached its maximum in early summer and decreased afterwards. By contrast, the hypoxic area was small in early summer of 2002 and peaked during the short period of upwelling-favorable wind in late summer. The model revealed that the wind influences the evolution of the hypoxic area by changing the vertical and horizontal distributions of the low salinity, high chlorophyll water on the shelf.

  13. Bound on the Slope of Steady Water Waves with Favorable Vorticity

    NASA Astrophysics Data System (ADS)

    Strauss, Walter A.; Wheeler, Miles H.

    2016-12-01

    We consider the angle {θ} of inclination (with respect to the horizontal) of the profile of a steady two dimensional inviscid symmetric periodic or solitary water wave subject to gravity. Although {θ} may surpass 30° for some irrotational waves close to the extreme wave, Amick (Arch Ration Mech Anal 99(2):91-114, 1987) proved that for any irrotational wave the angle must be less than 31.15°. Is the situation similar for periodic or solitary waves that are not irrotational? The extreme Gerstner wave has infinite depth, adverse vorticity and vertical cusps ( θ = 90°). Moreover, numerical calculations show that even waves of finite depth can overturn if the vorticity is adverse. In this paper, on the other hand, we prove an upper bound of 45° on {θ} for a large class of waves with favorable vorticity and finite depth. In particular, the vorticity can be any constant with the favorable sign. We also prove a series of general inequalities on the pressure within the fluid, including the fact that any overturning wave must have a pressure sink.

  14. Chain-reaction crash in traffic flow controlled by taillights

    NASA Astrophysics Data System (ADS)

    Nagatani, Takashi

    2015-02-01

    We study the chain-reaction crash (multiple-vehicle collision) in low-visibility condition on a road. In the traffic situation, drivers brake according to taillights of the forward vehicle. The first crash may induce more collisions. We investigate whether or not the first collision induces the chain-reaction crash, numerically and analytically. The dynamic transitions occur from no collisions through a single collision, double collisions and triple collisions, to multiple collisions with decreasing the headway. Also, we find that the dynamic transition occurs from the finite chain reaction to the infinite chain reaction when the headway is less than the critical value. We derive, analytically, the transition points and the region maps for the chain-reaction crash in traffic flow controlled by taillights.

  15. Electronic energy density in chemical reaction systems

    NASA Astrophysics Data System (ADS)

    Tachibana, Akitomo

    2001-08-01

    The energy of chemical reaction is visualized in real space using the electronic energy density nE(r⃗) associated with the electron density n(r⃗). The electronic energy density nE(r⃗) is decomposed into the kinetic energy density nT(r⃗), the external potential energy density nV(r⃗), and the interelectron potential energy density nW(r⃗). Using the electronic energy density nE(r⃗) we can pick up any point in a chemical reaction system and find how the electronic energy E is assigned to the selected point. We can then integrate the electronic energy density nE(r⃗) in any region R surrounding the point and find out the regional electronic energy ER to the global E. The kinetic energy density nT(r⃗) is used to identify the intrinsic shape of the reactants, the electronic transition state, and the reaction products along the course of the chemical reaction coordinate. The intrinsic shape is identified with the electronic interface S that discriminates the region RD of the electronic drop from the region RA of the electronic atmosphere in the density distribution of the electron gas. If the R spans the whole space, then the integral gives the total E. The regional electronic energy ER in thermodynamic ensemble is realized in electrochemistry as the intrinsic Volta electric potential φR and the intrinsic Herring-Nichols work function ΦR. We have picked up first a hydrogen-like atom for which we have analytical exact expressions of the relativistic kinetic energy density nTM(r⃗) and its nonrelativistic version nT(r⃗). These expressions are valid for any excited bound states as well as the ground state. Second, we have selected the following five reaction systems and show the figures of the nT(r⃗) as well as the other energy densities along the intrinsic reaction coordinates: a protonation reaction to He, addition reactions of HF to C2H4 and C2H2, hydrogen abstraction reactions of NH3+ from HF and NH3. Valence electrons possess their unique

  16. Cross-Diels-Alder reactions of 6-oxo-1-sulfonyl-1,6-dihydropyridine-3-carboxylates.

    PubMed

    Teyssot, Marie-Laure; Lormier, Anh-Tuan; Chataigner, Isabelle; Piettre, Serge R

    2007-03-30

    Electron-poor 6-oxo-1-sulfonyl-1,6-dihydropyridine-3-carboxylates 1b-d undergo cross-Diels-Alder reactions with electron-rich dienes 4a-f under hyperbaric conditions, reacting either as dienophiles to yield normal-electron-demand (NED) cycloadducts 10 and/or 11 or as dienes to give inverse-electron-demand (IED) cycloadducts 12 and/or 13. The latter are converted into 14 and/or 15 through an NED cycloaddition with a second equivalent of electron-rich diene. Acyclic dienes display a propensity to yield NED products, whereas cyclic dienes tend to favor IED cycloadducts. High-pressure activation compares favorably with thermal or microwave activation in terms of both yields and suppression of the transformation of 1 into unreactive pyridines 3. Whereas the Cope rearrangement from IED to NED occurs under thermal conditions, no evidence of its involvement under high pressure could be detected. These and other data point to similar activation energies for the NED and IED processes under these conditions.

  17. Social heuristics and social roles: Intuition favors altruism for women but not for men.

    PubMed

    Rand, David G; Brescoll, Victoria L; Everett, Jim A C; Capraro, Valerio; Barcelo, Hélène

    2016-04-01

    Are humans intuitively altruistic, or does altruism require self-control? A theory of social heuristics, whereby intuitive responses favor typically successful behaviors, suggests that the answer may depend on who you are. In particular, evidence suggests that women are expected to behave altruistically, and are punished for failing to be altruistic, to a much greater extent than men. Thus, women (but not men) may internalize altruism as their intuitive response. Indeed, a meta-analysis of 13 new experiments and 9 experiments from other groups found that promoting intuition relative to deliberation increased giving in a Dictator Game among women, but not among men (Study 1, N = 4,366). Furthermore, this effect was shown to be moderated by explicit sex role identification (Study 2, N = 1,831): the more women described themselves using traditionally masculine attributes (e.g., dominance, independence) relative to traditionally feminine attributes (e.g., warmth, tenderness), the more deliberation reduced their altruism. Our findings shed light on the connection between gender and altruism, and highlight the importance of social heuristics in human prosociality. (c) 2016 APA, all rights reserved).

  18. Time-based partitioning model for predicting neurologically favorable outcome among adults with witnessed bystander out-of-hospital CPA.

    PubMed

    Abe, Toshikazu; Tokuda, Yasuharu; Cook, E Francis

    2011-01-01

    Optimal acceptable time intervals from collapse to bystander cardiopulmonary resuscitation (CPR) for neurologically favorable outcome among adults with witnessed out-of-hospital cardiopulmonary arrest (CPA) have been unclear. Our aim was to assess the optimal acceptable thresholds of the time intervals of CPR for neurologically favorable outcome and survival using a recursive partitioning model. From January 1, 2005 through December 31, 2009, we conducted a prospective population-based observational study across Japan involving consecutive out-of-hospital CPA patients (N = 69,648) who received a witnessed bystander CPR. Of 69,648 patients, 34,605 were assigned to the derivation data set and 35,043 to the validation data set. Time factors associated with better outcomes: the better outcomes were survival and neurologically favorable outcome at one month, defined as category one (good cerebral performance) or two (moderate cerebral disability) of the cerebral performance categories. Based on the recursive partitioning model from the derivation dataset (n = 34,605) to predict the neurologically favorable outcome at one month, 5 min threshold was the acceptable time interval from collapse to CPR initiation; 11 min from collapse to ambulance arrival; 18 min from collapse to return of spontaneous circulation (ROSC); and 19 min from collapse to hospital arrival. Among the validation dataset (n = 35,043), 209/2,292 (9.1%) in all patients with the acceptable time intervals and 1,388/2,706 (52.1%) in the subgroup with the acceptable time intervals and pre-hospital ROSC showed neurologically favorable outcome. Initiation of CPR should be within 5 min for obtaining neurologically favorable outcome among adults with witnessed out-of-hospital CPA. Patients with the acceptable time intervals of bystander CPR and pre-hospital ROSC within 18 min could have 50% chance of neurologically favorable outcome.

  19. Heightened exposure to parasites favors the evolution of immunity in brood parasitic cowbirds

    USGS Publications Warehouse

    Hahn, Caldwell; Reisen, William K.

    2011-01-01

    Immunologists and evolutionary biologists are interested in how the immune system evolves to fit an ecological niche. We studied the relationship between exposure to parasites and strength of immunity by investigating the response of two species of New World cowbirds (genus Molothrus, Icteridae), obligate brood parasites with contrasting life history strategies, to experimental arboviral infection. The South American shiny cowbird (M. bonariensis) is an extreme host-generalist that lays its eggs in the nests of >225 different avian species. The Central American bronzed cowbird (M. aeneus) is a relative host-specialist that lays its eggs preferentially in the nests of approximately 12 orioles in a single sister genus. West Nile virus provided a strong challenge and delineated immune differences between these species. The extreme host-generalist shiny cowbird, like the North American host-generalist, the brown-headed cowbird, showed significantly lower viremia to three arboviruses than related icterid species that were not brood parasites. The bronzed cowbird showed intermediate viremia. These findings support the interpretation that repeated exposure to a high diversity of parasites favors the evolution of enhanced immunity in brood parasitic cowbirds and makes them useful models for future studies of innate immunity.

  20. [Comparison of the quick Gram stain method to the B&M modified and favor methods].

    PubMed

    Osawa, Kayo; Kataoka, Nobumasa; Maruo, Toshio

    2011-01-01

    The Gram stain is an established method for bacterial identification, but the time needed to carry out this stain is 2-3 min. We attempted to shorten this time and stained a total of 70 clinical specimens isolated from using the Bartholomew & Mittwer (B&M) modified or Favor methods with a 3 s duration for washing and staining steps. Results were plotted and analyzed using a Hue Saturation Intensity (HSI) model. The range based on a plot of the two methods with the HSI model was presented as a reference interval. Our results indicated that 100% (35/35) of strains were Gram positive and 97.1% (34/35) were Gram negative for the quick B&M modified method. In the quick Favor method, 80.0% (28/35) were Gram positive and 68.6% (24/35) of strains were Gram negative. We propose that the quick B&M modified method is equivalent to the standard Gram staining method and is superior to the quick Favor method.

  1. Anger and the Speed of Full-Body Approach and Avoidance Reactions

    PubMed Central

    Mayan, Iddo; Meiran, Nachshon

    2011-01-01

    The notion that anger is linked to approach motivation received support from behavioral studies, which measured various motor responses to angering stimuli. However, none of these studies examined full-body motions which characterize many if not most everyday instances of anger. The authors incorporate a novel behavioral motor task that tests motivational direction by measuring the reaction times (RTs) of stepping forward and backward in response to the words “toward” and “away.” The results show that, relative to anxiety and control conditions, anger induction resulted in a steeper approach–avoidance RT gradient which was shifted in favor of approach. PMID:21713132

  2. Dynamics of surface-migration: Electron-induced reaction of 1,2-dihaloethanes on Si(100)

    NASA Astrophysics Data System (ADS)

    Huang, Kai; MacLean, Oliver; Guo, Si Yue; McNab, Iain R.; Ning, Zhanyu; Wang, Chen-Guang; Ji, Wei; Polanyi, John C.

    2016-10-01

    Scanning Tunneling Microscopy was used to investigate the electron-induced reaction of 1,2-dibromoethane (DBE) and 1,2-dichloroethane (DCE) on Si(100).We observed a long-lived physisorbed molecular state of DBE at 75 K and of DCE at 110 K. As a result we were able to characterize by experiment and also by ab initio theory the dynamics of ethylene production in the electron-induced surface-reaction of these physisorbed species. For both DBE and DCE the ethylene product was observed to migrate across the surface. In the case of DBE the recoil of the ethylene favored the silicon rows, migrating by an average distance of 22 Å, and up to 100 Å. Trajectory calculations were performed for this electron-induced reaction, using an 'Impulsive Two-State' model involving an anionic excited state and a neutral ground-potential. The model agreed with experiment in reproducing both migration and desorption of the ethylene product. The computed migration exhibited a 'ballistic' launch and subsequent 'bounces', thereby accounting for the observed long-range migratory dynamics.

  3. Aqueous catalysis: Methylrhenium trioxide (MTO) as a homogeneous catalyst for the Diels-Alder reaction

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

    Zhu, Z.; Espenson, J.H.

    1997-04-16

    The title compound proves to be an effective and efficient catalyst for the Diels-Alder reaction when the dienophile is an {alpha},{beta}-unsaturated ketone or aldehyde. It is especially effective in water. Equal amounts of any such dienophile and any of six representative dienes (isoprene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, cyclopentadiene, 1,2,3,4,5,-pentamethylcyclopentadiene, and 1,3-cyclohexadiene) were used, along with 1% MTO. The reactions gave usually > 90% isolated yield of the cycloaddition product except for the larger dienophiles. Nearly exclusively, there was formed one product isomer, the same one that usually predominates. The reactions were often run in chloroform (mostly) and in other organic solvents. Amore » select number were carried out in water, where the reactions gave a greater product yield in a considerably shorter time. Water, itself, is known to enhance the rates of Diels-Alder reactions, but MTO exerts an additional accelerating effect. Kinetics studies were carried out to show that the rate is proportional to the catalyst concentration. The products do not inhibit the reaction. The desirability of MTO as a Diels-Alder catalyst stems from a combination of favorable properties: the inertness to air/oxygen, the tolerance for many substrates, the use of an aqueous medium, and the absence of product inhibition. The initial step appears to be the (weak) coordination of the carbonyl oxygen to the electropositive rhenium center. Steric crowding around rhenium inhibits reactions of the larger dienophiles. 26 refs., 3 figs., 4 tabs.« less

  4. Pre and Post-copulatory Selection Favor Similar Genital Phenotypes in the Male Broad Horned Beetle

    PubMed Central

    House, Clarissa M.; Sharma, M. D.; Okada, Kensuke; Hosken, David J.

    2016-01-01

    Sexual selection can operate before and after copulation and the same or different trait(s) can be targeted during these episodes of selection. The direction and form of sexual selection imposed on characters prior to mating has been relatively well described, but the same is not true after copulation. In general, when male–male competition and female choice favor the same traits then there is the expectation of reinforcing selection on male sexual traits that improve competitiveness before and after copulation. However, when male–male competition overrides pre-copulatory choice then the opposite could be true. With respect to studies of selection on genitalia there is good evidence that male genital morphology influences mating and fertilization success. However, whether genital morphology affects reproductive success in more than one context (i.e., mating versus fertilization success) is largely unknown. Here we use multivariate analysis to estimate linear and nonlinear selection on male body size and genital morphology in the flour beetle Gnatocerus cornutus, simulated in a non-competitive (i.e., monogamous) setting. This analysis estimates the form of selection on multiple traits and typically, linear (directional) selection is easiest to detect, while nonlinear selection is more complex and can be stabilizing, disruptive, or correlational. We find that mating generates stabilizing selection on male body size and genitalia, and fertilization causes a blend of directional and stabilizing selection. Differences in the form of selection across these bouts of selection result from a significant alteration of nonlinear selection on body size and a marginally significant difference in nonlinear selection on a component of genital shape. This suggests that both bouts of selection favor similar genital phenotypes, whereas the strong stabilizing selection imposed on male body size during mate acquisition is weak during fertilization. PMID:27371390

  5. Pre and Post-copulatory Selection Favor Similar Genital Phenotypes in the Male Broad Horned Beetle.

    PubMed

    House, Clarissa M; Sharma, M D; Okada, Kensuke; Hosken, David J

    2016-10-01

    Sexual selection can operate before and after copulation and the same or different trait(s) can be targeted during these episodes of selection. The direction and form of sexual selection imposed on characters prior to mating has been relatively well described, but the same is not true after copulation. In general, when male-male competition and female choice favor the same traits then there is the expectation of reinforcing selection on male sexual traits that improve competitiveness before and after copulation. However, when male-male competition overrides pre-copulatory choice then the opposite could be true. With respect to studies of selection on genitalia there is good evidence that male genital morphology influences mating and fertilization success. However, whether genital morphology affects reproductive success in more than one context (i.e., mating versus fertilization success) is largely unknown. Here we use multivariate analysis to estimate linear and nonlinear selection on male body size and genital morphology in the flour beetle Gnatocerus cornutus, simulated in a non-competitive (i.e., monogamous) setting. This analysis estimates the form of selection on multiple traits and typically, linear (directional) selection is easiest to detect, while nonlinear selection is more complex and can be stabilizing, disruptive, or correlational. We find that mating generates stabilizing selection on male body size and genitalia, and fertilization causes a blend of directional and stabilizing selection. Differences in the form of selection across these bouts of selection result from a significant alteration of nonlinear selection on body size and a marginally significant difference in nonlinear selection on a component of genital shape. This suggests that both bouts of selection favor similar genital phenotypes, whereas the strong stabilizing selection imposed on male body size during mate acquisition is weak during fertilization. © The Author 2016. Published by

  6. Favorable Risk Selection in Medicare Advantage: Trends in Mortality and Plan Exits Among Nursing Home Beneficiaries

    PubMed Central

    Goldberg, Elizabeth M.; Trivedi, Amal N.; Mor, Vincent; Jung, Hye-Young; Rahman, Momotazur

    2016-01-01

    The 2003 Medicare Modernization Act (MMA) increased payments to Medicare Advantage plans and instituted a new risk-adjustment payment model to reduce plans' incentives to enroll healthier Medicare beneficiaries and avoid those with higher costs. Whether the MMA reduced risk selection remains debatable. This study uses mortality differences, nursing home utilization, and switch rates to assess whether the MMA successfully decreased risk selection from 2000 to 2012. We found no decrease in the mortality difference or adjusted difference in nursing home use between plan beneficiaries pre- and post the MMA. Among beneficiaries with nursing home use, disenrollment from Medicare Advantage plans declined from 20% to 12%, but it remained 6 times higher than the switch rate from traditional Medicare to Medicare Advantage. These findings suggest that the MMA was not associated with reductions in favorable risk selection, as measured by mortality, nursing home use, and switch rates. PMID:27516452

  7. PumpKin: A tool to find principal pathways in plasma chemical models

    NASA Astrophysics Data System (ADS)

    Markosyan, A. H.; Luque, A.; Gordillo-Vázquez, F. J.; Ebert, U.

    2014-10-01

    PumpKin is a software package to find all principal pathways, i.e. the dominant reaction sequences, in chemical reaction systems. Although many tools are available to integrate numerically arbitrarily complex chemical reaction systems, few tools exist in order to analyze the results and interpret them in relatively simple terms. In particular, due to the large disparity in the lifetimes of the interacting components, it is often useful to group reactions into pathways that recycle the fastest species. This allows a researcher to focus on the slow chemical dynamics, eliminating the shortest timescales. Based on the algorithm described by Lehmann (2004), PumpKin automates the process of finding such pathways, allowing the user to analyze complex kinetics and to understand the consumption and production of a certain species of interest. We designed PumpKin with an emphasis on plasma chemical systems but it can also be applied to atmospheric modeling and to industrial applications such as plasma medicine and plasma-assisted combustion.

  8. Drug metabolism and hypersensitivity reactions to drugs.

    PubMed

    Agúndez, José A G; Mayorga, Cristobalina; García-Martin, Elena

    2015-08-01

    The aim of the present review was to discuss recent advances supporting a role of drug metabolism, and particularly of the generation of reactive metabolites, in hypersensitivity reactions to drugs. The development of novel mass-spectrometry procedures has allowed the identification of reactive metabolites from drugs known to be involved in hypersensitivity reactions, including amoxicillin and nonsteroidal antiinflammatory drugs such as aspirin, diclofenac or metamizole. Recent studies demonstrated that reactive metabolites may efficiently bind plasma proteins, thus suggesting that drug metabolites, rather than - or in addition to - parent drugs, may elicit an immune response. As drug metabolic profiles are often determined by variability in the genes coding for drug-metabolizing enzymes, it is conceivable that an altered drug metabolism may predispose to the generation of reactive drug metabolites and hence to hypersensitivity reactions. These findings support the potential for the use of pharmacogenomics tests in hypersensitivity (type B) adverse reactions, in addition to the well known utility of these tests in type A adverse reactions. Growing evidence supports a link between genetically determined drug metabolism, altered metabolic profiles, generation of highly reactive metabolites and haptenization. Additional research is required to developing robust biomarkers for drug-induced hypersensitivity reactions.

  9. Systematic study of the reaction kinetics for HMX.

    PubMed

    Long, Yao; Chen, Jun

    2015-05-07

    The reaction process of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in wide temperature and pressure ranges is simulated by molecular dynamics. A set of postprocessing programs is written to evaluate the intermediate molecules and chemical reactions. On the basis of these evaluations, the reaction rates, reactive Hugoniot curves, and detonation wave profile are calculated. The detonation velocity and detonation pressure are determined as 9984 m/s and 38.3349 GPa, in agreement with the experimental results, 9110 m/s and 39.5 GPa. The width of the reaction zone is 10 μm, and the main products are N2, H2O, and CO2. We find some molecules play an important role in intermediate reactions but are not exhibited in final products, such as N2O2, N2O5, and C3H3N3.

  10. Radical-molecule reaction C3H+H2O: a mechanistic study.

    PubMed

    Dong, Hao; Ding, Yi-Hong; Sun, Chia-Chung

    2005-02-08

    Despite the importance of the C(3)H radical in both combustion and interstellar space, the reactions of C(3)H toward stable molecules have never been studied. In this paper, we report our detailed mechanistic study on the radical-molecule reaction C(3)H+H(2)O at the Becke's three parameter Lee-Yang-Parr-B3LYP6-311G(d,p) and coupled cluster with single, double, and triple excitations-CCSD(T)6-311G(2d,p) (single-point) levels. It is shown that the C(3)H+H(2)O reaction initially favors formation of the carbene-insertion intermediates HCCCHOH (1a,1b) rather than the direct H- or OH-abstraction process. Subsequently, the isomers (1a,1b) can undergo a direct H- extrusion to form the well-known product propynal HCCCHO (P(5)). Highly competitively, (1a,1b) can take the successive 1,4- and 1,2-H-shift interconversion to isomer H(2)CCCHO(2a,2b) and then to isomer H(2)CCHCO(3a,3b), which can finally take a direct C-C bond cleavage to give product C(2)H(3) and CO (P(1)). The other products are kinetically much less feasible. With the overall entrance barrier 10.6 kcal/mol, the title reaction can be important in postburning processes. Particularly, our calculations suggest that the title reaction may play a role in the formation of the intriguing interstellar molecule, propynal HCCCHO. The calculated results will also be useful for the analogous C(3)H reactions such as with ammonia and alkanes.

  11. Path finding methods accounting for stoichiometry in metabolic networks

    PubMed Central

    2011-01-01

    Graph-based methods have been widely used for the analysis of biological networks. Their application to metabolic networks has been much discussed, in particular noting that an important weakness in such methods is that reaction stoichiometry is neglected. In this study, we show that reaction stoichiometry can be incorporated into path-finding approaches via mixed-integer linear programming. This major advance at the modeling level results in improved prediction of topological and functional properties in metabolic networks. PMID:21619601

  12. Developing effective campaign messages to prevent neural tube defects: a qualitative assessment of women's reactions to advertising concepts.

    PubMed

    Massi Lindsey, Lisa L; Silk, Kami J; Von Friederichs-Fitzwater, Marlene M; Hamner, Heather C; Prue, Christine E; Boster, Franklin J

    2009-03-01

    The incidence of neural tube defects (NTDs), serious birth defects of the brain and spine that affect approximately 3,000 pregnancies in the United States each year, can be reduced by 50-70% with daily periconceptional consumption of the B vitamin folic acid. Two studies were designed to assess college women's reactions to and perceptions of potential campaign advertising concepts derived from preproduction formative research to increase folic acid consumption through the use of a daily multivitamin. Study one assessed draft advertising concepts in eight focus groups (N = 71) composed of college-enrolled women in four cities geographically dispersed across the United States. Based on study one results, the concepts were revised and reassessed in study two with a different sample (eight focus groups; N = 73) of college women in the same four cities. Results indicated that participants generally responded favorably to concepts in each of the two studies, and provided insight into individual concepts to increase their overall appeal and effectiveness. The specific findings and implications of these results are discussed.

  13. Understanding pretest and posttest reactions to cognitive ability and personality tests.

    PubMed

    Chan, D; Schmitt, N; Sacco, J M; DeShon, R P

    1998-06-01

    To understand the nature of test reactions and their relationship to test performance, the relationships among belief in tests, pretest reactions, test performance, and posttest reactions were modeled for cognitive ability and personality tests. Results from structural equation models that were fitted to responses from 197 undergraduate examinees supported the hypothesized relationships. On the cognitive ability test, pretest reactions affected test performance and mediated the relationship between belief in tests and test performance. Test performance affected posttest reactions even after taking into account the effect of pretest reactions. On the personality test, belief in tests affected pretest and posttest reactions, but the three variables were unrelated to test performance (Conscientiousness scores). Conceptual, methodological, and practical implications of the findings are discussed in the context of research on test reactions and test performance.

  14. Stereospecific nickel-catalyzed cross-coupling reactions of benzylic ethers and esters.

    PubMed

    Tollefson, Emily J; Hanna, Luke E; Jarvo, Elizabeth R

    2015-08-18

    This Account presents the development of a suite of stereospecific alkyl-alkyl cross-coupling reactions employing nickel catalysts. Our reactions complement related nickel-catalyzed stereoconvergent cross-coupling reactions from a stereochemical and mechanistic perspective. Most reactions of alkyl electrophiles with low-valent nickel complexes proceed through alkyl radicals and thus are stereoablative; the correct enantioselective catalyst can favor the formation of one enantiomer. Our reactions, in contrast, are stereospecific. Enantioenriched ethers and esters are cleanly converted to cross-coupled products with high stereochemical fidelity. While mechanistic details are still to be refined, our results are consistent with a polar, two-electron oxidative addition that avoids the formation of radical intermediates. This reactivity is unusual for a first-row transition metal. The cross-coupling reactions engage a range of benzylic ethers and esters, including methyl ethers, tetrahydropyrans, tetrahydrofurans, esters, and lactones. Coordination of the arene substituent to the nickel catalyst accelerates the reactions. Arenes with low aromatic stabilization energies, such as naphthalene, benzothiophene, and furan, serve as the best ligands and provide the highest reactivity. Traceless directing groups that accelerate reactions of sluggish substrates are described, providing partial compensation for arene coordination. Kumada, Negishi, and Suzuki reactions provide incorporation of a broad range of transmetalating agents. In Kumada coupling reactions, a full complement of Grigard reagents, including methyl, n-alkyl, and aryl Grignard reagents, are employed. In reactions employing methylmagnesium iodide, ligation of the nickel catalyst by rac-BINAP or DPEphos provides the highest yield and stereospecificity. For all other Grignard reagents, Ni(dppe)Cl2 has emerged as the best catalyst. Negishi cross-coupling reactions employing dimethylzinc are reported as a strategy to

  15. [Early interaction is a prerequisite for favorable psychic development].

    PubMed

    Pesonen, Anu-Katriina

    2010-01-01

    Empirical studies on the parent-baby interaction have greatly influenced our insight into the child's psychological development. Initial stages of the research attempted to reveal features in the mother's action that would predict the child's favorable development. Since then, also fathers and the child's development in a more broad sense have been studied. The most prominent progress has taken place in microanalytical methods for these interactions. The research has increased our knowledge of the baby's interactive capabilities and the significance of successful interactive events for the child's development, laying the basis for various interventions related to parenthood.

  16. Clinical quality is independently associated with favorable bond ratings.

    PubMed

    Haydar, Ziad; Nicewander, David; Convery, Paul; Black, Michael; Ballard, David

    2010-01-01

    The relation between clinical quality and bond rating for nonprofit hospitals has been proposed but never fully studied. We analyzed the relation between bond rating, clinical quality measures (The Joint Commission/Centers for Medicare and Medicaid Services [CMS] core measures), and balance sheet and income statement financial measures of 236 hospitals across the United States that are rated by Moody's Investors Service and that reported clinical quality measures to CMS during the study period. We found a statistically significant relation between higher quality measures and more favorable bond ratings. This association remained significant after controlling for traditional financial parameters.

  17. Micro-flow photosynthesis of new dienophiles for inverse-electron-demand Diels–Alder reactions. Potential applications for pretargeted in vivo PET imaging† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc02933g Click here for additional data file.

    PubMed Central

    Billaud, Emilie M. F.; Shahbazali, Elnaz; Ahamed, Muneer; Cleeren, Frederik; Noël, Timothy; Koole, Michel; Verbruggen, Alfons; Hessel, Volker

    2017-01-01

    Pretargeted PET imaging has emerged as an effective two-step in vivo approach that combines the superior affinity and selectivity of antibodies with the rapid pharmacokinetics and favorable dosimetry of smaller molecules radiolabeled with short-lived radionuclides. This approach can be based on the bioorthogonal inverse-electron-demand Diels–Alder (IEDDA) reaction between tetrazines and trans-cyclooctene (TCO) derivatives. We aimed to develop new [18F]TCO–dienophiles with high reactivity for IEDDA reactions, and favorable in vivo stability and pharmacokinetics. New dienophiles were synthesized using an innovative micro-flow photochemistry process, and their reaction kinetics with a tetrazine were determined. In vivo stability and biodistribution of the most promising 18F-radiolabeled-TCO-derivative ([18F]3) was investigated, and its potential for in vivo pretargeted PET imaging was assessed in tumor-bearing mice. We demonstrated that [18F]3 is a suitable dienophile for IEDDA reactions and for pretargeting applications. PMID:28451267

  18. Reactions of teachers versus non-teachers toward people who stutter.

    PubMed

    Li, Jian; Arnold, Hayley S

    2015-01-01

    The primary purpose of this study was to assess whether kindergarten through twelfth grade teachers differ from people in non-teaching occupations in their reactions to people who stutter (PWS). Taking differences in age and education into account, we compared reactions to PWS between 263 teachers and 1336 non-teachers in the United States based on their responses on the Public Opinion Survey on Human Attributes-Stuttering (POSHA-S, St. Louis, 2012). Findings indicated that teachers use a greater number and variety of information sources about PWS than the general public and that male teachers do so even more than female teachers. With regard to the other POSHA-S components, accommodating/helping, knowledge/experience, and sympathy/social distancing of PWS, teachers' responses were not significantly different from their non-teaching counterparts. Regardless of occupation, women reported reactions to PWS that are considered more accommodating and helpful to PWS than the reported reactions of men. Readers should be able to: (1) identify the challenges that students who stutter encounter in the K-12 school setting, (2) identify recommended ways teachers can react to their students who stutter, (3) summarize findings regarding teachers' reactions to people who stutter (PWS), and (4) identify key variables that are associated with reactions to PWS. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. Reactions of electronically excited molecular nitrogen with H2 and H2O molecules: theoretical study

    NASA Astrophysics Data System (ADS)

    Pelevkin, Alexey V.; Sharipov, Alexander S.

    2018-05-01

    Comprehensive quantum chemical analysis with the usage of the second-order perturbation multireference XMCQDPT2 approach was carried out to study the processes in the   +  H2 and   +  H2O systems. The energetically favorable reaction pathways have been revealed based on the exploration of potential energy surfaces. It has been shown that the reactions   +  H2 and   +  H2O occur with small activation barriers and, primarily, lead to the formation of N2H  +  H and N2H  +  OH products, respectively. Further, the interaction of these species could give rise to the ground state and H2 (or H2O) products, however, the estimations, based on RRKM theory and dynamic reaction coordinate calculations, exhibited that the   +  H2 and   +  H2O reactions lead to the dissociative quenching predominately. Appropriate rate constants for revealed reaction channels have been estimated by using a canonical variational theory and capture approximation. Corresponding three-parameter Arrhenius expressions for the temperature range T  =  300  ‑  3000 K were reported.

  20. Study of stability of methotrexate in acidic solution spectrofluorimetric determination of methotrexate in pharmaceutical preparations through acid-catalyzed degradation reaction.

    PubMed

    Sabry, Suzy M; Abdel-Hady, M; Elsayed, M; Fahmy, Osama T; Maher, Hadir M

    2003-07-14

    Study of the degradation reaction of methotrexate (MTX) in acidic solution was carried out. Optimization of the experimental parameters of MTX acid hydrolysis was investigated. Spectrofluorimetric method for determination of MTX through measurement of its acid-degradation product, 4-amino-4-deoxy-10-methylpteroic acid (AMP), was developed. Stability of the standard solution of MTX prepared in sulfuric acid was discussed in the view of accelerated stability analysis. Two other comparative spectroflourimetric methods based on measuring the fluorescence intensities from either a condensation reaction with acetylacetone-formaldehyde (Hantzsch reaction) or a reaction with fluorescamine were also described. Beer's law validation, accuracy, precision, limits of detection, limits of quantification, and other aspects of analytical merit are presented in the text. The proposed methods were successfully applied for the analysis of MTX in pure drug and tablets dosage form. The sensitivity of the developed methods was favorable, so it was possible to be adopted for determination of MTX in plasma samples for routine use in high-dose MTX therapy.

  1. Iterated reaction graphs: simulating complex Maillard reaction pathways.

    PubMed

    Patel, S; Rabone, J; Russell, S; Tissen, J; Klaffke, W

    2001-01-01

    This study investigates a new method of simulating a complex chemical system including feedback loops and parallel reactions. The practical purpose of this approach is to model the actual reactions that take place in the Maillard process, a set of food browning reactions, in sufficient detail to be able to predict the volatile composition of the Maillard products. The developed framework, called iterated reaction graphs, consists of two main elements: a soup of molecules and a reaction base of Maillard reactions. An iterative process loops through the reaction base, taking reactants from and feeding products back to the soup. This produces a reaction graph, with molecules as nodes and reactions as arcs. The iterated reaction graph is updated and validated by comparing output with the main products found by classical gas-chromatographic/mass spectrometric analysis. To ensure a realistic output and convergence to desired volatiles only, the approach contains a number of novel elements: rate kinetics are treated as reaction probabilities; only a subset of the true chemistry is modeled; and the reactions are blocked into groups.

  2. Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction

    DOE PAGES

    Yao, Siyu; Zhang, Xiao; Zhou, Wu; ...

    2017-06-22

    Here, the water-gas shift (WGS) reaction (where carbon monoxide plus water yields dihydrogen and carbon dioxide) is an essential process for hydrogen generation and carbon monoxide removal in various energy-related chemical operations. This equilibrium-limited reaction is favored at a low working temperature. Potential application in fuel cells also requires a WGS catalyst to be highly active, stable, and energy-efficient and to match the working temperature of on-site hydrogen generation and consumption units. We synthesized layered gold (Au) clusters on a molybdenum carbide (α-MoC) substrate to create an interfacial catalyst system for the ultralow-temperature WGS reaction. Water was activated over α-MoCmore » at 303 kelvin, whereas carbon monoxide adsorbed on adjacent Au sites was apt to react with surface hydroxyl groups formed from water splitting, leading to a high WGS activity at low temperatures.« less

  3. Quantum-chemical studies on the favored and rare tautomers of neutral and redox adenine.

    PubMed

    Raczyńska, Ewa D; Makowski, Mariusz; Zientara-Rytter, Katarzyna; Kolczyńska, Katarzyna; Stępniewski, Tomasz M; Hallmann, Małgorzata

    2013-02-21

    All possible twenty-three prototropic tautomers of neutral and redox adenine (nine amine and fourteen imine forms, including geometric isomerism of the exo ═NH group) were examined in vacuo {DFT(B3LYP)/6-311+G(d,p)}. The NH → NH conversions as well as those usually omitted, NH → CH and CH → CH, were considered. An interesting change of the tautomeric preference occurs when proceeding from neutral to reduced adenine. One-electron reduction favors the nonaromatic amine C8H-N10H tautomer. This tautomeric preference is similar to that (C2H) for reduced imidazole. Water molecules (PCM model) seem to not change this trend. They influence solely the relative energies. The DFT vertical detachment energy in the gas phase is positive for each tautomer, e.g., 0.03 eV for N9H-N10H and 1.84 eV for C8H-N10H. The DFT adiabatic electron affinity for the favored process, neutral N9H-N10H → reduced C8H-N10H (ground states), is equal to 0.18 eV at 0 K (ZPE included). One-electron oxidation does not change the tautomeric preference in the gas phase. The aromatic amine N9H-N10H tautomer is favored for the oxidized molecule similarly as for the neutral one. The DFT adiabatic ionization potential for the favored process, neutral N9H-N10H → oxidized N9H-N10H (ground states), is equal to 8.12 eV at 0 K (ZPE included). Water molecules (PCM model) seem to influence solely the composition of the tautomeric mixture and the relative energies. They change the energies of the oxidation and reduction processes by ca. 2 eV.

  4. Definition and Validation of “Favorable High-Risk Prostate Cancer”: Implications for Personalizing Treatment of Radiation-Managed Patients

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

    Muralidhar, Vinayak; Chen, Ming-Hui; Reznor, Gally

    Purpose: To define and validate a classification of favorable high-risk prostate cancer that could be used to personalize therapy, given that consensus guidelines recommend similar treatments for all radiation-managed patients with high-risk disease. Methods and Materials: We studied 3618 patients with cT1-T3aN0M0 high-risk or unfavorable intermediate-risk prostate adenocarcinoma treated with radiation at a single institution between 1997 and 2013. Favorable high-risk was defined as T1c disease with either Gleason 4 + 4 = 8 and prostate-specific antigen <10 ng/mL or Gleason 6 and prostate-specific antigen >20 ng/mL. Competing risks regression was used to determine differences in the risk of prostate cancer–specific mortality (PCSM) after controlling formore » baseline factors and treatment. Our results were validated in a cohort of 13,275 patients using the Surveillance, Epidemiology, and End Results (SEER)-Medicare linked database. Results: Patients with favorable high-risk disease had significantly better PCSM than other men with high-risk disease (adjusted hazard ratio [AHR] 0.42, 95% confidence interval [CI] 0.18-0.996, P=.049) and similar PCSM as men with unfavorable intermediate-risk disease (AHR 1.17, 95% CI 0.50-2.75, P=.710). We observed very similar results within the SEER-Medicare cohort (favorable high-risk vs other high-risk: AHR 0.21, 95% CI 0.11-0.41, P<.001; favorable high-risk vs unfavorable intermediate-risk: AHR 0.67, 95% CI 0.33-1.36, P=.268). Conclusions: Patients with favorable high-risk prostate cancer have significantly better PCSM than other patients with high-risk disease and similar PCSM as those with unfavorable intermediate-risk disease, who are typically treated with shorter-course androgen deprivation therapy. This new classification system may allow for personalization of treatment within high-risk disease, such as consideration of shorter-course androgen deprivation therapy for favorable high-risk disease.« less

  5. Immunohistochemical findings of the granulomatous reaction associated with tuberculosis.

    PubMed

    Karimi, Shirin; Shamaei, Masoud; Pourabdollah, Mihan; Sadr, Makan; Karbasi, Mehrdad; Kiani, Arda; Bahadori, Moslem

    2016-12-01

    staining of TB granulomatous reactions, this stain not only highlights the presence of mycobacterial antigens for tissue diagnosis, but also could morphologically localize their distribution in different cells. Pathologists must be familiar with adequate staining pattern, elimination of background staining, and type of selected antibody. This method is especially important for application in countries with high prevalence of TB as a technique with early diagnostic value in tissue specimens. Early diagnosis using this technique can reduce related morbidity and mortality and decrease the rate of complications due to misdiagnosis and mistreatment of TB. Copyright © 2016.

  6. A Global Overview of the Impact of Peritoneal Dialysis First or Favored Policies: An Opinion

    PubMed Central

    Liu, Frank Xiaoqing; Gao, Xin; Inglese, Gary; Chuengsaman, Piyatida; Pecoits-Filho, Roberto; Yu, Alex

    2015-01-01

    Given the ever-increasing burden of end-stage renal disease (ESRD) in a global milieu of limited financial and health resources, interested parties continue to search for ways to optimize dialysis access. Government and payer initiatives to increase access to renal replacement therapies (RRTs), particularly peritoneal dialysis (PD) and hemodialysis (HD), may have meaningful impacts from clinical and health-economic perspectives; and despite similar clinical and humanistic outcomes between the two dialysis modalities, PD may be the more convenient and resource-conscious option. This review assessed country-specific PD-First/Favored policies and their associated background, implementation, and outcomes. It was found that barriers to policy-implementation are broadly associated with government policy, economics, provider or healthcare professional education, modality-related factors, and patient-related factors. Notably, the success of a given country's PD-Favored policy was inversely associated with the extent of HD infrastructure. It is hoped that this review will provide a foundation across countries to share lessons learned during the development and implementation of PD-First/Favored policies. PMID:25082840

  7. Allergic and immunologic reactions to food additives.

    PubMed

    Gultekin, Fatih; Doguc, Duygu Kumbul

    2013-08-01

    For centuries, food additives have been used for flavouring, colouring and extension of the useful shelf life of food, as well as the promotion of food safety. During the last 20 years, the studies implicating the additives contained in foods and medicine as a causative factor of allergic reactions have been proliferated considerably. In this review, we aimed to overview all of the food additives which were approved to consume in EU and find out how common and serious allergic reactions come into existence following the consuming of food additives.

  8. Reduced-Dimensionality Semiclassical Transition State Theory: Application to Hydrogen Atom Abstraction and Exchange Reactions of Hydrocarbons.

    PubMed

    Greene, Samuel M; Shan, Xiao; Clary, David C

    2015-12-17

    Quantum mechanical methods for calculating rate constants are often intractable for reactions involving many atoms. Semiclassical transition state theory (SCTST) offers computational advantages over these methods but nonetheless scales exponentially with the number of degrees of freedom (DOFs) of the system. Here we present a method with more favorable scaling, reduced-dimensionality SCTST (RD SCTST), that treats only a subset of DOFs of the system explicitly. We apply it to three H abstraction and exchange reactions for which two-dimensional potential energy surfaces (PESs) have previously been constructed and evaluated using RD quantum scattering calculations. We differentiated these PESs to calculate harmonic frequencies and anharmonic constants, which were then used to calculate cumulative reaction probabilities and rate constants by RD SCTST. This method yielded rate constants in good agreement with quantum scattering results. Notably, it performed well for a heavy-light-heavy reaction, even though it does not explicitly account for corner-cutting effects. Recent extensions to SCTST that improve its treatment of deep tunneling were also evaluated within the reduced-dimensionality framework. The success of RD SCTST in this study suggests its potential applicability to larger systems.

  9. Enzymatic reaction paths as determined by transition path sampling

    NASA Astrophysics Data System (ADS)

    Masterson, Jean Emily

    Enzymes are biological catalysts capable of enhancing the rates of chemical reactions by many orders of magnitude as compared to solution chemistry. Since the catalytic power of enzymes routinely exceeds that of the best artificial catalysts available, there is much interest in understanding the complete nature of chemical barrier crossing in enzymatic reactions. Two specific questions pertaining to the source of enzymatic rate enhancements are investigated in this work. The first is the issue of how fast protein motions of an enzyme contribute to chemical barrier crossing. Our group has previously identified sub-picosecond protein motions, termed promoting vibrations (PVs), that dynamically modulate chemical transformation in several enzymes. In the case of human heart lactate dehydrogenase (hhLDH), prior studies have shown that a specific axis of residues undergoes a compressional fluctuation towards the active site, decreasing a hydride and a proton donor--acceptor distance on a sub-picosecond timescale to promote particle transfer. To more thoroughly understand the contribution of this dynamic motion to the enzymatic reaction coordinate of hhLDH, we conducted transition path sampling (TPS) using four versions of the enzymatic system: a wild type enzyme with natural isotopic abundance; a heavy enzyme where all the carbons, nitrogens, and non-exchangeable hydrogens were replaced with heavy isotopes; and two versions of the enzyme with mutations in the axis of PV residues. We generated four separate ensembles of reaction paths and analyzed each in terms of the reaction mechanism, time of barrier crossing, dynamics of the PV, and residues involved in the enzymatic reaction coordinate. We found that heavy isotopic substitution of hhLDH altered the sub-picosecond dynamics of the PV, changed the favored reaction mechanism, dramatically increased the time of barrier crossing, but did not have an effect on the specific residues involved in the PV. In the mutant systems

  10. Mesoscale simulations of shockwave energy dissipation via chemical reactions.

    PubMed

    Antillon, Edwin; Strachan, Alejandro

    2015-02-28

    We use a particle-based mesoscale model that incorporates chemical reactions at a coarse-grained level to study the response of materials that undergo volume-reducing chemical reactions under shockwave-loading conditions. We find that such chemical reactions can attenuate the shockwave and characterize how the parameters of the chemical model affect this behavior. The simulations show that the magnitude of the volume collapse and velocity at which the chemistry propagates are critical to weaken the shock, whereas the energetics in the reactions play only a minor role. Shock loading results in transient states where the material is away from local equilibrium and, interestingly, chemical reactions can nucleate under such non-equilibrium states. Thus, the timescales for equilibration between the various degrees of freedom in the material affect the shock-induced chemistry and its ability to attenuate the propagating shock.

  11. Chain-reaction crash on a highway in high visibility

    NASA Astrophysics Data System (ADS)

    Nagatani, Takashi

    2016-05-01

    We study the chain-reaction crash (multiple-vehicle collision) in high-visibility condition on a highway. In the traffic situation, drivers control their vehicles by both gear-changing and braking. Drivers change the gears according to the headway and brake according to taillights of the forward vehicle. We investigate whether or not the first collision induces the chain-reaction crash numerically. It is shown that dynamic transitions occur from no collisions, through a single collision, to multiple collisions with decreasing the headway. Also, we find that the dynamic transition occurs from the finite chain reaction to the infinite chain reaction when the headway is less than the critical value. We compare the multiple-vehicle collisions in high-visibility with that in low-visibility. We derive the transition points and the region maps for the chain-reaction crash in high visibility.

  12. How reaction to cigarette packet health warnings influence quitting: Findings from the ITC Four Country survey

    PubMed Central

    Borland, Ron; Yong, Hua-Hie; Wilson, Nick; Fong, Geoffrey T.; Hammond, David; Michael Cummings, K.; Hosking, Warwick; McNeill, Ann

    2015-01-01

    Objectives To examine prospectively the impact of health warnings on quitting activity. Design Five waves (2002–2006) of a cohort survey where reactions to health warnings at one survey wave are used to predict cessation activity at the next wave, controlling for country (proxy for warning differences) and other factors. These analyses were replicated on four wave-to-wave transitions. Setting and participants Smokers from Australia, Canada, the UK and USA. Samples were Waves 1–2: n=6525; Waves 2–3: n=5257; Waves 3–4:n=4439; and Waves 4–5: n=3993. Measures Warning salience, cognitive responses (thoughts of harm and of quitting), forgoing of cigarettes and avoidance of warnings were examined as predictors of quit attempts, and of quitting success among those who tried (1 month sustained abstinence), replicated across four wave-to-wave transitions. Results All four responses to warnings were independently predictive of quitting activity in bivariate analyses. In multivariate analyses, forgoing cigarettes and cognitive responses to the warnings both prospectively predicted making quit attempts in all replications. However, avoiding warnings did not consistently add predictive value, and there was no consistent pattern for warning salience. There were no interactions by country. Some, but not all, of the effects were mediated by quitting intentions. There were no consistent effects on quit success. Conclusions This study adds to the evidence that forgoing cigarettes as a result of noticing warnings and quit-related cognitive reactions to warnings are consistent prospective predictors of making quit attempts. This work strengthens the evidence base for governments to go beyond the FCTC to mandate health warnings on tobacco products that stimulate the highest possible levels of these reactions. PMID:19215595

  13. Factors associated with favorable response to hyperbaric oxygen therapy among patients presenting with iatrogenic cerebral arterial gas embolism.

    PubMed

    Tekle, Wondwossen G; Adkinson, Cheryl D; Chaudhry, Saqib A; Jadhav, Vikram; Hassan, Ameer E; Rodriguez, Gustavo J; Qureshi, Adnan I

    2013-04-01

    Iatrogenic cerebral arterial gas embolism (CAGE) is an uncommon but potentially a fatal condition. Hyperbaric oxygen (HBO2) therapy is the only definitive treatment for patients with CAGE presenting with acute neurologic deficits. We reviewed medical records and neuroimaging of consecutive CAGE patients treated with HBO2 at a state referral hyperbaric facility over a 22-year period. We analyzed the effect of demographics, source of intra-arterial gas, signs and symptoms, results of imaging studies, time between event and HBO2 treatment, and response to HBO2 treatment in 36 consecutive patients. Favorable outcome was defined by complete resolution or improvement of CAGE signs and symptoms at 24 h after HBO2 treatment. Unfavorable outcome was defined by unchanged or worsened neurologic signs and symptoms or in hospital death. A total of 26 (72%) of the 36 patients had favorable outcome. Patients with favorable outcome were younger compared to those with unfavorable outcome (mean age [years, SD] 44.7 ± 17.8 vs. 58.1 ± 24.1, p = 0.08). Cardiopulmonary symptoms were significantly more common in CAGE related to venous source of gas compared to arterial source (p = 0.024) but did not influence the rate of favorable outcomes. Adjusted multivariate analysis demonstrated that time from event to HBO2 ≤ 6 h (positively) and the presence of infarct/edema on head computerized tomography (CT)/magnetic resonance imaging (MRI) before HBO2 (negatively) were independent predictors of favorable outcome at 24 h after HBO2 treatment [odds ratio (OR) 9.08 confidence interval (CI) (1.13-72.69), p = 0.0376, and (OR) 0.034 (CI) (0.002-0.58), p = 0.0200, respectively]. Two of the 36 patients were treated with thrombolytics because of acute focal deficits and suspected ischemia-one with intravenous and the second with intra-arterial thrombolysis. The latter patient developed fatal intracerebral hemorrhage. A high proportion of CAGE patients treated with HBO2 had favorable outcomes. Time

  14. Favorable Geochemistry from Springs and Wells in Colorado

    DOE Data Explorer

    Richard E. Zehner

    2012-02-01

    This layer contains favorable geochemistry for high-temperature geothermal systems, as interpreted by Richard "Rick" Zehner. The data is compiled from the data obtained from the USGS. The original data set combines 15,622 samples collected in the State of Colorado from several sources including 1) the original Geotherm geochemical database, 2) USGS NWIS (National Water Information System), 3) Colorado Geological Survey geothermal sample data, and 4) original samples collected by R. Zehner at various sites during the 2011 field season. These samples are also available in a separate shapefile FlintWaterSamples.shp. Data from all samples were reportedly collected using standard water sampling protocols (filtering through 0.45 micron filter, etc.) Sample information was standardized to ppm (micrograms/liter) in spreadsheet columns. Commonly-used cation and silica geothermometer temperature estimates are included.

  15. Physarum machines: encapsulating reaction-diffusion to compute spanning tree

    NASA Astrophysics Data System (ADS)

    Adamatzky, Andrew

    2007-12-01

    The Physarum machine is a biological computing device, which employs plasmodium of Physarum polycephalum as an unconventional computing substrate. A reaction-diffusion computer is a chemical computing device that computes by propagating diffusive or excitation wave fronts. Reaction-diffusion computers, despite being computationally universal machines, are unable to construct certain classes of proximity graphs without the assistance of an external computing device. I demonstrate that the problem can be solved if the reaction-diffusion system is enclosed in a membrane with few ‘growth points’, sites guiding the pattern propagation. Experimental approximation of spanning trees by P. polycephalum slime mold demonstrates the feasibility of the approach. Findings provided advance theory of reaction-diffusion computation by enriching it with ideas of slime mold computation.

  16. An efficient graph theory based method to identify every minimal reaction set in a metabolic network

    PubMed Central

    2014-01-01

    Background Development of cells with minimal metabolic functionality is gaining importance due to their efficiency in producing chemicals and fuels. Existing computational methods to identify minimal reaction sets in metabolic networks are computationally expensive. Further, they identify only one of the several possible minimal reaction sets. Results In this paper, we propose an efficient graph theory based recursive optimization approach to identify all minimal reaction sets. Graph theoretical insights offer systematic methods to not only reduce the number of variables in math programming and increase its computational efficiency, but also provide efficient ways to find multiple optimal solutions. The efficacy of the proposed approach is demonstrated using case studies from Escherichia coli and Saccharomyces cerevisiae. In case study 1, the proposed method identified three minimal reaction sets each containing 38 reactions in Escherichia coli central metabolic network with 77 reactions. Analysis of these three minimal reaction sets revealed that one of them is more suitable for developing minimal metabolism cell compared to other two due to practically achievable internal flux distribution. In case study 2, the proposed method identified 256 minimal reaction sets from the Saccharomyces cerevisiae genome scale metabolic network with 620 reactions. The proposed method required only 4.5 hours to identify all the 256 minimal reaction sets and has shown a significant reduction (approximately 80%) in the solution time when compared to the existing methods for finding minimal reaction set. Conclusions Identification of all minimal reactions sets in metabolic networks is essential since different minimal reaction sets have different properties that effect the bioprocess development. The proposed method correctly identified all minimal reaction sets in a both the case studies. The proposed method is computationally efficient compared to other methods for finding minimal

  17. Drug desensitization in the management of hypersensitivity reactions to monoclonal antibodies and chemotherapy.

    PubMed

    Mezzano, Veronica; Giavina-Bianchi, Pedro; Picard, Matthieu; Caiado, Joana; Castells, Mariana

    2014-04-01

    Hypersensitivity reactions to monoclonal antibodies and chemotherapy, which may vary in severity from mild to life-threatening, can lead to their discontinuation and replacement by alternative agents that are often less effective, more toxic, and/or more expensive. Drug desensitization has emerged as the best treatment modality capable of allowing re-introduction of the hypersensitivity reaction-inducing medication in highly sensitized patients in need of first line therapies. In recent years, the availability of new anti-neoplastic drugs and therapeutic monoclonal antibodies has increased, as has the potential for hypersensitivity reactions. Development of desensitization protocols for these new medications requires a careful assessment of the potential risks and benefits. The purposes of this review are to provide an overview of the presentation of hypersensitivity reactions amenable to desensitization and to increase awareness of the indications for and outcomes of desensitization protocols. Rapid drug desensitization has proven to be a safe and effective way of administering first line therapy to patients with hypersensitivity reactions, providing an extremely powerful treatment modality for patients for whom alternative drugs are deemed unacceptable. Rapid drug desensitization protocols should be administered only by highly trained allergists and nurses who have experience in determining which reactions are amenable to desensitization, and can identify high risk patients and provide them with appropriate care. Efforts should be made to increase awareness of the remarkable safety and efficacy of rapid drug desensitization among non-allergists, especially in the fields of oncology and rheumatology, so as to favor its universal application. Development of desensitization units to provide state-of-the-art care is possible only through coordinated teamwork.

  18. Coriolis coupling and nonadiabaticity in chemical reaction dynamics.

    PubMed

    Wu, Emilia L

    2010-12-01

    The nonadiabatic quantum dynamics and Coriolis coupling effect in chemical reaction have been reviewed, with emphasis on recent progress in using the time-dependent wave packet approach to study the Coriolis coupling and nonadiabatic effects, which was done by K. L. Han and his group. Several typical chemical reactions, for example, H+D(2), F+H(2)/D(2)/HD, D(+)+H(2), O+H(2), and He+H(2)(+), have been discussed. One can find that there is a significant role of Coriolis coupling in reaction dynamics for the ion-molecule collisions of D(+)+H(2), Ne+H(2)(+), and He+H(2)(+) in both adiabatic and nonadiabatic context. © 2010 Wiley Periodicals, Inc.

  19. Sensitivity and network topology in chemical reaction systems

    NASA Astrophysics Data System (ADS)

    Okada, Takashi; Mochizuki, Atsushi

    2017-08-01

    In living cells, biochemical reactions are catalyzed by specific enzymes and connect to one another by sharing substrates and products, forming complex networks. In our previous studies, we established a framework determining the responses to enzyme perturbations only from network topology, and then proved a theorem, called the law of localization, explaining response patterns in terms of network topology. In this paper, we generalize these results to reaction networks with conserved concentrations, which allows us to study any reaction system. We also propose network characteristics quantifying robustness. We compare E. coli metabolic network with randomly rewired networks, and find that the robustness of the E. coli network is significantly higher than that of the random networks.

  20. Feynman-Kac equations for reaction and diffusion processes

    NASA Astrophysics Data System (ADS)

    Hou, Ru; Deng, Weihua

    2018-04-01

    This paper provides a theoretical framework for deriving the forward and backward Feynman-Kac equations for the distribution of functionals of the path of a particle undergoing both diffusion and reaction processes. Once given the diffusion type and reaction rate, a specific forward or backward Feynman-Kac equation can be obtained. The results in this paper include those for normal/anomalous diffusions and reactions with linear/nonlinear rates. Using the derived equations, we apply our findings to compute some physical (experimentally measurable) statistics, including the occupation time in half-space, the first passage time, and the occupation time in half-interval with an absorbing or reflecting boundary, for the physical system with anomalous diffusion and spontaneous evanescence.

  1. Why Do Lithium-Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect.

    PubMed

    Yao, Xiahui; Dong, Qi; Cheng, Qingmei; Wang, Dunwei

    2016-09-12

    As an electrochemical energy-storage technology with the highest theoretical capacity, lithium-oxygen batteries face critical challenges in terms of poor stabilities and low charge/discharge round-trip efficiencies. It is generally recognized that these issues are connected to the parasitic chemical reactions at the anode, electrolyte, and cathode. While the detailed mechanisms of these reactions have been studied separately, the possible synergistic effects between these reactions remain poorly understood. To fill in the knowledge gap, this Minireview examines literature reports on the parasitic chemical reactions and finds the reactive oxygen species a key chemical mediator that participates in or facilitates nearly all parasitic chemical reactions. Given the ubiquitous presence of oxygen in all test cells, this finding is important. It offers new insights into how to stabilize various components of lithium-oxygen batteries for high-performance operations and how to eventually materialize the full potentials of this promising technology. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  2. A multi-criteria approach to identify favorable areas for goat production systems in Veracruz, México.

    PubMed

    Ramírez-Rivera, Emmanuel de Jesús; Lopez-Collado, Jose; Díaz-Rivera, Pablo; Ortega-Jiménez, Eusebio; Torres-Hernández, Glafiro; Jacinto-Padilla, Jazmín; Herman-Lara, Erasmo

    2017-04-01

    This research identifies favorable areas for goat production systems in the state of Veracruz, Mexico. Through the use of the analytic hierarchy process, layers of biophysical and soil information were combined to generate a model of favorability. Model validation was performed by calculating the area under the curve, the true skill statistic, and a qualitative comparison with census records. The results showed the existence of regions with high (4494.3 km 2 ) and moderate (2985.8 km 2 ) favorability, and these areas correspond to 6.25 and 4.15%, respectively, of the state territory and are located in the regions of Sierra de Huayacocotla, Perote, and Orizaba. These regions are characterized as mountainous and having predominantly temperate-wet or cold climates, and having montane mesophilic forests, containing pine, fir, and desert scrub. The reliability of the distribution model was supported by the area under the curve value (0.96), the true skill statistic (0.86), and consistency with census records.

  3. Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.

    PubMed

    Cheng, Hanyang; Song, Dean; Chang, Yangyang; Liu, Huijuan; Qu, Jiuhui

    2015-12-01

    Tramadol (TRA) is one of the most detected analgesics in environmental matrices, and it is of high significance to study the reactivity of TRA during chlorination considering its potential toxicity to the environment. The chlorine/TRA reaction is first order with respect to the TRA concentration, and a combination of first-order and second-order with respect to chlorine concentration. The pH dependence of the observed rate constants (kobs) showed that the TRA oxidation reactivity increased with increasing pH. kobs can be quantitatively described by considering all active species including Cl2, Cl2O and HOCl, and the individual rate constants of HOCl/TRA(0), HOCl/TRAH(+), Cl2/TRA and Cl2O/TRA reactions were calculated to be (2.61±0.29)×10(3)M(-1)s(-1), 14.73±4.17M(-1)s(-1), (3.93±0.34)×10(5)M(-1)s(-1) and (5.66±1.83)×10(6)M(-1)s(-1), respectively. Eleven degradation products were detected with UPLC-Q-TOF-MS, and the corresponding structures of eight products found under various pH conditions were proposed. The amine group was proposed to be the initial attack site under alkaline pH conditions, where reaction of the deprotonated amine group with HOCl is favorable. Under acidic and neutral pH conditions, however, two possible reaction pathways were proposed. One is an electrophilic substitution on the aromatic ring, and another is an electrophilic substitution on the nitrogen, leading to an N-chlorinated intermediate, which can be further oxidized. Finally, the SOS/umu test showed that the genotoxicity of TRA chlorination products increased with increasing dosage of chlorine, which was mostly attributed to the formation of some chlorine substitution products. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Electrophilic Pt(II) Complexes: Precision Instruments for the Initiation of Transformations Mediated by the Cation–Olefin Reaction

    PubMed Central

    2015-01-01

    A discontinuity exists between the importance of the cation–olefin reaction as the principal C–C bond forming reaction in terpene biosynthesis and the synthetic tools for mimicking this reaction under catalyst control; that is, having the product identity, stereochemistry, and functionality under the control of a catalyst. The main reason for this deficiency is that the cation–olefin reaction starts with a reactive intermediate (a carbocation) that reacts exothermically with an alkene to reform the reactive intermediate; not to mention that reactive intermediates can also react in nonproductive fashions. In this Account, we detail our efforts to realize catalyst control over this most fundamental of reactions and thereby access steroid like compounds. Our story is organized around our progress in each component of the cascade reaction: the metal controlled electrophilic initiation, the propagation and termination of the cyclization (the cyclase phase), and the turnover deplatinating events. Electrophilic Pt(II) complexes efficiently initiate the cation–olefin reaction by first coordinating to the alkene with selection rules that favor less substituted alkenes over more substituted alkenes. In complex substrates with multiple alkenes, this preference ensures that the least substituted alkene is always the better ligand for the Pt(II) initiator, and consequently the site at which all electrophilic chemistry is initiated. This control element is invariant. With a suitably electron deficient ligand set, the catalyst then activates the coordinated alkene to intramolecular addition by a second alkene, which initiates the cation–olefin reaction cascade and generates an organometallic Pt(II)-alkyl. Deplatination by a range of mechanisms (β-H elimination, single electron oxidation, two-electron oxidation, etc.) provides an additional level of control that ultimately enables A-ring functionalizations that are orthogonal to the cyclase cascade. We particularly

  5. More experiences with the Tzanck smear test: cytologic findings in cutaneous granulomatous disorders.

    PubMed

    Durdu, Murat; Baba, Mete; Seçkin, Deniz

    2009-09-01

    Granulomatous dermatitis is a distinctive histopathologic cutaneous reaction pattern against various infectious and noninfectious agents. Cytologically, granulomatous dermatitis shows granulomas and multinucleated giant cells. Various etiologic agents of granulomatous diseases can also be identified. We aimed to investigate Tzanck smear findings in granulomatous skin diseases. Patients who had granulomas and/or multinucleated giant cells of Langhans, foreign body- and/or Touton type in Tzanck smear tests were included in the study. In these patients, Tzanck preparations were then further evaluated for additional cytologic findings. Samples stained with May-Grünwald-Giemsa stain were evaluated by the same dermatologist throughout the study. In some patients, methylene blue, Gram and/or Erlich-Ziehl-Nielsen stains were also performed. In all of the study cases, the final diagnosis was established after the evaluation of clinical and laboratory findings (including, when appropriate, potassium hydroxide examination; bacterial, leishmanial, and fungal cultures; histopathology; tuberculosis and leishmania polymerase chain reaction). We also calculated the sensitivity and specificity of the Leishman-Donovan body for cutaneous leishmaniasis. Over a 2-year period, 94 of 950 patients (9.9%) in whom Tzanck smear tests were performed had cytologic findings consistent with a granulomatous reaction. In 74 (78.7%) and 20 (21.3%) patients, the granulomatous reaction was due to infectious and noninfectious causes, respectively. Infectious causes included cutaneous leishmaniasis in 65 patients (87.8%), candidal granuloma in two patients, botyromycosis in two patients, and aspergillosis, blastomycosis, mucormycosis, leprosy, and cutaneous tuberculosis in one patient each. In 58 of 74 patients (78.4%) with infectious granulomatous dermatitis, the causes of the granulomas were identified. Noninfectious granulomatous reactions were due to granuloma annulare in 7 patients, sarcoidosis

  6. Estimation of interhemispheric dynamics from simple unimanual reaction time to extrafoveal stimuli.

    PubMed

    Braun, C M

    1992-12-01

    This essay reviews research on interhemispheric transfer time derived from simple unimanual reaction time to hemitachistoscopically presented visual stimuli. Part 1 reviews major theoretical themes including (a) the significance of the eccentricity effect on interhemispheric transfer time in the context of proposed underlying neurohistological constraints; (b) the significance of gender differences in interhemispheric transfer time and findings in dyslexics and left-handers in the context of a fetal brain testosterone model; and (c) the significance of complexity effects on interhemispheric transfer time in a context of "dynamic" vs. "hard-wired" concepts of the underlying interhemispheric communication systems. Part 2 consists of a meta-analysis of 49 published behavioral experiments, in view of drawing a portrait of the best set of experimental conditions apt to produce salient, reliable, and statistically significant measures of interhemispheric transfer time, namely (a) index rather than thumb response, (b) low rather than high target luminance, (c) short rather than prolonged target display, and (d) very eccentric rather than near-foveal stimulus location. Part 3 proposes a theoretical model of interhemispheric transfer time, postulating the measurable existence of fast and slow interhemispheric channels. The proposed mechanism's evolutionary adaptive value, the neurophysiological evidence in its support, and favorable functional evidence from studies of callosotomized patients are then presented followed by proposals for critical experimental tests of the model.

  7. Non-enzymatic-browning-reaction: a versatile route for production of nitrogen-doped carbon dots with tunable multicolor luminescent display.

    PubMed

    Wei, Weili; Xu, Can; Wu, Li; Wang, Jiasi; Ren, Jinsong; Qu, Xiaogang

    2014-01-06

    The non-enzymatic browning, namely Maillard reaction is commonly invoked to account for abiotic chemical transformations of organic matter. Here we report a new reaction pathway via the Maillard reaction to systematically synthesize a series of nitrogen-doped carbon dots (C-dots) with superhigh quantum yield (QY) and tunable multicolor luminescent displayment. The starting materials are glucose and the serial amino acid analogues which allow systemically controlling luminescent and physicochemical properties of C-dots at will. Unexpectedly, the as-prepared C-dots possess bright photoluminescence with QY up to 69.1% which is almost the highest ever reported, favorable biocompatibility, excellent aqueous and nonaqueous dispersibility, ultrahigh photostability, and readily functionalization. We have demonstrated that they are particularly suitable for multicolor luminescent display and long-term and real-time cellular imaging. Furthermore, the methodology is readily scalable to large yield, and can provide sufficient amount of C-dots for practical demands.

  8. Non-Enzymatic-Browning-Reaction: A Versatile Route for Production of Nitrogen-Doped Carbon Dots with Tunable Multicolor Luminescent Display

    NASA Astrophysics Data System (ADS)

    Wei, Weili; Xu, Can; Wu, Li; Wang, Jiasi; Ren, Jinsong; Qu, Xiaogang

    2014-01-01

    The non-enzymatic browning, namely Maillard reaction is commonly invoked to account for abiotic chemical transformations of organic matter. Here we report a new reaction pathway via the Maillard reaction to systematically synthesize a series of nitrogen-doped carbon dots (C-dots) with superhigh quantum yield (QY) and tunable multicolor luminescent displayment. The starting materials are glucose and the serial amino acid analogues which allow systemically controlling luminescent and physicochemical properties of C-dots at will. Unexpectedly, the as-prepared C-dots possess bright photoluminescence with QY up to 69.1% which is almost the highest ever reported, favorable biocompatibility, excellent aqueous and nonaqueous dispersibility, ultrahigh photostability, and readily functionalization. We have demonstrated that they are particularly suitable for multicolor luminescent display and long-term and real-time cellular imaging. Furthermore, the methodology is readily scalable to large yield, and can provide sufficient amount of C-dots for practical demands.

  9. Quantum mechanical/molecular mechanical modeling finds Diels-Alder reactions are accelerated less on the surface of water than in water.

    PubMed

    Thomas, Laura L; Tirado-Rives, Julian; Jorgensen, William L

    2010-03-10

    Quantum and molecular mechanics calculations for the Diels-Alder reactions of cyclopentadiene with 1,4-naphthoquinone, methyl vinyl ketone, and acrylonitrile have been carried out at the vacuum-water interface and in the gas phase. In conjunction with previous studies of these cycloadditions in dilute solution, a more complete picture of aqueous environmental effects emerges with implications for the origin of observed rate accelerations using heterogeneous aqueous suspensions, "on water" conditions. The pure TIP4P water slab maintains the bulk density and hydrogen-bonding properties in central water layers. The bulk region merges to vacuum over a ca. 5 A band with progressive diminution of the density and hydrogen bonding. The relative free energies of activation and transition structures for the reactions at the interface are found to be intermediate between those calculated in the gas phase and in bulk water; i.e., for the reaction with 1,4-naphthoquinone, the DeltaDeltaG(++) values relative to the gas phase are -3.6 and -7.3 kcal/mol at the interface and in bulk water, respectively. Thus, the results do not support the notion that a water surface is more effective than bulk water for catalysis of such pericyclic reactions. The trend is in qualitative agreement with expectations based on density considerations and estimates of experimental rate constants for the gas phase, a heterogeneous aqueous suspension, and a dilute aqueous solution for the reaction of cyclopentadiene with methyl vinyl ketone. Computed energy pair distributions reveal a uniform loss of 0.5-1.0 hydrogen bond for the reactants and transition states in progressing from bulk water to the vacuum-water interface. Orientational effects are apparent at the surface; e.g., the carbonyl group in the methyl vinyl ketone transition structure is preferentially oriented into the surface. Also, the transition structure for the 1,4-naphthoquinone case is buried more in the surface, and the free energy of

  10. Overexpression of epithelial cell adhesion molecule protein is associated with favorable prognosis in an unselected cohort of ovarian cancer patients.

    PubMed

    Battista, Marco Johannes; Cotarelo, Cristina; Jakobi, Sina; Steetskamp, Joscha; Makris, Georgios; Sicking, Isabel; Weyer, Veronika; Schmidt, Marcus

    2014-07-01

    The aim of this study was to evaluate the prognostic influence of epithelial cell adhesion molecule (EpCAM) in an unselected cohort of ovarian cancer (OC) patients. Expression of EpCAM was determined by immunohistochemistry in an unselected cohort of 117 patients with OC. Univariable and multivariable Cox regression analyses adjusted for age, tumor stage, histological grading, histological subtype, postoperative tumor burden and completeness of chemotherapy were performed in order to determine the prognostic influence of EpCAM. The Kaplan-Meier method is used to estimate survival rates. Univariable Cox regression analysis showed that overexpression of EpCAM is associated with favorable prognosis in terms of progression-free survival (PFS) (p = 0.011) and disease-specific survival (DSS) (p = 0.003). In multivariable Cox regression analysis, overexpression of EpCAM retains its significance independent of established prognostic factors for longer PFS [hazard ratios (HR) 0.408, 95 % confidence interval (CI) 0.197-0.846, p = 0.003] but not for PFS (HR 0.666, 95 % CI 0.366-1.212, p = 0.183). Kaplan-Meier plots demonstrate an influence on 5-year PFS rates (0 vs. 27.6 %, p = 0.048) and DSS rates (11.8 vs. 54.0 %, p = 0.018). These findings support the hypothesis that the expression of EpCAM is associated with favorable prognosis in OC.

  11. Extracting Spectroscopic Factors of Argon Isotopes from Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Manfredi, Juan; Tsang, M. B.; Lynch, W. G.; Brown, K. W.; Cerizza, G.; Barney, J.; Estee, J.; Loelius, C.; Sweany, S.; Anderson, C.; Setiawan, H.; Winkelbauer, J.; Smith, K.; Lee, J.; Xu, Z.; Rogers, A.; Pruitt, C.; Chajecki, Z.; Chen, G.; Langer, C.; Xiao, Z.; Li, Z.; Niu, C.

    2017-09-01

    A spectroscopic factor (SF) quantifies the single particle structure of a given state in a nucleus. There is a discrepancy in extracted SF's between studies that use transfer reactions and those that use knockout reactions. Resolving this discrepancy is important both for understanding reaction probes as well as constraining nuclear structure theory. Kinematically complete measurements of the transfer reactions 34Ar(p,d) and 46Ar(p,d) were performed at the National Superconducting Cyclotron Laboratory. The same beam energy (70 MeV/u) was used as in a previous knockout measurement to account for energy dependence in the relevant optical potentials. Preliminary results will be presented. In addition, findings from measurement of the two-neutron transfer reactions 34Ar(p,t) and 4 6 Ar(p,t) will be discussed. This work was supported by the NSF (PHY 1565546) and the DOE NNSA Stewardship Science Graduate Fellowship.

  12. Inflammatory and redox reactions in colorectal carcinogenesis.

    PubMed

    Guina, Tina; Biasi, Fiorella; Calfapietra, Simone; Nano, Mario; Poli, Giuseppe

    2015-03-01

    It has been established that there is a relationship between chronic inflammation and cancer development. The constant colonic inflammation typical of inflammatory bowel diseases is now considered a risk factor for colorectal carcinoma (CRC) development. The inflammatory network of signaling molecules is also required during the late phases of carcinogenesis, to enable cancer cells to survive and to metastasize. Oxidative reactions are an integral part of the inflammatory response, and are generally associated with CRC development. However, when the malignant phenotype is acquired, increased oxidative status induces antioxidant defenses in cancer cells, favoring their aggressiveness. This contradictory behavior of cancer cells toward redox status is of great significance for potential anticancer therapies. This paper summarizes the essential background information relating to the molecules involved in regulating oxidative stress and inflammation during carcinogenesis. Understanding more of their function in CRC stages might provide the foundation for future developments in CRC treatment. © 2015 New York Academy of Sciences.

  13. Cellular metabolic network analysis: discovering important reactions in Treponema pallidum.

    PubMed

    Chen, Xueying; Zhao, Min; Qu, Hong

    2015-01-01

    T. pallidum, the syphilis-causing pathogen, performs very differently in metabolism compared with other bacterial pathogens. The desire for safe and effective vaccine of syphilis requests identification of important steps in T. pallidum's metabolism. Here, we apply Flux Balance Analysis to represent the reactions quantitatively. Thus, it is possible to cluster all reactions in T. pallidum. By calculating minimal cut sets and analyzing topological structure for the metabolic network of T. pallidum, critical reactions are identified. As a comparison, we also apply the analytical approaches to the metabolic network of H. pylori to find coregulated drug targets and unique drug targets for different microorganisms. Based on the clustering results, all reactions are further classified into various roles. Therefore, the general picture of their metabolic network is obtained and two types of reactions, both of which are involved in nucleic acid metabolism, are found to be essential for T. pallidum. It is also discovered that both hubs of reactions and the isolated reactions in purine and pyrimidine metabolisms play important roles in T. pallidum. These reactions could be potential drug targets for treating syphilis.

  14. Role of the Edge Properties in the Hydrogen Evolution Reaction on MoS2.

    PubMed

    Lazar, Petr; Otyepka, Michal

    2017-04-06

    Molybdenum disulfide, in particular its edges, has attracted considerable attention as possible substitute for platinum catalysts in the hydrogen evolution reaction (HER). The complex nature of the reaction complicates its detailed experimental investigations, which are mostly indirect and sample dependent. Therefore, density functional theory calculations were employed to study how the properties of the MoS 2 Mo-edge influence the thermodynamics of hydrogen adsorption onto the edge. The effect of the computational model (one-dimensional nanostripe), border symmetry imposed by its length, sulfur saturation of the edge, and dimensionality of the material are discussed. Hydrogen adsorption was found to depend critically on the coverage of extra sulfur at the Mo edge. The bare Mo-edge and fully sulfur-covered Mo-edge are catalytically inactive. The most favorable hydrogen binding towards HER was found for the Mo-edge covered by sulfur monomers. This edge provides hydrogen adsorption free energies positioned around -0.25 eV at up to 50 % hydrogen coverage, close to the experimental values of overpotential needed for the HER reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Extreme reaction times determine fluctuation scaling in human color vision

    NASA Astrophysics Data System (ADS)

    Medina, José M.; Díaz, José A.

    2016-11-01

    In modern mental chronometry, human reaction time defines the time elapsed from stimulus presentation until a response occurs and represents a reference paradigm for investigating stochastic latency mechanisms in color vision. Here we examine the statistical properties of extreme reaction times and whether they support fluctuation scaling in the skewness-kurtosis plane. Reaction times were measured for visual stimuli across the cardinal directions of the color space. For all subjects, the results show that very large reaction times deviate from the right tail of reaction time distributions suggesting the existence of dragon-kings events. The results also indicate that extreme reaction times are correlated and shape fluctuation scaling over a wide range of stimulus conditions. The scaling exponent was higher for achromatic than isoluminant stimuli, suggesting distinct generative mechanisms. Our findings open a new perspective for studying failure modes in sensory-motor communications and in complex networks.

  16. Water-Rock Reactions on Non-Planetary Bodies in the Early Solar System

    NASA Astrophysics Data System (ADS)

    Zolotov, M. Y.

    2005-12-01

    Reactions of aqueous fluids with rocks shortly after formation of the solar system affected the oxidation states, mineralogy, organic speciation, ice composition, and surface/atmospheric chemistry of asteroids, icy satellites of giant plants, and possibly Kuiper belt objects. Water condensed as ice in the solar nebula, was incorporated into the composition of these bodies together with rocky components represented by extremely reduced and anhydrous nebular condensates (e.g., Fe-rich metal, forsterite, low-Ca pyroxene, troilite, Ca-Mg-Al oxides, phosphides), presolar grains (SiC, graphite, diamond, Al-, Mg-, Ti-oxides) and organic compounds and polymers. Radioactive decay of short-lived radionuclides on small bodies, and accretionary heat and decay of long-lived radionuclides on large bodies provided energy to melt ice. On smaller bodies, low gravity precluded separation of water from rocks and restricted fluid dynamics. On larger bodies, water was separated from descending rocks, limiting the duration of water-rock reactions. Competitive oxidation and hydration by water affected both inorganic and organic compounds in rocks. Oxidation of minerals led to formation of ferrous silicates, magnetite, pyrrhotite, Ni sulfides, Ni-rich metal alloys, chromite, phosphates, carbonates and sulfates. Hydration caused formation of phyllosilicates (serpentine, chlorites, smectite clays, amphiboles, and micas), hydroxides, and hydrated sulfides and salts. High water/rock ratios, elevated temperatures and low pressures favored oxidation. Low temperatures supported hydration. In some icy satellites (Europa, Ganymede) high water content and hydrothermal processes during differentiation may have caused profound oxidation leading to carbonates and even sulfates. Since water was the only early oxidizing agent, the elevated oxidation state of Io implies its early aqueous history. Hydrogen was produced in all oxidation reactions and preferentially separated into the gas phase. Escape of H

  17. Linear systems on balancing chemical reaction problem

    NASA Astrophysics Data System (ADS)

    Kafi, R. A.; Abdillah, B.

    2018-01-01

    The concept of linear systems appears in a variety of applications. This paper presents a small sample of the wide variety of real-world problems regarding our study of linear systems. We show that the problem in balancing chemical reaction can be described by homogeneous linear systems. The solution of the systems is obtained by performing elementary row operations. The obtained solution represents the finding coefficients of chemical reaction. In addition, we present a computational calculation to show that mathematical software such as Matlab can be used to simplify completion of the systems, instead of manually using row operations.

  18. Outbreak of Adverse Reactions Associated with Contaminated Heparin

    PubMed Central

    Blossom, David B.; Kallen, Alexander J.; Patel, Priti R.; Elward, Alexis; Robinson, Luke; Gao, Ganpan; Langer, Robert; Perkins, Kiran M.; Jaeger, Jennifer L.; Kurkjian, Katie M.; Jones, Marilyn; Schillie, Sarah F.; Shehab, Nadine; Ketterer, Daniel; Venkataraman, Ganesh; Kishimoto, Takashi Kei; Shriver, Zachary; McMahon, Ann W.; Austen, K. Frank; Kozlowski, Steven; Srinivasan, Arjun; Turabelidze, George; Gould, Carolyn V.; Arduino, Matthew J.; Sasisekharan, Ram

    2013-01-01

    BACKGROUND In January 2008, the Centers for Disease Control and Prevention began a nationwide investigation of severe adverse reactions that were first detected in a single hemodialysis facility. Preliminary findings suggested that heparin was a possible cause of the reactions. METHODS Information on clinical manifestations and on exposure was collected for patients who had signs and symptoms that were consistent with an allergic-type reaction after November 1, 2007. Twenty-one dialysis facilities that reported reactions and 23 facilities that reported no reactions were included in a case–control study to identify facility-level risk factors. Unopened heparin vials from facilities that reported reactions were tested for contaminants. RESULTS A total of 152 adverse reactions associated with heparin were identified in 113 patients from 13 states from November 19, 2007, through January 31, 2008. The use of heparin manufactured by Baxter Healthcare was the factor most strongly associated with reactions (present in 100.0% of case facilities vs. 4.3% of control facilities, P<0.001). Vials of heparin manufactured by Baxter from facilities that reported reactions contained a contaminant identified as oversulfated chondroitin sulfate (OSCS). Adverse reactions to the OSCS-contaminated heparin were often characterized by hypotension, nausea, and shortness of breath occurring within 30 minutes after administration. Of 130 reactions for which information on the heparin lot was available, 128 (98.5%) occurred in a facility that had OSCS-contaminated heparin on the premises. Of 54 reactions for which the lot number of administered heparin was known, 52 (96.3%) occurred after the administration of OSCS-contaminated heparin. CONCLUSIONS Heparin contaminated with OSCS was epidemiologically linked to adverse reactions in this nationwide outbreak. The reported clinical features of many of the cases further support the conclusion that contamination of heparin with OSCS was the cause

  19. Design Factors Affecting the Reaction Time for Identifying Toilet Signs: A Preliminary Study.

    PubMed

    Chen, Yi-Lang; Sie, Cai-Cin

    2016-04-01

    This study focused on the manner in which design factors affect the reaction time for identifying toilet signs. Taiwanese university students and staff members (50 men, 50 women; M age = 23.5 year, SD = 5.7) participated in the study. The 36 toilet signs were modified on three factors (six presenting styles, two figure-ground exchanges, and three colors), and the reaction time data of all participants were collected when the signs were presented in a simulation onscreen. Participants were quickest when reading Chinese text, followed by graphics and English texts. The findings also showed that men and women had different reaction times across various design combinations. These findings can serve as a reference for practically designing toilet signs, since design factors can lead to difficulties with comprehension based on reaction time measurements. © The Author(s) 2016.

  20. Children's need for favorable acoustics in schools

    NASA Astrophysics Data System (ADS)

    Nelson, Peggy B.

    2003-10-01

    Children continue to improve their understanding of speech in noise and reverberation throughout childhood and adolescence. They do not typically achieve adult performance levels until their late teenage years. As a result, schools that are designed to be acoustically adequate for adult understanding may be insufficient for full understanding by young children. In addition, children with hearing loss, those with attention problems, and those learning in a non-native language require even more favorable signal-to-noise ratios. This tutorial will review the literature gathered by the ANSl/ASA working group on classroom acoustics that shaped the recommendations of the working group. Special topics will include speech perception data from typically developing infants and children, from children with hearing loss, and from adults and children listening in a non-native language. In addition, the tutorial will overview recommendations contained within ANSI standard 12.60-2002: Acoustical Performance Criteria, Design Requirements, and Guidelines for Schools. The discussion will also include issues related to designing quiet classrooms and working with local schools and professionals.

  1. Appeals court reverses verdict favoring drug companies.

    PubMed

    1995-06-02

    An appeals court reversed a verdict favoring drug companies after the widow of a hemophiliac, whose death was linked to HIV-tainted blood products, sued four pharmaceutical companies to pay damages. The four companies, Alpha Therapeutic Corp., Miles Laboratories Inc., Armour Pharmaceutical Co., and Baxter Travenol Laboratories Inc., provided Factor VIII, a clotting concentrate, to [name removed] [name removed], the plaintiff's husband, from 1972 until his death in 1987. [Name removed]'s wife sued the companies, alleging that the defendants negligently solicited blood plasma from paid donors who had a high risk of having HIV, failed to determine whether any lots of Factor VIII contained plasma from an at-risk donor, failed to warn consumers of possible risks, and failed to heat-treat HIV and other viruses in Factor VIII, despite industry-wide knowledge of the risk of infection. The three-judge panel said the trial judge's decision to avoid ruling on the antigenic stimulation theory, based on insufficient evidence, was improper. In addition, the appeals court said a retrial is necessary because of improper remarks made by Alpha's attorney.

  2. Expanding the histologic findings in smallpox-related post-vaccinial non-viral folliculitis.

    PubMed

    Bunick, Christopher G; Mariwalla, Kavita; Ibrahim, Omer; Modi, Badri; Imaeda, Suguru; McNiff, Jennifer M

    2013-03-01

    Post-vaccinial non-viral folliculitis has been recognized in the past decade as a new adverse cutaneous reaction to smallpox vaccination. Contrary to more serious smallpox vaccine reactions, post-vaccinial non-viral folliculitis has a benign course and resolves spontaneously within approximately 7 days. We describe additional histopathologic findings associated with post-vaccinial non-viral folliculitis, which has only been described once previously. New findings include the presence of a neutrophilic or lymphohistiocytic infiltrate that is concentrated around the hair follicles. We compare our findings to the follicular nature of varicella and herpes zoster infections, generating the hypothesis of deposition of vaccinia protein within folliculosebaceous units as a potential pathophysiologic mechanism behind post-vaccinial non-viral folliculitis. © 2012 John Wiley & Sons A/S. Published by Blackwell Publishing Ltd.

  3. Challenging the Courtesy Bias Interpretation of Favorable Clients' Perceptions of Family Planning Delivery

    ERIC Educational Resources Information Center

    Len, Federico R.; Lundgren, Rebecka; Huapaya, Ana; Sinai, Irit; Jennings, Victoria

    2007-01-01

    Favorable client perceptions of provider's interpersonal behavior in contraceptive delivery, documented in clinic exit questionnaires, appear to contradict results from qualitative evaluations and are attributed to clients' courtesy bias. In this study, trained simulated clients requested services from Ministry of Health providers in three…

  4. Age differences in emotional reactions: arousal and age-relevance count.

    PubMed

    Streubel, Berit; Kunzmann, Ute

    2011-12-01

    Recent findings suggest positivity effects in older adults' attention and memory, but few studies have examined such effects on the level of emotional reactivity. In this study, 52 young and 52 older adults rated 172 pictures of the International Affective Picture System, differing in arousal and age-relevance, in terms of valence and discrete emotions. Age differences in the ratio of pleasantness reactions to pleasant pictures vs. unpleasantness reactions to unpleasant pictures as well as age differences in absolute levels of unpleasantness and pleasantness reactions suggest that positivity effects in older adults' subjective emotional reactions are reduced under high arousal. There is also evidence that positivity effects may be restricted to stimuli with low relevance in old age.

  5. The energetics of rearrangement and water elimination reactions in the radiolysis of the DNA bases in aqueous solution (eaq- and *OH attack): DFT calculations.

    PubMed

    Naumov, Sergej; von Sonntag, Clemens

    2008-03-01

    DFT calculations on the relative stability of various nucleobase radicals induced by e(aq)(-) and (*)OH have been carried out for assessing the energetics of rearrangements and water elimination reactions, taking the solvent effect of water into account. Uracil and thymine radical anions are protonated fast at O2 and O4, whereby the O2-protonated anions are higher in energy (50 kJ mol(-1), equivalent to a 9-unit lower pK(a)). The experimentally observed pK(a)=7 is thus that of the O4-protonated species. Thermodynamically favored protonation occurs slowly at C6 (driving force, thymine: 49 kJ mol(-1), uracil: 29 kJ mol(-1)). The cytosine radical anion is rapidly protonated by water at N3. Final protonation at C6 is disfavored here. The kinetically favored pyrimidine C5 (*)OH adducts rearrange into the thermodynamically favored C6 (*)OH adducts (driving force, thymine: 42 kJ mol(-1)). Very similar in energy is a water elimination that leads to the Ura-5-methyl radical. Purine (*)OH adducts at C4 and C5 (plus C2 in guanine) eliminate water in exothermic reactions, while water elimination from the C8 (*)OH adducts is endothermic. The latter open the ring en route to the FAPY products, an H transfer from the C8(*)OH to N9 being the most likely process.

  6. Finding a Second Sample of Life on Earth

    NASA Astrophysics Data System (ADS)

    Davies, P. C. W.; Lineweaver, Charles H.

    2005-06-01

    If life emerges readily under Earth-like conditions, the possibility arises of multiple terrestrial genesis events. We seek to quantify the probability of this scenario using estimates of the Archean bombardment rate and the fact that life established itself fairly rapidly on Earth once conditions became favorable. We find a significant likelihood that at least one more sample of life, referred to here as alien life, may have emerged on Earth, and could have coexisted with known life. Indeed, it is difficult to rule out the possibility of extant alien life. We offer some suggestions for how an alternative sample of life might be detected.

  7. Aluminum and Fenton reaction: how can the reaction be modulated by speciation? A computational study using citrate as a test case.

    PubMed

    Mujika, Jon I; Dalla Torre, Gabriele; Lopez, Xabier

    2018-06-13

    The pro-oxidant ability of aluminum is behind many of the potential toxic effects of this exogenous element in the human organism. Although the overall process is still far from being understood at the molecular level, the well known ability of aluminum to promote the Fenton reaction is mediated through the formation of stable aluminum-superoxide radical complexes. However, the properties of metal complexes are highly influenced by the speciation of the metal. In this paper, we investigate the effect that speciation could have on the pro-oxidant activity of aluminum. We choose citrate as a test case, because it is the main low-molecular-mass chelator of aluminum in blood serum, forming very stable aluminum-citrate complexes. The influence of citrate in the interaction of aluminum with the superoxide radical is investigated, determining how the formation of aluminum-citrate complexes affects the promotion of the Fenton reaction. The results indicate that citrate increases the stability of the aluminum-superoxide complexes through the formation of ternary compounds, and that the Fenton reaction is even more favorable when aluminum is chelated to citrate. Nevertheless, our results demonstrate that overall, citrate may prevent the pro-oxidant activity of aluminum: on one hand, in an excess of citrate, the formation of 1 : 2 aluminum-citrate complexes is expected. On the other hand, the chelation of iron by citrate makes the reduction of iron thermodynamically unfavorable. In summary, the results suggest that citrate can have both a promotion and protective role, depending on subtle factors, such as initial concentration, non-equilibrium behavior and the exchange rate of ligands in the first shell of the metals.

  8. Academic freedom, public reactions, and anonymity.

    PubMed

    Häyry, Matti

    2014-05-01

    Academic freedom can be defined as immunity against adverse reactions from the general public, designed to keep scholars unintimidated and productive even after they have published controversial ideas. Francesca Minerva claims that this notion of strict instrumental academic freedom is supported by Ronald Dworkin, and that anonymity would effectively defend the sphere of immunity implied by it. Against this, I argue that the idea defended by Minerva finds no support in the work by Dworkin referred to; that anonymity would not in most cases effectively protect the kind of immunity sought after; and that in some cases it would not even be desirable to protect scholars from public reactions to their controversial claims. © 2014 John Wiley & Sons Ltd.

  9. Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.

    PubMed

    Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng

    2014-08-01

    The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable. Copyright © 2014. Published by Elsevier B.V.

  10. A continuous GRASP to determine the relationship between drugs and adverse reactions

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

    Hirsch, Michael J.; Meneses, Claudio N.; Pardalos, Panos M.

    2007-11-05

    Adverse drag reactions (ADRs) are estimated to be one of the leading causes of death. Many national and international agencies have set up databases of ADR reports for the express purpose of determining the relationship between drugs and adverse reactions that they cause. We formulate the drug-reaction relationship problem as a continuous optimization problem and utilize C-GRASP, a new continuous global optimization heuristic, to approximately determine the relationship between drugs and adverse reactions. Our approach is compared against others in the literature and is shown to find better solutions.

  11. Reactions of Copper and Silver Cations with Carbon Dioxide: An Infrared Photodissociation Spectroscopic and Theoretical Study.

    PubMed

    Zhao, Zhi; Kong, Xiangtao; Yang, Dong; Yuan, Qinqin; Xie, Hua; Fan, Hongjun; Zhao, Jijun; Jiang, Ling

    2017-05-04

    The reaction of copper and silver cations with carbon dioxide was studied by mass-selected infrared photodissociation spectroscopy. Quantum chemical calculations were performed on these products, which aided the experimental assignments of the infrared spectra and helped to elucidate the geometrical and electronic structures. The Cu + and Ag + cations bind to an oxygen atom of CO 2 in an end-on configuration via a charge-quadrupole electrostatic interaction in the [M(CO 2 ) n ] + complexes. The formation of oxide-carbonyl and carbonyl-carbonate structures is not favored for the interaction of CO 2 with Cu + and Ag + . For n = 3 and 4, the n + 0 structure is preferred. [Note on the nomenclature: Using i + j, i denotes the number of CO 2 molecules in the first coordination shell, and j denotes the number of CO 2 molecules in the second coordination shell.] The two nearly energy-identical n + 0 and (n - 1) + 1 structures coexist in n = 5 and 6. While the six-coordinated structure is favored for [Cu(CO 2 ) n=7,8 ] + , the n + 0 configuration is dominated in [Ag(CO 2 ) n=7,8 ] + . The reaction of CO 2 with the cationic metal atoms has been compared to that with the neutral and anionic metal atoms, which would have important implications for understanding the interaction of CO 2 with reduction catalysts and rationally designing catalysts for CO 2 reduction based on cost-effective transition metals.

  12. Improved Photoinduced Fluorogenic Alkene-Tetrazole Reaction for Protein Labeling.

    PubMed

    Shang, Xin; Lai, Rui; Song, Xi; Li, Hui; Niu, Wei; Guo, Jiantao

    2017-11-15

    The 1,3-dipolar cycloaddition reaction between an alkene and a tetrazole represents one elegant and rare example of fluorophore-forming bioorthogonal chemistry. This is an attractive reaction for imaging applications in live cells that requires less intensive washing steps and/or needs spatiotemporal resolutions. In the present work, as an effort to improve the fluorogenic property of the alkene-tetrazole reaction, an aromatic alkene (styrene) was investigated as the dipolarophile. Over 30-fold improvement in quantum yield of the reaction product was achieved in aqueous solution. According to our mechanistic studies, the observed improvement is likely due to an insufficient protonation of the styrene-tetrazole reaction product. This finding provides useful guidance to the future design of alkene-tetrazole reactions for biological studies. Fluorogenic protein labeling using the styrene-tetrazole reaction was demonstrated both in vitro and in vivo. This was realized by the genetic incorporation of an unnatural amino acid containing the styrene moiety. It is anticipated that the combination of styrene with different tetrazole derivatives can generally improve and broaden the application of alkene-tetrazole chemistry in real-time imaging in live cells.

  13. Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear.

    PubMed

    Khajeh, Arash; He, Xin; Yeon, Jejoon; Kim, Seong H; Martini, Ashlie

    2018-05-29

    Shear-driven chemical reaction mechanisms are poorly understood because the relevant reactions are often hidden between two solid surfaces moving in relative motion. Here, this phenomenon is explored by characterizing shear-induced polymerization reactions that occur during vapor phase lubrication of α-pinene between sliding hydroxylated and dehydroxylated silica surfaces, complemented by reactive molecular dynamics simulations. The results suggest that oxidative chemisorption of the α-pinene molecules at reactive surface sites, which transfers oxygen atoms from the surface to the adsorbate molecule, is the critical activation step. Such activation takes place more readily on the dehydroxylated surface. During this activation, the most strained part of the α-pinene molecules undergoes a partial distortion from its equilibrium geometry, which appears to be related to the critical activation volume for mechanical activation. Once α-pinene molecules are activated, association reactions occur between the newly attached oxygen and one of the carbon atoms in another molecule, forming ether bonds. These findings have general implications for mechanochemistry because they reveal that shear-driven reactions may occur through reaction pathways very different from their thermally induced counterparts and specifically the critical role of molecular distortion in such reactions.

  14. Self-exchange reaction of [Ni(mnt)2](1-,2-) in nonaqueous solutions.

    PubMed

    Kowert, Bruce A; Fehr, Michael J; Sheaff, Pamela J

    2008-07-07

    The rate constant, k, for the homogeneous electron transfer (self-exchange) reaction between the diamagnetic bis(maleonitriledithiolato)nickel dianion, [Ni(mnt) 2] (2-), and the paramagnetic monoanion, [Ni(mnt) 2] (1-), has been determined in acetone and nitromethane (CH 3NO 2) using (13)C NMR line widths at 22 degrees C (mnt = 1,2-S 2C 2(CN) 2). The values of k (2.91 x 10 (6) M (-1) s (-1) in acetone, 5.78 x 10 (6) M (-1) s (-1) in CH 3NO 2) are faster than those for the electron transfer reactions of other Ni(III,II) couples; the structures of [Ni(mnt) 2] (1-) and [Ni(mnt) 2] (2-) allow for a favorable overlap that lowers the free energy of activation. The values of k are consistent with the predictions of Marcus theory. In addition to k, the spin-lattice relaxation time, T 1e, of [Ni(mnt) 2] (1-) is obtained from the NMR line width analysis; the values are consistent with those predicted by spin relaxation theory.

  15. Colleges, Fighting U.S. Trade Proposal, Say It Favors For-Profit Distance Education.

    ERIC Educational Resources Information Center

    Foster, Andrea

    2002-01-01

    Describes how many colleges are opposing a U.S. plan that they say favors for-profit distance education. The proposal before the World Trade Organization asks member countries to begin formal negotiations to reduce barriers that keep higher education institutions from offering courses in other countries. (EV)

  16. A Gibbs Energy Minimization Approach for Modeling of Chemical Reactions in a Basic Oxygen Furnace

    NASA Astrophysics Data System (ADS)

    Kruskopf, Ari; Visuri, Ville-Valtteri

    2017-12-01

    In modern steelmaking, the decarburization of hot metal is converted into steel primarily in converter processes, such as the basic oxygen furnace. The objective of this work was to develop a new mathematical model for top blown steel converter, which accounts for the complex reaction equilibria in the impact zone, also known as the hot spot, as well as the associated mass and heat transport. An in-house computer code of the model has been developed in Matlab. The main assumption of the model is that all reactions take place in a specified reaction zone. The mass transfer between the reaction volume, bulk slag, and metal determine the reaction rates for the species. The thermodynamic equilibrium is calculated using the partitioning of Gibbs energy (PGE) method. The activity model for the liquid metal is the unified interaction parameter model and for the liquid slag the modified quasichemical model (MQM). The MQM was validated by calculating iso-activity lines for the liquid slag components. The PGE method together with the MQM was validated by calculating liquidus lines for solid components. The results were compared with measurements from literature. The full chemical reaction model was validated by comparing the metal and slag compositions to measurements from industrial scale converter. The predictions were found to be in good agreement with the measured values. Furthermore, the accuracy of the model was found to compare favorably with the models proposed in the literature. The real-time capability of the proposed model was confirmed in test calculations.

  17. Reaction between the Pt(II)-complexes and the amino acids of the β-amyloid peptide

    NASA Astrophysics Data System (ADS)

    Novato, Willian T. G.; Stroppa, Pedro Henrique F.; Da Silva, Adilson D.; Botezine, Naiara P.; Machado, Flávia C.; Costa, Luiz Antônio S.; Dos Santos, Hélio F.

    2017-01-01

    Reaction between [Pt(ophen)Cl2] and HIS was monitored and the solvolysis (k1) and Cl/HIS ligand exchange (k2) rate constants obtained. The k1 and k2 were (6.2 ± 0.4) × 10-5 s-1 and 52.8 × 10-2 M-1 s-1, respectively. The corresponding calculated values were 47.5 × 10-5 s-1 and 52.2 × 10-2 M-1 s-1, in agreement with the experiment. Calculations were used to establish the reactivity order for a set of amino acids: MET ∼ LYS ∼ HIS(ε) > GLU ∼ ASP >> ASN ∼ GLN. In spite of the similar reactivity among MET, LYS and HIS, the thermodynamics suggests the reactions with LYS and HIS more favorable than with MET. Therefore, N-containing amino acids should be potential targets of Pt(II)-complexes in β-amyloid.

  18. Origin of chemoselectivity in N-heterocyclic carbene catalyzed cross-benzoin reactions: DFT and experimental insights.

    PubMed

    Langdon, Steven M; Legault, Claude Y; Gravel, Michel

    2015-04-03

    An exploration into the origin of chemoselectivity in the NHC-catalyzed cross-benzoin reaction reveals several key factors governing the preferred pathway. In the first computational study to explore the cross-benzoin reaction, a piperidinone-derived triazolium catalyst produces kinetically controlled chemoselectivity. This is supported by (1)H NMR studies as well as a series of crossover experiments. Major contributors include the rapid and preferential formation of an NHC adduct with alkyl aldehydes, a rate-limiting carbon-carbon bond formation step benefiting from a stabilizing π-stacking/π-cation interaction, and steric penalties paid by competing pathways. The energy profile for the analogous pyrrolidinone-derived catalyst was found to be remarkably similar, despite experimental data showing that it is less chemoselective. The chemoselectivity could not be improved through kinetic control; however, equilibrating conditions show substantial preference for the same cross-benzoin product kinetically favored by the piperidinone-derived catalyst.

  19. Misperceiving Bullshit as Profound Is Associated with Favorable Views of Cruz, Rubio, Trump and Conservatism

    PubMed Central

    Pfattheicher, Stefan; Schindler, Simon

    2016-01-01

    The present research investigates the associations between holding favorable views of potential Democratic or Republican candidates for the US presidency 2016 and seeing profoundness in bullshit statements. In this contribution, bullshit is used as a technical term which is defined as communicative expression that lacks content, logic, or truth from the perspective of natural science. We used the Bullshit Receptivity scale (BSR) to measure seeing profoundness in bullshit statements. The BSR scale contains statements that have a correct syntactic structure and seem to be sound and meaningful on first reading but are actually vacuous. Participants (N = 196; obtained via Amazon Mechanical Turk) rated the profoundness of bullshit statements (using the BSR) and provided favorability ratings of three Democratic (Hillary Clinton, Martin O’Malley, and Bernie Sanders) and three Republican candidates for US president (Ted Cruz, Marco Rubio, and Donald Trump). Participants also completed a measure of political liberalism/conservatism. Results revealed that favorable views of all three Republican candidates were positively related to judging bullshit statements as profound. The smallest correlation was found for Donald Trump. Although we observe a positive association between bullshit and support for the three Democrat candidates, this relationship is both substantively small and statistically insignificant. The general measure of political liberalism/conservatism was also related to judging bullshit statements as profound in that individuals who were more politically conservative had a higher tendency to see profoundness in bullshit statements. Of note, these results were not due to a general tendency among conservatives to see profoundness in everything: Favorable views of Republican candidates and conservatism were not significantly related to profoundness ratings of mundane statements. In contrast, this was the case for Hillary Clinton and Martin O’Malley. Overall

  20. Misperceiving Bullshit as Profound Is Associated with Favorable Views of Cruz, Rubio, Trump and Conservatism.

    PubMed

    Pfattheicher, Stefan; Schindler, Simon

    2016-01-01

    The present research investigates the associations between holding favorable views of potential Democratic or Republican candidates for the US presidency 2016 and seeing profoundness in bullshit statements. In this contribution, bullshit is used as a technical term which is defined as communicative expression that lacks content, logic, or truth from the perspective of natural science. We used the Bullshit Receptivity scale (BSR) to measure seeing profoundness in bullshit statements. The BSR scale contains statements that have a correct syntactic structure and seem to be sound and meaningful on first reading but are actually vacuous. Participants (N = 196; obtained via Amazon Mechanical Turk) rated the profoundness of bullshit statements (using the BSR) and provided favorability ratings of three Democratic (Hillary Clinton, Martin O'Malley, and Bernie Sanders) and three Republican candidates for US president (Ted Cruz, Marco Rubio, and Donald Trump). Participants also completed a measure of political liberalism/conservatism. Results revealed that favorable views of all three Republican candidates were positively related to judging bullshit statements as profound. The smallest correlation was found for Donald Trump. Although we observe a positive association between bullshit and support for the three Democrat candidates, this relationship is both substantively small and statistically insignificant. The general measure of political liberalism/conservatism was also related to judging bullshit statements as profound in that individuals who were more politically conservative had a higher tendency to see profoundness in bullshit statements. Of note, these results were not due to a general tendency among conservatives to see profoundness in everything: Favorable views of Republican candidates and conservatism were not significantly related to profoundness ratings of mundane statements. In contrast, this was the case for Hillary Clinton and Martin O'Malley. Overall, small

  1. A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

    NASA Technical Reports Server (NTRS)

    Goldstein, D.; Magnotti, F.; Chinitz, W.

    1983-01-01

    Reaction rates in turbulent, reacting flows are reviewed. Assumed probability density functions (pdf) modeling of reaction rates is being investigated in relation to a three variable pdf employing a 'most likely pdf' model. Chemical kinetic mechanisms treating hydrogen air combustion is studied. Perfectly stirred reactor modeling of flame stabilizing recirculation regions was used to investigate the stable flame regions for silane, hydrogen, methane, and propane, and for certain mixtures thereof. It is concluded that in general, silane can be counted upon to stabilize flames only when the overall fuel air ratio is close to or greater than unity. For lean flames, silane may tend to destabilize the flame. Other factors favoring stable flames are high initial reactant temperatures and system pressure.

  2. Nestin predicts a favorable prognosis in early ampullary adenocarcinoma and functions as a promoter of metastasis in advanced cancer.

    PubMed

    Shan, Yan-Shen; Chen, Yi-Ling; Lai, Ming-Derg; Hsu, Hui-Ping

    2015-01-01

    Nestin exhibits stemness characteristics and is overexpressed in several types of cancers. Downstream signaling of nestin [cyclin-dependent kinase 5 (CDK5) and Ras-related C3 botulinum toxin substrate 1 (Rac1)] functions in cancer to modulate cellular behaviors. We studied the function of nestin in ampullary adenocarcinoma. Immunohistochemistry (IHC), reverse transcription-polymerase chain reaction, and cDNA microarray of nestin in ampullary adenocarcinoma was compared with normal duodenum. CDK5 and Rac1 were assessed by western blotting. We hypothesized that nestin/CDK5/Rac1 signaling behaves different in early and advanced cancer. We found that the presence of nestin mRNA was increased in the early stages of cancer (T2N0 or T3N0) and advanced cancer with lymph node metastasis (T4N1). A total of 102 patients were enrolled in the IHC staining. Weak nestin expression was correlated with favorable characteristics of cancer, decreased incidence of local recurrence and lower risk of recurrence within 12 months after surgery. Patients with weak nestin expression had the most favorable recurrence‑free survival rates. Patients with mild to strong nestin expression exhibited an advanced behavior of cancer and increased possibility of cancer recurrence. The reciprocal expression of nestin and RAC1 were explored using a cDNA microarray analysis in the early stages of ampullary adenocarcinoma. Increased level of CDK5 with simultaneously decreased expression of Rac1 was detected by western blotting of ampullary adenocarcinoma in patients without cancer recurrence. The activation of multiple oncogenic pathways, combined with the stemness characteristics of nestin, formed a complex network in advanced ampullary adenocarcinoma. Our study demonstrated that nestin performs a dual role in ampullary adenocarcinoma. Appropriate amount of nestin enhances CDK5 function to suppress Rac1 and excessive nestin/CDK5 participates in multiple oncogenic pathways to promote cancer invasiveness

  3. Domain expertise insulates against judgment bias by monetary favors through a modulation of ventromedial prefrontal cortex

    PubMed Central

    Kirk, Ulrich; Harvey, Ann; Montague, P. Read

    2011-01-01

    Recent work using an art-viewing paradigm shows that monetary sponsorship of the experiment by a company (a favor) increases the valuation of paintings placed next to the sponsoring corporate logo, an effect that correlates with modulation of the ventromedial prefrontal cortex (VMPFC). We used the same art-viewing paradigm to test a prevailing idea in the domain of conflict-of-interest: that expertise in a domain insulates against judgment bias even in the presence of a monetary favor. Using a cohort of art experts, we show that monetary favors do not bias the experts’ valuation of art, an effect that correlates with a lack of modulation of the VMPFC across sponsorship conditions. The lack of sponsorship effect in the VMPFC suggests the hypothesis that their brains remove the behavioral sponsorship effect by censoring sponsorship-dependent modulation of VMPFC activity. We tested the hypothesis that prefrontal regions play a regulatory role in mediating the sponsorship effect. We show that the dorsolateral prefrontal cortex (DLPFC) is recruited in the expert group. Furthermore, we tested the hypothesis in nonexpert controls by contrasting brain responses in controls who did not show a sponsorship effect to controls who did. Changes in effective connectivity between the DLPFC and VMPFC were greater in nonexpert controls, with an absence of the sponsorship effect relative to those with a presence of the sponsorship effect. The role of the DLPFC in cognitive control and emotion regulation suggests that it removes the influence of a monetary favor by controlling responses in known valuation regions of the brain including the the VMPFC. PMID:21646526

  4. Preprogramming Complex Hydrogel Responses using Enzymatic Reaction Networks.

    PubMed

    Postma, Sjoerd G J; Vialshin, Ilia N; Gerritsen, Casper Y; Bao, Min; Huck, Wilhelm T S

    2017-02-06

    The creation of adaptive matter is heavily inspired by biological systems. However, it remains challenging to design complex material responses that are governed by reaction networks, which lie at the heart of cellular complexity. The main reason for this slow progress is the lack of a general strategy to integrate reaction networks with materials. Herein we use a systematic approach to preprogram the response of a hydrogel to a trigger, in this case the enzyme trypsin, which activates a reaction network embedded within the hydrogel. A full characterization of all the kinetic rate constants in the system enabled the construction of a computational model, which predicted different hydrogel responses depending on the input concentration of the trigger. The results of the simulation are in good agreement with experimental findings. Our methodology can be used to design new, adaptive materials of which the properties are governed by reaction networks of arbitrary complexity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Reactions to Racial Trespassing.

    PubMed

    Maykovich, Minako K

    1978-10-01

    Three trespassers into the "body territory" of racial groups-a white woman with an Afro wig, a black with a blond wig, and a Japanese American with a blond wig-invoked reactions among 144 white, black, and Japanese American female university students. The major findings were as follows: (a) Dominant group trespassing was more likely to be viewed in cultural perspectives, while minority trespassing was viewed in a racial context; (b) Minority members tended to view minority trespassing more negatively than dominant group trespassing.

  6. Formation of Reactive Intermediates, Color, and Antioxidant Activity in the Maillard Reaction of Maltose in Comparison to d-Glucose.

    PubMed

    Kanzler, Clemens; Schestkowa, Helena; Haase, Paul T; Kroh, Lothar W

    2017-10-11

    In this study, the Maillard reaction of maltose and d-glucose in the presence of l-alanine was investigated in aqueous solution at 130 °C and pH 5. The reactivity of both carbohydrates was compared in regards of their degradation, browning, and antioxidant activity. In order to identify relevant differences in the reaction pathways, the concentrations of selected intermediates such as 1,2-dicarbonyl compounds, furans, furanones, and pyranones were determined. It was found, that the degradation of maltose predominantly yields 1,2-dicarbonyls that still carry a glucosyl moiety and thus subsequent reactions to HMF, furfural, and 2-acetylfuran are favored due to the elimination of d-glucose, which is an excellent leaving group in aqueous solution. Consequently, higher amounts of these heterocycles are formed from maltose. 3-deoxyglucosone and 3-deoxygalactosone represent the only relevant C 6 -1,2-dicarbonyls in maltose incubations and are produced in nearly equimolar amounts during the first 60 min of heating as byproducts of the HMF formation.

  7. Hypersensitivity reactions to non-steroidal anti-inflammatory drugs.

    PubMed

    Cornejo-Garcia, José Antonio; Blanca-López, Natalia; Doña, Inmaculada; Andreu, Inmaculada; Agúndez, José A G; Carballo, Miguel; Blanca, Miguel; Canto, María Gabriela

    2009-11-01

    NSAIDs are the most important group of drugs involved in hypersensitivity drug reactions, and include heterogeneous compounds with very different chemical structures. These reactions can be IgE dependent (immediate reactions), T cell-mediated (non-immediate), or induced by a non-specific immunological mechanism related with the blocking of the COX-1 enzyme and the shunting to the lipooxygenase pathway (cross-intolerant reactions). Cutaneous symptoms are the most frequent, with ibuprofen, naproxen and diclofenac being common culprit drugs worldwide, although others can be involved because patterns of consumption and exposure rates vary between countries. A very important proportion of immunological reactions are immediate, with urticaria and anaphylaxis being the typical clinical manifestations. Non-immediate reactions comprise a number of heterogeneous entities ranging from mild exanthema to severe TEN or DRESS syndrome, as well as organ-specific reactions such as hepatitis or pneumonitis. Cross-intolerant reactions appear to non-chemically related drugs, and involve respiratory airways, skin or both. In vivo diagnostic tests are based on the capacity of the skin to respond to the culprit drug, but their sensitivity is in many instances rather low. The approach for in vitro testing consists of either detecting specific IgE antibodies or studying the proliferation of T lymphocytes toward the eliciting drug. No appropriate tests are yet available for the in vitro validation of cross-intolerance reactions, although techniques based on the stimulation of basophils have been proposed. Based on these findings, the diagnostic approach is often based on the controlled administration of the drug to assess tolerance. In this work we review current knowledge on hypersensitivity reactions to NSAIDs, including diagnostic approach and genetic studies.

  8. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    DOE PAGES

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-19

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O₂ bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H₂O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH boundmore » structures have the highest calculated activity to date.« less

  9. Reaction time for trimolecular reactions in compartment-based reaction-diffusion models

    NASA Astrophysics Data System (ADS)

    Li, Fei; Chen, Minghan; Erban, Radek; Cao, Yang

    2018-05-01

    Trimolecular reaction models are investigated in the compartment-based (lattice-based) framework for stochastic reaction-diffusion modeling. The formulae for the first collision time and the mean reaction time are derived for the case where three molecules are present in the solution under periodic boundary conditions. For the case of reflecting boundary conditions, similar formulae are obtained using a computer-assisted approach. The accuracy of these formulae is further verified through comparison with numerical results. The presented derivation is based on the first passage time analysis of Montroll [J. Math. Phys. 10, 753 (1969)]. Montroll's results for two-dimensional lattice-based random walks are adapted and applied to compartment-based models of trimolecular reactions, which are studied in one-dimensional or pseudo one-dimensional domains.

  10. The formation of the dolomite-analogue norsethite: Reaction pathway and cation ordering

    NASA Astrophysics Data System (ADS)

    Pimentel, Carlos; Pina, Carlos M.

    2014-10-01

    Reaction pathways and cation ordering mechanisms involved in the formation of the mineral dolomite in nature still remain poorly understood. This is mainly due to the experimental problems posed by the synthesis of dolomite at ambient conditions, which preclude monitoring its formation in reasonable time scales. However, processes leading to the crystallization of fully-ordered dolomite-like structures can be studied by conducting experiments with mineral analogues, which are more readily precipitated. In this paper we present a study of the formation of the dolomite-analogue norsethite [BaMg(CO3)2] from a slurry which was aged at room temperature during 14 days. We found that norsethite forms by two dissolution-crystallization reactions from an initial amorphous nano-sized precipitate. The first reaction produces a mineral assemblage composed by witherite [BaCO3], northupite [Na3Mg(CO3)2Cl] and norsethite. The second dissolution-crystallization process leads to the almost complete depletion of witherite and northupite in favor of norsethite. While the composition of norsethite crystals rapidly reaches a Ba/Mg = 1 ratio, X-ray diffraction peaks indicate an increase in the crystallinity of those crystals during the first 48 h of reaction. Simultaneously, Ba-Mg cation ordering increases, as shown by the evolution of intensity ratios of certain superstructure and structure reflections. Altogether, these results demonstrate that the formation of fully-ordered norsethite occurs by a sequence of solvent-mediated processes which involve a number of precursors. Our study also suggests that similar processes might lead to the formation of dolomite in natural environments.

  11. Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species with Application to DSMC Simulations

    NASA Technical Reports Server (NTRS)

    Liechty, Derek S.

    2014-01-01

    The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for near-equilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion.

  12. Platelet count recovery after intravenous immunoglobulin predicts a favorable outcome in children with immune thrombocytopenia

    PubMed Central

    Ji, Mi Hong; Kim, Sung Jin; Ahn, Hyo Seop

    2016-01-01

    Background Childhood immune thrombocytopenic purpura (ITP) is a common acquired bleeding disorder. Even though most children recover, either spontaneously or with therapy, 10-20% of newly diagnosed ITP cases have a chronic course beyond 12 months. This study evaluated whether clinical and laboratory findings can predict the response to intravenous immunoglobulin (IVIG) and progression to persistent or chronic ITP in children. Methods During the period between March 2003 and June 2015, we retrospectively analyzed 72 children, newly diagnosed with ITP, who received IVIG treatment. Peripheral blood counts were obtained at diagnosis and at 1, 3, 6, and 12 months after IVIG treatment. Results After 6 months of IVIG treatment, 14 of 72 patients (19.4%) had persistent ITP, and after 12 months, 7 of 40 patients (17.5%) had chronic ITP. Age at diagnosis, gender, history of viral infection, or vaccination before disease onset were not statistically correlated with platelet recovery at 6 and 12 months. However, a platelet count recovery of ≥100×103/µL at 1 and 3 months was significantly correlated with platelet recovery at 6 (P<0.001 and P<0.001, respectively) and 12 (P=0.007 and P=0.004, respectively) months. Conclusion This study demonstrated that early platelet count recovery, at 1 and 3 months after IVIG treatment, predicts a short disease duration and a favorable outcome in children with newly diagnosed ITP. Further investigation in a larger group of patients is warranted to validate these findings. PMID:27382553

  13. Surface-Activated Coupling Reactions Confined on a Surface.

    PubMed

    Dong, Lei; Liu, Pei Nian; Lin, Nian

    2015-10-20

    Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density

  14. Scheme for generating distillation-favorable continuous-variable entanglement via three concurrent parametric down-conversions in a single χ(2) nonlinear photonic crystal.

    PubMed

    Gong, Yan-Xiao; Zhang, ShengLi; Xu, P; Zhu, S N

    2016-03-21

    We propose to generate a single-mode-squeezing two-mode squeezed vacuum state via a single χ(2) nonlinear photonic crystal. The state is favorable for existing Gaussian entanglement distillation schemes, since local squeezing operations can enhance the final entanglement and the success probability. The crystal is designed for enabling three concurrent quasi-phase-matching parametric-down conversions, and hence relieves the auxiliary on-line bi-side local squeezing operations. The compact source opens up a way for continuous-variable quantum technologies and could find more potential applications in future large-scale quantum networks.

  15. Density Functional Study for Chemical Reaction between Cr and Fe with Sodium Diethyldithiocarbamate (NaDDC)

    NASA Astrophysics Data System (ADS)

    Setiyanto, Henry; Muhida, Rifki; Kishi, Tomoya; Rahman, Md. Mahmudur; Dipojono, Hermawan K.; Diño, Wilson A.; Matsumoto, Shigeno; Kasai, Hideaki

    Analytical chemistry in the perspective of ab initio molecular orbital calculation is introduced by investigating the chemical reaction between transition metals Cr and Fe with sodium diethyldithiocarbamate (NaDDC), a complexing agent to detect and extract Cr in human blood sample. Using density functional theory—based calculations, we determine the stable structure of the Cr-DDC and Fe-DDC complexes and obtain its dissociation energies. We found dissociation energy values of -3.24 and -2.67 eV for Cr and Fe complexes, respectively; and hence the formation of the former complex is more favorable than the formation of the latter.

  16. A new type of power energy for accelerating chemical reactions: the nature of a microwave-driving force for accelerating chemical reactions.

    PubMed

    Zhou, Jicheng; Xu, Wentao; You, Zhimin; Wang, Zhe; Luo, Yushang; Gao, Lingfei; Yin, Cheng; Peng, Renjie; Lan, Lixin

    2016-04-27

    The use of microwave (MW) irradiation to increase the rate of chemical reactions has attracted much attention recently in nearly all fields of chemistry due to substantial enhancements in reaction rates. However, the intrinsic nature of the effects of MW irradiation on chemical reactions remains unclear. Herein, the highly effective conversion of NO and decomposition of H2S via MW catalysis were investigated. The temperature was decreased by several hundred degrees centigrade. Moreover, the apparent activation energy (Ea') decreased substantially under MW irradiation. Importantly, for the first time, a model of the interactions between microwave electromagnetic waves and molecules is proposed to elucidate the intrinsic reason for the reduction in the Ea' under MW irradiation, and a formula for the quantitative estimation of the decrease in the Ea' was determined. MW irradiation energy was partially transformed to reduce the Ea', and MW irradiation is a new type of power energy for speeding up chemical reactions. The effect of MW irradiation on chemical reactions was determined. Our findings challenge both the classical view of MW irradiation as only a heating method and the controversial MW non-thermal effect and open a promising avenue for the development of novel MW catalytic reaction technology.

  17. A new type of power energy for accelerating chemical reactions: the nature of a microwave-driving force for accelerating chemical reactions

    PubMed Central

    Zhou, Jicheng; Xu, Wentao; You, Zhimin; Wang, Zhe; Luo, Yushang; Gao, Lingfei; Yin, Cheng; Peng, Renjie; Lan, Lixin

    2016-01-01

    The use of microwave (MW) irradiation to increase the rate of chemical reactions has attracted much attention recently in nearly all fields of chemistry due to substantial enhancements in reaction rates. However, the intrinsic nature of the effects of MW irradiation on chemical reactions remains unclear. Herein, the highly effective conversion of NO and decomposition of H2S via MW catalysis were investigated. The temperature was decreased by several hundred degrees centigrade. Moreover, the apparent activation energy (Ea’) decreased substantially under MW irradiation. Importantly, for the first time, a model of the interactions between microwave electromagnetic waves and molecules is proposed to elucidate the intrinsic reason for the reduction in the Ea’ under MW irradiation, and a formula for the quantitative estimation of the decrease in the Ea’ was determined. MW irradiation energy was partially transformed to reduce the Ea’, and MW irradiation is a new type of power energy for speeding up chemical reactions. The effect of MW irradiation on chemical reactions was determined. Our findings challenge both the classical view of MW irradiation as only a heating method and the controversial MW non-thermal effect and open a promising avenue for the development of novel MW catalytic reaction technology. PMID:27118640

  18. The von Auwers reaction - history and synthetic applications.

    PubMed

    Dumeunier, Raphaël; Jaeckh, Simon

    2014-01-01

    Dienones obtained from the facile dearomatization of phenols, can be further transformed to semi-benzenes prone to rearomatize in clean, but sometimes unexpected, fashion. Over a hundred years ago, K. von Auwers found that adding Grignards on dienones would lead spontaneously to subsequent dehydration and a novel aromatizing rearrangement. This reaction was ignored for 50 years before Melvin Newman re-investigated these findings, studied the mechanism, and developed variations on the same theme. Since then, despite the tremendous potential of the reactions, those studies were only rarely mentioned, before finally falling into oblivion. This review aims to provide the reader with a detailed history and comprehensive bibliography of the von Auwers rearrangement, some of its synthetic applications, and new unpublished material in the hope to open new perspectives on this forgotten reaction.

  19. Mapping students' ideas about chemical reactions at different educational levels

    NASA Astrophysics Data System (ADS)

    Yan, Fan

    Understanding chemical reactions is crucial in learning chemistry at all educational levels. Nevertheless, research in science education has revealed that many students struggle to understand chemical processes. Improving teaching and learning about chemical reactions demands that we develop a clearer understanding of student reasoning in this area and of how this reasoning evolves with training in the discipline. Thus, we have carried out a qualitative study using semi-structured interviews as the main data collection tool to explore students reasoning about reaction mechanism and causality. The participants of this study included students at different levels of training in chemistry: general chemistry students (n=22), organic chemistry students (n=16), first year graduate students (n=13) and Ph.D. candidates (n=14). We identified major conceptual modes along critical dimensions of analysis, and illustrated common ways of reasoning using typical cases. Main findings indicate that although significant progress is observed in student reasoning in some areas, major conceptual difficulties seem to persist even at the more advanced educational levels. In addition, our findings suggest that students struggle to integrate important concepts when thinking about mechanism and causality in chemical reactions. The results of our study are relevant to chemistry educators interested in learning progressions, assessment, and conceptual development.

  20. [Effect of tea extracts, catechin and caffeine against type-I allergic reaction].

    PubMed

    Shiozaki, T; Sugiyama, K; Nakazato, K; Takeo, T

    1997-07-01

    The antiallergic effects of green tea, oolong tea, and black tea extracts by hot water were examined. These extracts inhibited the passive cutaneous anaphylaxis (PCA) reaction of rat after oral administration. Three tea catechins, (--)-epigallocatechin (EGC), (--)-epicatechin gallate (ECg), and (--)-epigallocatechin gallate (EGCg) isolated from green tea showed stronger inhibitory effects than that of a green tea extract on the PCA reaction. The inhibitory effects of EGC and EGCg on the PCA reaction were greater than that of ECg. Caffeine also showed a inhibitory effect on the PCA reaction. These results indicate that tea could provide a significant protection against the type-I allergic reaction. These findings also suggest that tea catechins and caffeine play an important role in having an inhibitory effect on the type-I allergic reaction.

  1. Financial competing interests were associated with favorable conclusions and greater author productivity in nonsystematic reviews of neuraminidase inhibitors.

    PubMed

    Dunn, Adam G; Zhou, Xujuan; Hudgins, Joel; Arachi, Diana; Mandl, Kenneth D; Coiera, Enrico; Bourgeois, Florence T

    2016-12-01

    To characterize the conclusions and production of nonsystematic reviews about neuraminidase inhibitors relative to financial competing interests held by the authors. We searched for articles about neuraminidase inhibitors and influenza (January 2005 to April 2015), identifying nonsystematic reviews and grading them according to the favorable/nonfavorable presentation of evidence on safety and efficacy. We recorded financial competing interests disclosed in the reviews and from other articles written by their authors. We measured associations between competing interests, author productivity, and conclusions. Among 213 nonsystematic reviews, 138 (65%) presented favorable conclusions. Financial competing interests were identified for 26% (137/532) of authors; 51% (108/213) of reviews were associated with a financial competing interest. Reviews produced exclusively by authors with financial competing interests (33%; 71/213) were more likely to present favorable conclusions than reviews with no competing interests (risk ratio 1.27; 95% confidence interval 1.03-1.55). Authors with financial competing interests published more articles about neuraminidase inhibitors than their counterparts. Half of nonsystematic reviews about neuraminidase inhibitors included an author with a financial competing interest. Reviews produced exclusively by these authors were more likely to present favorable conclusions, and authors with financial competing interests published a greater number of reviews. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. Matrix isolation infrared spectra of O2 and N2 insertion reactions with atomic uranium

    NASA Astrophysics Data System (ADS)

    Hunt, Rodney D.; Toth, L. Mac; Yustein, Jason T.; Andrews, Lester

    1993-10-01

    Laser ablation of refractory metals can be an effective source of vapor for matrix isolation IR studies. This combination of techniques was used for the first time to study the mechanisms of U vapor reactions with atmospheric components. U atoms and O2 were codeposited with excess Ar at 12 K. The dominant codeposition products were UO2 and UO3. In contrast, the UO yield was always small because UO2 is formed by an insertion mechanism. This mechanism was verified in the 16O2/18O2 experiments which failed to produce 16OU18O. The effects of UV photolysis and matrix annealings were also examined. The U atoms and O2 reaction requires little or no activation energy since UO2 was formed from cold reagents. New charge-transfer species, (UO2+2)(O2-2) and (UO+2)(O-2), and a weak complex, UO3-O2, were primarily produced under conditions which favored further O2 reactions. Similar U atom and N2 experiments produced only linear NUN which is also produced by an insertion mechanism. This U reaction represents the first time that atom was observed breaking and inserting into the triple bond of N2. Photolysis dramatically increased the NUN yield by 3-fold. Matrix annealings produced weak UN2-N2 and UN2-2N2 complexes.

  3. A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface

    NASA Astrophysics Data System (ADS)

    Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

    2017-09-01

    Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of \\text{O}2* hydrogenation reaction is much lower than that of \\text{O}2* dissociation, indicating that \\text{O}2* hydrogenation reaction is more appropriate at the first step than \\text{O}2* dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e - ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e - reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

  4. Reactions to threatening health messages.

    PubMed

    Ten Hoor, Gill A; Peters, Gjalt-Jorn Y; Kalagi, Janice; de Groot, Lianne; Grootjans, Karlijne; Huschens, Alexander; Köhninger, Constanze; Kölgen, Lizan; Pelssers, Isabelle; Schütt, Toby; Thomas, Sophia; Ruiter, Robert A C; Kok, Gerjo

    2012-11-21

    Threatening health messages that focus on severity are popular, but frequently have no effect or even a counterproductive effect on behavior change. This paradox (i.e. wide application despite low effectiveness) may be partly explained by the intuitive appeal of threatening communication: it may be hard to predict the defensive reactions occurring in response to fear appeals. We examine this hypothesis by using two studies by Brown and colleagues, which provide evidence that threatening health messages in the form of distressing imagery in anti-smoking and anti-alcohol campaigns cause defensive reactions. We simulated both Brown et al. experiments, asking participants to estimate the reactions of the original study subjects to the threatening health information (n = 93). Afterwards, we presented the actual original study outcomes. One week later, we assessed whether this knowledge of the actual study outcomes helped participants to more successfully estimate the effectiveness of the threatening health information (n = 72). Results showed that participants were initially convinced of the effectiveness of threatening health messages and were unable to anticipate the defensive reactions that in fact occurred. Furthermore, these estimates did not improve after participants had been explained the dynamics of threatening communication as well as what the effects of the threatening communication had been in reality. These findings are consistent with the hypothesis that the effectiveness of threatening health messages is intuitively appealing. What is more, providing empirical evidence against the use of threatening health messages has very little effect on this intuitive appeal.

  5. On Favorable Thermal Fields for Detached Bridgman Growth

    NASA Technical Reports Server (NTRS)

    Stelian, Carmen; Volz, Martin P.; Derby, Jeffrey J.

    2009-01-01

    The thermal fields of two Bridgman-like configurations, representative of real systems used in prior experiments for the detached growth of CdTe and Ge crystals, are studied. These detailed heat transfer computations are performed using the CrysMAS code and expand upon our previous analyses [14] that posited a new mechanism involving the thermal field and meniscus position to explain stable conditions for dewetted Bridgman growth. Computational results indicate that heat transfer conditions that led to successful detached growth in both of these systems are in accordance with our prior assertion, namely that the prevention of crystal reattachment to the crucible wall requires the avoidance of any undercooling of the melt meniscus during the growth run. Significantly, relatively simple process modifications that promote favorable thermal conditions for detached growth may overcome detrimental factors associated with meniscus shape and crucible wetting. Thus, these ideas may be important to advance the practice of detached growth for many materials.

  6. Mechanistic insight into the hydrazine decomposition on Rh(111): effect of reaction intermediate on catalytic activity.

    PubMed

    Deng, Zhigang; Lu, Xiaoqing; Wen, Zengqiang; Wei, Shuxian; Liu, Yunjie; Fu, Dianling; Zhao, Lianming; Guo, Wenyue

    2013-10-14

    Periodic density functional theory (DFT) calculations have been performed to systematically investigate the effect of reaction intermediate on catalytic activity for hydrazine (N2H4) decomposition on Rh(111). Reaction mechanisms via intramolecular and NH2-assisted N2H4 decompositions are comparatively analyzed, including adsorption configuration, reaction energy and barrier of elementary step, and reaction network. Our results show that the most favorable N2H4 decomposition pathway starts with the initial N-N bond scission to the NH2 intermediate, followed by stepwise H stripping from adsorbed N2Hx (x = 1-4) species, and finally forms the N2 and NH3 products. Comparatively, the stepwise intramolecular dehydrogenation via N2H4→ N2H3→ N2H2→ N2H → N2, and N2H4→ NH2→ NH → N with or without NH2 promotion effect, are unfavorable due to higher energy barriers encountered. Energy barrier analysis, reaction rate constants, and electronic structures are used to identify the crucial competitive route. The promotion effect of the NH2 intermediate is structurally reflected in the weakening of the N-H bond and strengthening of the N-N bond in N2Hx in the coadsorption system; it results intrinsically from the less structural deformation of the adsorbate, and weakening of the interaction between dehydrogenated fragment and departing H in transition state. Our results highlight the crucial effect of reaction intermediate on catalytic activity and provide a theoretical approach to analyze the effect.

  7. Identification of lethal reactions in the Esherichia coli metabolic network: Graph theory approach

    NASA Astrophysics Data System (ADS)

    Ghim, C.-M.; Goh, K.-I.; Kahng, B.; Kim, D.

    2004-03-01

    As a first step toward holistic modeling of cells, we analyze the biochemical reactions occurring in the genome-scale metabolism of Esherichia coli. To this end, we construct a directed bipartite graph by assigning metabolite or reaction to each node. We apply various measures of centrality, a well-known concept in the graph theory, and their modifications to the metabolic network, finding that there exist lethal reactions involved in the central metabolism. Such lethal reactions or associated enzymes under diverse environments in silico are identified and compared with earlier results obtained from flux balance analysis.

  8. Response preparation and intra-individual reaction time variability in schizophrenia.

    PubMed

    Dankinas, Denisas; Mėlynytė, Sigita; Šiurkutė, Aldona; Dapšys, Kastytis

    2016-01-01

    Background. It is important to prepare response in advance to increase the efficiency of its execution. The process of response preparation is usually studied using the precueing paradigm. In this paradigm subjects have to employ the preceding information about further imperative stimulus to perform proper response preparation, which shortens the reaction time of subsequent response execution. Previous studies detected the impairment of response preparation in schizophrenia only with the help of electroencephalographic parameters, but not with the assessing of reaction time. Therefore, in this study we attempted to find a behavioural parameter that could detect impairment in response preparation of schizophrenia patients. It was recently found that appropriate response preparation not only shortens the reaction time but also increases its stability, which is measured with the intra-individual reaction time variability. It was also revealed that response stability could better find cognitive dysfunction in some studies of schizophrenia disorder than classical behavioural parameters. Hence, the main goal of this study was to verify if intra-individual reaction time variability could detect the impairment of response preparation in schizophrenia patients. Materials and methods. In order to achieve the main purpose, we carried out a study with 14 schizophrenia patients and 14 control group subjects. We used precueing paradigm in our research, in which participants had to employ information about stimulus probability for the proper response preparation. Results. Our main result showed that despite the responses of schizophrenia patients were faster to the high-probability stimulus than to the low-probability one ( F (1, 13) = 30.9, p < 0.001), intra-individual reaction time variability did not differ in this group between the responses to more and less probable stimuli ( F (1, 13) = 0.64, p = 0.44). Conclusions. Results of the study suggest that people with

  9. Oxidation reactions of 1- and 2-naphthols: an experimental and theoretical study.

    PubMed

    Sreekanth, R; Prasanthkumar, Kavanal P; Sunil Paul, M M; Aravind, Usha K; Aravindakumar, C T

    2013-11-07

    The transients formed during the reactions of oxidizing radicals with 1-naphthol (1) and 2-naphthol (2) in aqueous medium have been investigated by pulse radiolysis with detection by absorption spectroscopy and density functional theory (DFT) calculations. The transient spectra formed on hydroxyl radical ((•)OH) reactions of 1 and 2 exhibited λ(max) at 340 and 350 nm at neutral pH. The rate constants of the (•)OH reactions of 1 (2) were determined from build-up kinetics at λ(max) of the transients as (9.63 ± 0.04) × 10(9) M(-1) s(-1) ((7.31 ± 0.11) × 10(9) M(-1) s(-1)). DFT calculations using the B3LYP/6-31+G(d,p) method have been performed to locate favorable reaction sites in both 1 and 2 and identification of the pertinent transients responsible for experimental results. Calculations demonstrated that (•)OH additions can occur mostly at C1 and C4 positions of 1, and at C1 and C8 positions of 2. Among several isomeric (•)OH adducts possible, the C1 adduct was found to be energetically most stable both in 1 and 2. Time-dependent density functional theory (TDDFT) calculations in the solution phase has shown that the experimental spectrum of 1 was mainly attributed by 1a4 (kinetically driven (•)OH-adduct) formed via the addition of (•)OH at the C4 position which was 0.73 kcal/mol endergonic compared to 1a1 (thermodynamic (•)OH adduct), whereas 2a1 (thermodynamic/kinetic (•)OH-adduct) was mainly responsible for the experimental spectrum of 2. Naphthoxyl radicals of 1 and 2 have been predicted as the transient formed in the reaction of (•)OH at basic pH. In addition, the same transient species resulted from the reactions of oxide radical ion (O(•-)) at pH ≈ 13 and azide radical (N3(•)) at pH 7 with 1 and 2. Further, UV photolysis of aqueous solutions of 1 and 2 containing H2O2 (UV/H2O2) were used for the (•)OH induced oxidation product formations up on 60% degradations of 1 and 2; profiling of the oxidation products were performed by

  10. Towards reducing DBP formation potential of drinking water by favouring direct ozone over hydroxyl radical reactions during ozonation.

    PubMed

    De Vera, Glen Andrew; Stalter, Daniel; Gernjak, Wolfgang; Weinberg, Howard S; Keller, Jurg; Farré, Maria José

    2015-12-15

    When ozonation is employed in advanced water treatment plants to produce drinking water, dissolved organic matter reacts with ozone (O3) and/or hydroxyl radicals (OH) affecting disinfection byproduct (DBP) formation with subsequently used chlorine-based disinfectants. This study presents the effects of varying exposures of O3 and •OH on DBP concentrations and their associated toxicity generated after subsequent chlorination. DBP formation potential tests and in vitro bioassays were conducted after batch ozonation experiments of coagulated surface water with and without addition of tertiary butanol (t-BuOH, 10 mM) and hydrogen peroxide (H2O2, 1 mg/mg O3), and at different pH (6-8) and transferred ozone doses (0-1 mg/mg TOC). Although ozonation led to a 24-37% decrease in formation of total trihalomethanes, haloacetic acids, haloacetonitriles, and trihaloacetamides, an increase in formation of total trihalonitromethanes, chloral hydrate, and haloketones was observed. This effect however was less pronounced for samples ozonated at conditions favoring molecular ozone (e.g., pH 6 and in the presence of t-BuOH) over •OH reactions (e.g., pH 8 and in the presence of H2O2). Compared to ozonation only, addition of H2O2 consistently enhanced formation of all DBP groups (20-61%) except trihalonitromethanes. This proves that •OH-transformed organic matter is more susceptible to halogen incorporation. Analogously, adsorbable organic halogen (AOX) concentrations increased under conditions that favor •OH reactions. The ratio of unknown to known AOX, however, was greater at conditions that promote direct O3 reactions. Although significant correlation was found between AOX and genotoxicity with the p53 bioassay, toxicity tests using 4 in vitro bioassays showed relatively low absolute differences between various ozonation conditions. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Evidence from Biochemical Pathways in Favor of Unfinished Evolution Rather than Intelligent Design

    ERIC Educational Resources Information Center

    Behrman, Edward J.; Marzluf, George A.

    2004-01-01

    An argument is made in favor of imperfect or unfinished evolution based on some metabolic pathways in which it seems that intelligent design would have done better. The case studies noted indicate the absence of highly intelligent design and are not intended as comprehensive collection but as a limited sample of inefficient situations in…

  12. Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

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

    Elimelech, Orian; Liu, Jing; Plonka, Anna M.

    Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sizedmore » NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.« less

  13. Precursor-Surface Reactions in Plasma Deposition of Silicon Thin Films

    NASA Astrophysics Data System (ADS)

    Bakos, Tamas

    2005-03-01

    Device-quality hydrogenated amorphous silicon (a-Si:H) thin films are usually grown by plasma deposition under conditions where the SiH3 radical is the dominant deposition precursor. In this presentation, we report results of first-principles density functional theory calculations on the interactions of the SiH3 radical with the crystalline Si(100)-(2x1):H surface in conjunction with molecular-dynamics simulations of a-Si:H thin film growth by SiH3 radicals, which elucidate the pathways and energetics of surface reactions that govern important film properties. In particular, we show that an SiH3 radical can insert into strained surface Si-Si dimer bonds, abstract surface H through an Eley-Rideal mechanism, and passivate surface dangling bonds; these reactions follow exothermic and barrierless pathways that lead to a temperature-independent growth rate in agreement with experimental measurements. We also identify a thermally activated surface H abstraction process, in which the SiH3 radical diffuses through overcoordinated surface Si atoms until it encounters a favorable site for H abstraction; the diffusion and H-abstraction steps have commensurate activation barriers. This mechanism explains partly the reduction of the film H content at elevated substrate temperatures.

  14. Targeted Control of Permeability Using Carbonate Dissolution/Precipitation Reactions

    NASA Astrophysics Data System (ADS)

    Clarens, A. F.; Tao, Z.; Plattenberger, D.

    2016-12-01

    Targeted mineral precipitation reactions are a promising approach for controlling fluid flow in the deep subsurface. Here we studied the potential to use calcium and magnesium bearing silicates as cation donors that would react with aqueous phase CO2 under reservoir conditions to form solid carbonate precipitates. Preliminary experiments in high pressure and temperature columns suggest that these reactions can effectively lower the permeability of a porous media. Wollastonite (CaSiO3) was used as the model silicate, injected as solid particles into the pore space of a packed column, which was then subsequently flooded with CO2(aq). The reactions occur spontaneously, leveraging the favorable kinetics that occur at the high temperature and pressure conditions characteristic of the deep subsurface, to form solid phase calcium carbonate (CaCO3) and amorphous silica (SiO2) within the pore space. Both x-ray tomography imaging of reacted columns and electron microscopy imaging of thin sections were used to characterize where dissolution/precipitation occurred within the porous media. The spatial distribution of the products was closely tied to the flow rate and the duration of the experiment. The SiO2 product precipitated in close spatial proximity to the CaSiO3 reactant. The CaCO3 product, which is sensitive to the low pH and high pCO2 brine, precipitated out of solution further down the column as Ca2+ ions moved with the brine. The permeability of the columns decreased by several orders of magnitude after injecting the CaSiO3 particles. Following carbonation, the permeability decreased even further as precipitates filled flow paths within the pore network. A pore network model was developed to help understand the interplay between precipitation kinetics and flow in altering the permeability of the porous media. The effect of particle concentration and size, pore size, reaction time, and pCO2, are explored on pore/fracture aperture and reaction extent. To provide better

  15. The Phase Behavior Effect on the Reaction Engineering of Transesterification Reactions and Reactor Design for Continuous Biodiesel Production

    NASA Astrophysics Data System (ADS)

    Csernica, Stephen N.

    transitions from two phases to a single phase, or pseudo-single phase. The transition to a single phase or pseudo-single phase is a function of the methanol content. Regardless, the maximum observed reaction rate occurs at the point of the phase transition, when the concentration of triglycerides in the methanol phase is largest. The phase transition occurs due to the accumulation of the primary product, biodiesel methyl esters. Through various experiments, it was determined that the rate of the triglyceride mass transfer into the methanol phase, as well as the solubility of triglycerides in methanol, increases with increasing methyl ester concentration. Thus, there exists some critical methyl ester concentration which favors the formation of a single or pseudo-single phase system. The effect of the by-product glycerol on the reaction kinetics was also investigated. It was determined that at low methanol to triglyceride molar ratios, glycerol acts to inhibit the reaction rate and limit the overall triglyceride conversion. This occurs because glycerol accumulates in the methanol phase, i.e. the primary reaction volume. When glycerol is at relatively high concentrations within the methanol phase, triglycerides become excluded from the reaction volume. This greatly reduces the reaction rate and limits the overall conversion. As the concentration of methanol is increased, glycerol becomes diluted and the inhibitory effects become dampened. Assuming pseudo-homogeneous phase behavior, a simple kinetic model incorporating the inhibitory effects of glycerol was proposed based on batch reactor data. The kinetic model was primarily used to theoretically compare the performance of different types of continuous flow reactors for continuous biodiesel production. It was determined that the inhibitory effects of glycerol result in the requirement of very large reactor volumes when using continuous stirred tank reactors (CSTR). The reactor volume can be greatly reduced using tubular style

  16. Reaction Decoder Tool (RDT): extracting features from chemical reactions.

    PubMed

    Rahman, Syed Asad; Torrance, Gilliean; Baldacci, Lorenzo; Martínez Cuesta, Sergio; Fenninger, Franz; Gopal, Nimish; Choudhary, Saket; May, John W; Holliday, Gemma L; Steinbeck, Christoph; Thornton, Janet M

    2016-07-01

    Extracting chemical features like Atom-Atom Mapping (AAM), Bond Changes (BCs) and Reaction Centres from biochemical reactions helps us understand the chemical composition of enzymatic reactions. Reaction Decoder is a robust command line tool, which performs this task with high accuracy. It supports standard chemical input/output exchange formats i.e. RXN/SMILES, computes AAM, highlights BCs and creates images of the mapped reaction. This aids in the analysis of metabolic pathways and the ability to perform comparative studies of chemical reactions based on these features. This software is implemented in Java, supported on Windows, Linux and Mac OSX, and freely available at https://github.com/asad/ReactionDecoder : asad@ebi.ac.uk or s9asad@gmail.com. © The Author 2016. Published by Oxford University Press.

  17. Maillard reaction versus other nonenzymatic modifications in neurodegenerative processes.

    PubMed

    Pamplona, Reinald; Ilieva, Ekaterina; Ayala, Victoria; Bellmunt, Maria Josep; Cacabelos, Daniel; Dalfo, Esther; Ferrer, Isidre; Portero-Otin, Manuel

    2008-04-01

    Nonenzymatic protein modifications are generated from direct oxidation of amino acid side chains and from reaction of the nucleophilic side chains of specific amino acids with reactive carbonyl species. These reactions give rise to specific markers that have been analyzed in different neurodegenerative diseases sharing protein aggregation, such as Alzheimer's disease, Pick's disease, Parkinson's disease, dementia with Lewy bodies, Creutzfeldt-Jakob disease, and amyotrophic lateral sclerosis. Collectively, available data demonstrate that oxidative stress homeostasis, mitochondrial function, and energy metabolism are key factors in determining the disease-specific pattern of protein molecular damage. In addition, these findings suggest the lack of a "gold marker of oxidative stress," and, consequently, they strengthen the need for a molecular dissection of the nonenzymatic reactions underlying neurodegenerative processes.

  18. Hidden charm pentaquark and Λ(1405) in the Λb0 →ηcK- p (πΣ) reaction

    NASA Astrophysics Data System (ADS)

    Xie, Ju-Jun; Liang, Wei-Hong; Oset, Eulogio

    2018-02-01

    We have performed a study of the Λb0 →ηcK- p and Λb0 →ηc πΣ reactions based on the dominant Cabibbo favored weak decay mechanism. We show that the K- p produced only couples to Λ* states, not Σ* and that the πΣ state is only generated from final state interaction of K bar N and ηΛ channels which are produced in a primary stage. This guarantees that the πΣ state is generated in isospin I = 0 and we see that the invariant mass produces a clean signal for the Λ (1405) of higher mass at 1420 MeV. We also study the ηc p final state interaction, which is driven by the excitation of a hidden charm resonance predicted before. We relate the strength of the different invariant mass distributions and find similar strengths that should be clearly visible in an ongoing LHCb experiment. In particular we predict that a clean peak should be seen for a hidden charm resonance that couples to the ηc p channel in the invariant ηc p mass distribution.

  19. Suppression of single-wall carbon nanotube redox reaction by adsorbed proteins

    NASA Astrophysics Data System (ADS)

    Nakayama, Tomohito; Tanaka, Takeshi; Shiraki, Kentaro; Hase, Muneaki; Hirano, Atsushi

    2018-07-01

    Single-wall carbon nanotubes (SWCNTs) are widely used in biological applications. In biological systems, proteins readily adsorb to SWCNTs. However, little is known about the effects of proteins on the physicochemical properties of SWCNTs, such as their redox reaction. In this study, we measured the absorption and Raman spectra of SWCNTs dispersed in the presence of proteins such as bovine serum albumin to observe the redox reaction of the protein-adsorbed SWCNTs. The adsorbed proteins suppressed the redox reaction by forming thick and dense layers around the SWCNTs. Our findings are useful for understanding the behaviors of SWCNTs in biological systems.

  20. Complete characterization of the constrained geometry bimolecular reaction O(1D)+N2O-->NO+NO by three-dimensional velocity map imaging

    NASA Astrophysics Data System (ADS)

    Gödecke, Niels; Maul, Christof; Chichinin, Alexey I.; Kauczok, Sebastian; Gericke, Karl-Heinz

    2009-08-01

    The bimolecular reaction O(D1)+N2O→NO+NO was photoinitiated in the (N2O)2 dimer at a wavelength of 193 nm and was investigated by three-dimensional (3D) velocity map imaging. State selective 3D momentum vector distributions were monitored and analyzed. For the first time, kinetic energy resolution and stereodynamic information about the reaction under constrained geometry conditions is available. Directly observable NO products exhibit moderate vibrational excitation and are rotationally and translationally cold. Speed and spatial distributions suggest a pronounced backward scattering of the observed products with respect to the direction of motion of the O(D1) atom. Forward scattered partner products, which are not directly detectable are also translationally cold, but carry very large internal energy as vibration or rotation. The results confirm and extend previous studies on the complex initiated reaction system. The restricted geometry of the van der Waals complex seems to favor an abstraction reaction of the terminal nitrogen atom by the O(D1) atom, which is in striking contrast to the behavior observed for the unrestricted gas phase reaction under bulk conditions.

  1. The reaction of formic acid with RaneyTM copper

    NASA Astrophysics Data System (ADS)

    Callear, Samantha K.; Silverwood, Ian P.; Chutia, Arunabhiram; Catlow, C. Richard A.; Parker, Stewart F.

    2016-04-01

    The interaction of formic acid with RaneyTM Cu proves to be complex. Rather than the expected generation of a monolayer of bidentate formate, we find the formation of a Cu(II) compound. This process occurs by direct reaction of copper and formic acid; in contrast, previous methods are by solution reaction. This is a rare example of formic acid acting as an oxidant rather than, as more commonly found, a reductant. The combination of diffraction, spectroscopic and computational methods has allowed this unexpected process to be characterized.

  2. Influence of reactions heats on variation of radius, temperature, pressure and chemical species amounts within a single acoustic cavitation bubble.

    PubMed

    Kerboua, Kaouther; Hamdaoui, Oualid

    2018-03-01

    The scientific interest toward the study of acoustic bubble is mainly explained by its practical benefit in providing a reactional media favorable to the rapid evolution of chemical mechanism. The evolution of this mechanism is related to the simultaneous and dependent variation of the volume, temperature and pressure within the bubble, retrieved by the resolution of a differential equations system, including among others the thermal balance. This last one is subject to different assumptions, some authors deem simply that the temperature varies adiabatically during the collapsing phase, without considering the reactions heat of the studied mechanism. This paper aims to evaluate the pertinence of neglecting reactions heats in the thermal balance, by analyzing their effect on the variation of radius, temperature, pressure and chemical species amounts. The results show that the introduction of reactions heats conducts to a decrease of the temperature, an increase of the pressure and a reduction of the bubble volume. As a consequence, this leads to a drop of the quantities of free radicals produced by the chemical mechanism evolving within the bubble. This paper also proved that the impact of the consideration of reactions heats is dependent of the frequency and the acoustic amplitude of the ultrasonic wave. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

    PubMed

    Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

    2016-09-01

    The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.

  4. Coming out during adolescence: Perceived parents' reactions and internalized sexual stigma.

    PubMed

    Baiocco, Roberto; Fontanesi, Lilybeth; Santamaria, Federica; Ioverno, Salvatore; Baumgartner, Emma; Laghi, Fiorenzo

    2016-08-01

    Disclosing sexual orientation to parents is a challenging developmental task for lesbian and gay adolescents. The aim of the study is to investigate parental negative reaction to coming out, which is associated with high levels of internalized sexual stigma and psychological problems. Participants' perceptions of their parents' reactions, age at coming out, gender, parental political orientation and religiosity, family functioning, and internalized sexual stigma were assessed in 150 Italian homosexual adolescents. Findings confirm that negative parental reactions are connected to poor family functioning and strong beliefs in traditional values. Path analysis results identified that negative reaction to coming out mediates the effect between a more rigid family functioning and internalized sexual stigma. Implications for clinical and social fields are discussed. © The Author(s) 2014.

  5. Al-, Y-, and La-doping effects favoring intrinsic and field induced ferroelectricity in HfO2: A first principles study

    NASA Astrophysics Data System (ADS)

    Materlik, Robin; Künneth, Christopher; Falkowski, Max; Mikolajick, Thomas; Kersch, Alfred

    2018-04-01

    III-valent dopants have shown to be most effective in stabilizing the ferroelectric, crystalline phase in atomic layer deposited, polycrystalline HfO2 thin films. On the other hand, such dopants are commonly used for tetragonal and cubic phase stabilization in ceramic HfO2. This difference in the impact has not been elucidated so far. The prospect is a suitable doping to produce ferroelectric HfO2 ceramics with a technological impact. In this paper, we investigate the impact of Al, Y, and La doping, which have experimentally proven to stabilize the ferroelectric Pca21 phase in HfO2, in a comprehensive first-principles study. Density functional theory calculations reveal the structure, formation energy, and total energy of various defects in HfO2. Most relevant are substitutional electronically compensated defects without oxygen vacancy, substitutional mixed compensated defects paired with a vacancy, and ionically compensated defect complexes containing two substitutional dopants paired with a vacancy. The ferroelectric phase is strongly favored with La and Y in the substitutional defect. The mixed compensated defect favors the ferroelectric phase as well, but the strongly favored cubic phase limits the concentration range for ferroelectricity. We conclude that a reduction of oxygen vacancies should significantly enhance this range in Y doped HfO2 thin films. With Al, the substitutional defect hardly favors the ferroelectric phase before the tetragonal phase becomes strongly favored with the increasing concentration. This could explain the observed field induced ferroelectricity in Al-doped HfO2. Further Al defects are investigated, but do not favor the f-phase such that the current explanation remains incomplete for Al doping. According to the simulation, doping alone shows clear trends, but is insufficient to replace the monoclinic phase as the ground state. To explain this fact, some other mechanism is needed.

  6. The Color Red Supports Avoidance Reactions to Unhealthy Food.

    PubMed

    Rohr, Michaela; Kamm, Friederike; Koenigstorfer, Joerg; Groeppel-Klein, Andrea; Wentura, Dirk

    2015-01-01

    Empirical evidence suggests that the color red acts like an implicit avoidance cue in food contexts. Thus specific colors seem to guide the implicit evaluation of food items. We built upon this research by investigating the implicit meaning of color (red vs. green) in an approach-avoidance task with healthy and unhealthy food items. Thus, we examined the joint evaluative effects of color and food: Participants had to categorize food items by approach-avoidance reactions, according to their healthfulness. Items were surrounded by task-irrelevant red or green circles. We found that the implicit meaning of the traffic light colors influenced participants' reactions to the food items. The color red (compared to green) facilitated automatic avoidance reactions to unhealthy foods. By contrast, approach behavior toward healthy food items was not moderated by color. Our findings suggest that traffic light colors can act as implicit cues that guide automatic behavioral reactions to food.

  7. Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species With Application to DSMC Simulations

    NASA Technical Reports Server (NTRS)

    Liechty, Derek S.

    2013-01-01

    The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for nearequilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion of the heating and is then compared to the total heating measured in flight.

  8. Theoretical study on the gas-phase reaction mechanism between palladium monoxide and methane.

    PubMed

    Yang, Hua-Qing; Hu, Chang-Wei; Gao, Chao; Yang, Meng-Yao; Li, Fang-Ming; Li, Cai-Qin; Li, Xiang-Yuan

    2011-12-01

    The gas-phase reaction mechanism between palladium monoxide and methane has been theoretically investigated on the singlet and triplet state potential energy surfaces (PESs) at the CCSD(T)/AVTZ//B3LYP/6-311+G(2d, 2p), SDD level. The major reaction channel leads to the products PdCH(2) + H(2)O, whereas the minor channel results in the products Pd + CH(3)OH, CH(2)OPd + H(2), and PdOH + CH(3). The minimum energy reaction pathway for the formation of main products (PdCH(2) + H(2)O), involving one spin inversion, prefers to start at the triplet state PES and afterward proceed along the singlet state PES, where both CH(3)PdOH and CH(3)Pd(O)H are the critical intermediates. Furthermore, the rate-determining step is RS-CH(3) PdOH → RS-2-TS1cb → RS-CH(2)Pd(H)OH with the rate constant of k = 1.48 × 10(12) exp(-93,930/RT). For the first C-H bond cleavage, both the activation strain ΔE(≠)(strain) and the stabilizing interaction ΔE(≠)(int) affect the activation energy ΔE(≠), with ΔE(≠)(int) in favor of the direct oxidative insertion. On the other hand, in the PdCH(2) + H(2) O reaction, the main products are Pd + CH(3)OH, and CH(3)PdOH is the energetically preferred intermediate. In the CH(2)OPd + H(2) reaction, the main products are Pd + CH(3)OH with the energetically preferred intermediate H(2)PdOCH(2). In the Pd + CH(3)OH reaction, the main products are CH(2)OPd + H(2), and H(2)PdOCH(2) is the energetically predominant intermediate. The intermediates, PdCH(2), H(2) PdCO, and t-HPdCHO are energetically preferred in the PdC + H(2), PdCO + H(2), and H(2)Pd + CO reactions, respectively. Besides, PdO toward methane activation exhibits higher reaction efficiency than the atom Pd and its first-row congener NiO. Copyright © 2011 Wiley Periodicals, Inc.

  9. Reactions to threatening health messages

    PubMed Central

    2012-01-01

    Background Threatening health messages that focus on severity are popular, but frequently have no effect or even a counterproductive effect on behavior change. This paradox (i.e. wide application despite low effectiveness) may be partly explained by the intuitive appeal of threatening communication: it may be hard to predict the defensive reactions occurring in response to fear appeals. We examine this hypothesis by using two studies by Brown and colleagues, which provide evidence that threatening health messages in the form of distressing imagery in anti-smoking and anti-alcohol campaigns cause defensive reactions. Methods We simulated both Brown et al. experiments, asking participants to estimate the reactions of the original study subjects to the threatening health information (n = 93). Afterwards, we presented the actual original study outcomes. One week later, we assessed whether this knowledge of the actual study outcomes helped participants to more successfully estimate the effectiveness of the threatening health information (n = 72). Results Results showed that participants were initially convinced of the effectiveness of threatening health messages and were unable to anticipate the defensive reactions that in fact occurred. Furthermore, these estimates did not improve after participants had been explained the dynamics of threatening communication as well as what the effects of the threatening communication had been in reality. Conclusions These findings are consistent with the hypothesis that the effectiveness of threatening health messages is intuitively appealing. What is more, providing empirical evidence against the use of threatening health messages has very little effect on this intuitive appeal. PMID:23171445

  10. Extent of reaction in open systems with multiple heterogeneous reactions

    USGS Publications Warehouse

    Friedly, John C.

    1991-01-01

    The familiar batch concept of extent of reaction is reexamined for systems of reactions occurring in open systems. Because species concentrations change as a result of transport processes as well as reactions in open systems, the extent of reaction has been less useful in practice in these applications. It is shown that by defining the extent of the equivalent batch reaction and a second contribution to the extent of reaction due to the transport processes, it is possible to treat the description of the dynamics of flow through porous media accompanied by many chemical reactions in a uniform, concise manner. This approach tends to isolate the reaction terms among themselves and away from the model partial differential equations, thereby enabling treatment of large problems involving both equilibrium and kinetically controlled reactions. Implications on the number of coupled partial differential equations necessary to be solved and on numerical algorithms for solving such problems are discussed. Examples provided illustrate the theory applied to solute transport in groundwater flow.

  11. Correlates of Perceived Favorability of Online Courses for Quantitative versus Qualitative Undergraduate Business Majors

    ERIC Educational Resources Information Center

    Blau, Gary; Pred, Robert; Drennan, Rob B., Jr.; Kapanjie, Darin

    2016-01-01

    An online survey tested the association among background, technological, and course-related variables with perceived favorability of online courses for two independent samples of fall 2015 and spring 2016 business undergraduates taking at least one online or hybrid course. Results showed that perceived learning was a consistent positive correlate…

  12. The risk for cross-reactions after a cutaneous delayed-type hypersensitivity reaction to heparin preparations is independent of their molecular weight: a systematic review.

    PubMed

    Weberschock, Tobias; Meister, Anna Christina; Bohrt, Kevin; Schmitt, Jochen; Boehncke, Wolf-Henning; Ludwig, Ralf J

    2011-10-01

    Heparins are a widely used class of drugs known to cause delayed-type hypersensitivity (DTH) reactions. Recent publications indicate that the incidence of these may be higher than previously thought. To date, patient-related but no drug-related risk factors for the development of DTH reactions to heparins have been identified, although molecular weight is discussed as a potentially relevant parameter. To address this, a systematic review was conducted on the frequency of cross-reactions after DTH reactions to heparin preparations. We electronically searched MEDLINE and EMBASE, hand-searched selected journals and references, and contacted experts for unpublished data. Sixty-six publications and unpublished data of 14 patients resulted in 198 patients with 1084 tests for cross-reactivity. The primary causative agents were mostly unfractionated heparin (50%) and low molecular weight heparins (49.5%). Cross-reactions were more likely after an initial DTH reaction to unfractionated heparin than after an initial DTH reaction to low molecular weight heparin. Our findings also indicate that molecular weight does not correlate with the risk for cross-reactivity, which is in line with recent observations, indicating that different heparins have to be individually considered. The available data demonstrated the lowest overall risk for cross-reactions for pentosan polysulfate (36.4%) and fondaparinux (10.4%). In the clinical context, fondaparinux is recommended as the current best alternative when a DTH reaction occurs. © 2011 John Wiley & Sons A/S.

  13. Effects of Favorable Alleles for Water-Soluble Carbohydrates at Grain Filling on Grain Weight under Drought and Heat Stresses in Wheat

    PubMed Central

    Chang, Xiaoping; Li, Runzhi; Jing, Ruilian

    2014-01-01

    Drought, heat and other abiotic stresses during grain filling can result in reductions in grain weight. Conserved water-soluble carbohydrates (WSC) at early grain filling play an important role in partial compensation of reduced carbon supply. A diverse population of 262 historical winter wheat accessions was used in the present study. There were significant correlations between 1000-grain weight (TGW) and four types of WSC, viz. (1) total WSC at the mid-grain filling stage (14 days after flowering) produced by leaves and non-leaf organs; (2) WSC contributed by current leaf assimilation during the mid-grain filling; (3) WSC in non-leaf organs at the mid-grain filling, excluding the current leaf assimilation; and (4) WSC used for respiration and remobilization during the mid-grain filling. Association and favorable allele analyses of 209 genome-wide SSR markers and the four types of WSC were conducted using a mixed linear model. Seven novel favorable WSC alleles exhibited positive individual contributions to TGW, which were verified under 16 environments. Dosage effects of pyramided favorable WSC alleles and significantly linear correlations between the number of favorable WSC alleles and TGW were observed. Our results suggested that pyramiding more favorable WSC alleles was effective for improving both WSC and grain weight in future wheat breeding programs. PMID:25036550

  14. Applicability of PM3 to transphosphorylation reaction path: Toward designing a minimal ribozyme

    NASA Technical Reports Server (NTRS)

    Manchester, John I.; Shibata, Masayuki; Setlik, Robert F.; Ornstein, Rick L.; Rein, Robert

    1993-01-01

    A growing body of evidence shows that RNA can catalyze many of the reactions necessary both for replication of genetic material and the possible transition into the modern protein-based world. However, contemporary ribozymes are too large to have self-assembled from a prebiotic oligonucleotide pool. Still, it is likely that the major features of the earliest ribozymes have been preserved as molecular fossils in the catalytic RNA of today. Therefore, the search for a minimal ribozyme has been aimed at finding the necessary structural features of a modern ribozyme (Beaudry and Joyce, 1990). Both a three-dimensional model and quantum chemical calculations are required to quantitatively determine the effects of structural features of the ribozyme on the reaction it catalyzes. Using this model, quantum chemical calculations must be performed to determine quantitatively the effects of structural features on catalysis. Previous studies of the reaction path have been conducted at the ab initio level, but these methods are limited to small models due to enormous computational requirements. Semiempirical methods have been applied to large systems in the past; however, the accuracy of these methods depends largely on a simple model of the ribozyme-catalyzed reaction, or hydrolysis of phosphoric acid. We find that the results are qualitatively similar to ab initio results using large basis sets. Therefore, PM3 is suitable for studying the reaction path of the ribozyme-catalyzed reaction.

  15. Perceptual Incongruity and Social Interaction as Determinants of Infants' Reaction to Novel Persons

    ERIC Educational Resources Information Center

    Greenberg, David J.; And Others

    1975-01-01

    A study on the effects of birth order on infants' reactions to novel persons was conducted to test the differing predictions of incongruity theory and social interaction theory. Findings indicated that infants' reactions to novel persons are determined by infants' social interaction within the family during the first year rather than by the number…

  16. Hyperthyroid dementia: clinicoradiological findings and response to treatment.

    PubMed

    Fukui, T; Hasegawa, Y; Takenaka, H

    2001-02-15

    Dementia associated with hyperthyroidism is less well documented than is hypothyroid dementia. Therapeutic response of hyperthyroid dementia and associated cerebral circulatory and/or metabolic abnormalities has not been elucidated. We described a patient with hyperthyroid dementia and clinicoradiological response to treatment. Single photon emission computed tomographic (SPECT) study was repeated and analyzed semiquantitatively. A 67-year-old man experienced progressive impairments of attention, memory, constructive skills and behavior as well as hand tremor and weight loss of two-year duration. Laboratory findings were compatible with Graves' disease. The initial SPECT showed diffuse tracer uptake defect with an accentuation in the bilateral temporoparietal regions. Clinical and SPECT findings both suggested concurrent "possible" Alzheimer's disease. However, initial treatment with a beta-blocker improved behavior and attention-related cognitive functions as well as tracer uptake in the frontal lobes. Subsequent treatment with additional methimazole then improved memory and constructive abilities when a euthyroid state was established. Uptake defect in the temporoparietal regions also responded gradually to the medication. We suggest that the present patient represent hyperthyroid dementia, which responds favorably to treatment with regard to clinical symptoms and SPECT findings. We also suggest that thyroid function be measured in patients with "possible" Alzheimer's disease because treatable hyperthyroid dementia may not be identified.

  17. Effect of edaravone on favorable outcome in patients with acute cerebral large vessel occlusion: subanalysis of RESCUE-Japan Registry.

    PubMed

    Miyaji, Yuki; Yoshimura, Shinichi; Sakai, Nobuyuki; Yamagami, Hiroshi; Egashira, Yusuke; Shirakawa, Manabu; Uchida, Kazutaka; Kageyama, Hirohito; Tomogane, Yusuke

    2015-01-01

    The data of the nationwide prospective registry of acute cerebral large vessel occlusion (LVO; RESCUE-Japan Registry) were analyzed to know the effect of edaravone, a free radical scavenger, on clinical outcome at 90 days after onset. In this registry, patients with acute cerebral LVO admitted within 24 h after onset were prospectively registered. The effect of various factors including endovascular treatment (EVT), intravenous recombinant tissue plasminogen activator (IV rt-PA), and other medication including edaravone on favorable outcome (modified Rankin scale 0-1) was analyzed. Of the 1,454 registered patients, 1,442 patients (99.2%) had the information of edaravone were analyzed. In total, edaravone group had more patients with favorable outcome compared to non-edaravone group (22.9% vs. 13.8%, p = 0.0006). Edaravone increased favorable outcome in patients treated with IV rt-PA (29.4% vs. 11.1%, p = 0.0107), but not with EVT (21.2% vs. 13.9%, p = 0.309). Logistic regression analysis revealed that higher National Institutes of Health Stroke Scale (NIHSS) score on admission [odds ratio (OR) 0.875, 95% confidence interval (CI) 0.858-0.894] and advanced age (OR 0.963, 95%CI 0.952-0.975) were significantly related to unfavorable outcome. In contrast, IV rt-PA (OR 2.489, 95%CI 1.867-3.319), EVT (OR 1.375, 95%CI 1.013-1.865), and edaravone (OR 1.483, 95%CI 1.027-2.143) were significantly associated with favorable outcome. This analysis indicated that IV rt-PA, EVT, and edaravone were effective to obtain favorable outcome in patients with acute LVO. Combination IV rt-PA with edaravone was more effective.

  18. Analyzing powers in the three-body break-up reactions from 3overlineHe + 2H

    NASA Astrophysics Data System (ADS)

    Okumuşoǧlu, Nazmi T.; Basak, A. K.; Blyth, C. O.

    1980-11-01

    Analyzing powers and cross sections of the 2H( 3overlineHe, pp ) 3H, 2H( 3overlineHe, pt) 1H and2H( 3overlineHe, p 3He) n reactions have been measured as a function of the energy of the detected proton. Two of the outgoing particles were identified and detected in coincidence with several forward-angle geometries. The analyzing powers found were generally small but non-zero. However, at kinematical conditions favoring the final-state interactions between proton and triton (or neutron and helion) large values up to 0.4 were found. The results are discussed with respect to the level structure of 4He.

  19. Does Spontaneous Favorability to Power (vs. Universalism) Values Predict Spontaneous Prejudice and Discrimination?

    PubMed

    Souchon, Nicolas; Maio, Gregory R; Hanel, Paul H P; Bardin, Brigitte

    2017-10-01

    We conducted five studies testing whether an implicit measure of favorability toward power over universalism values predicts spontaneous prejudice and discrimination. Studies 1 (N = 192) and 2 (N = 86) examined correlations between spontaneous favorability toward power (vs. universalism) values, achievement (vs. benevolence) values, and a spontaneous measure of prejudice toward ethnic minorities. Study 3 (N = 159) tested whether conditioning participants to associate power values with positive adjectives and universalism values with negative adjectives (or inversely) affects spontaneous prejudice. Study 4 (N = 95) tested whether decision bias toward female handball players could be predicted by spontaneous attitude toward power (vs. universalism) values. Study 5 (N = 123) examined correlations between spontaneous attitude toward power (vs. universalism) values, spontaneous importance toward power (vs. universalism) values, and spontaneous prejudice toward Black African people. Spontaneous positivity toward power (vs. universalism) values was associated with spontaneous negativity toward minorities and predicted gender bias in a decision task, whereas the explicit measures did not. These results indicate that the implicit assessment of evaluative responses attached to human values helps to model value-attitude-behavior relations. © 2016 The Authors. Journal of Personality Published by Wiley Periodicals, Inc.

  20. The Reactions of Polycyclic Aromatic Hydrocarbons with OH

    NASA Technical Reports Server (NTRS)

    Ricca, Alessandra; Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)

    2000-01-01

    The OH radical adds to naphthalene and naphthalene cation without a barrier. For the neutrals, the most favorable path for this intermediate is the loss of the OH, and the next most favorable option is the loss of an H atom to form the alcohol. For the cation, the most favorable path appears to be a hydrogen migration followed by the loss of a hydrogen to form the alcohol. The OH at carbon atom 1 is energetically most favorable for both the initial complex and final product. This is true for both the neutrals and cations.

  1. Useful visual field in patients with schizophrenia: a choice reaction time study.

    PubMed

    Matsuda, Yukihisa; Matsui, Mie; Tonoya, Yasuhiro; Ebihara, Naokuni; Kurachi, Masayoshi

    2011-04-01

    This study examined the size of the useful visual field in patients (9 men, 6 women) with schizophrenia. A choice reaction task was conducted, and performances at 2.5, 5, 7, 10, and 25 degrees in both visual fields were measured. Three key findings were shown. First, patients had slower choice reaction times (choice RTs) than normal controls. Second, patients had slower choice RTs in the right visual field than in the left visual field. Third, patients and normal controls showed the same U-shaped choice RT pattern. The first and second findings were consistent with those of other studies. The third finding was a clear indication of the patients' performance in peripheral vision, and a comparison with normal controls suggested that there was no difference in the size of the useful visual field, at least within

  2. Reaction Extrema: Extent of Reaction in General Chemistry

    ERIC Educational Resources Information Center

    Vandezande, Jonathon E.; Vander Griend, Douglas A.; DeKock, Roger L.

    2013-01-01

    Nearly 100 years ago de Donder introduced the term "extent of reaction", ?. We build on that work by defining the concept of reagent extrema for an arbitrary chemical reaction, aA + bB [reversible reaction] yY + zZ. The central equation is ?^[subscript i] = -n[subscript i,0]/?[subscript i]. The symbol ?^[subscript i] represents the…

  3. Attributions of responsibility and affective reactions to decision outcomes.

    PubMed

    Zeelenberg, M; van der Pligt, J; de Vries, N K

    2000-06-01

    Immediate affective reactions to outcomes are more intense following decisions to act than following decisions not to act. This finding holds for both positive and negative outcomes. We relate this "actor-effect" to attribution theory and argue that decision makers are seen as more responsible for outcomes when these are the result of a decision to act as compared to a decision not to act. Experiment 1 (N = 80) tests the main assumption underlying our reasoning and shows that affective reactions to decision outcomes are indeed more intense when the decision maker is seen as more responsible. Experiment 2 (N = 40) tests whether the actor effect can be predicted on the basis of differential attributions following action and inaction. Participants read vignettes in which active and passive actors obtained a positive or negative outcome. Action resulted in more intense affect than inaction, and positive outcomes resulted in more intense affect than negative outcomes. Experiment 2 further shows that responsibility attributions and affective reactions to outcomes are highly correlated; that is, more extreme affective reactions are associated with more internal attributions. We discuss the implications for research on post-decisional reactions.

  4. Microsomal oxidation of tribromoethylene and reactions of tribromoethylene oxide.

    PubMed

    Yoshioka, Tadao; Krauser, Joel A; Guengerich, F Peter

    2002-11-01

    Halogenated olefins are of interest because of their widespread use in industry and their potential toxicity to humans. Epoxides are among the enzymatic oxidation products and have been studied in regard to their toxicity. Most of the attention has been given to chlorinated epoxides, and we have previously studied the reactions of the mono-, di-, tri-, and tetrachloroethylene oxides. To further test some hypotheses concerning the reactivity of these compounds, we prepared tribromoethylene (TBE) oxide and compared it to trichloroethylene (TCE) oxide and other chlorinated epoxides. TBE oxide reacted with H(2)O about 3 times faster than did TCE oxide. Several hydrolysis products of TBE oxide were the same as formed from TCE oxide, i.e., glyoxylic acid, CO, and HCO(2)H. Br(2)CHCO(2)H was formed from TBE oxide; the yield was higher than for Cl(2)CHCO(2)H formed in the hydrolysis of TCE oxide. The yield of tribromoacetaldehyde was < 0.4% in aqueous buffer (pH 7.4). In rat liver microsomal incubations containing TBE and NADPH, Br(2)CHCO(2)H was a major product, and tribromoacetaldehyde was a minor product. These results are consistent with schemes previously developed for halogenated epoxides, with migration of bromine being more favorable than for chlorine. Reaction of TBE oxide with lysine yielded relatively more N-dihaloacetyllysine and less N-formyllysine than in the case of TCE oxide. This same pattern was observed in the products of the reaction of TBE oxide with the lysine residues in bovine serum albumin. We conclude that the proposed scheme of hydrolysis of halogenated epoxides follows the expected halide order and that this can be used to rationalize patterns of hydrolysis and reactivity of other halogenated epoxides.

  5. Social media for message testing: a multilevel approach to linking favorable viewer responses with message, producer, and viewer influence on YouTube.

    PubMed

    Paek, Hye-Jin; Hove, Thomas; Jeon, Jehoon

    2013-01-01

    To explore the feasibility of social media for message testing, this study connects favorable viewer responses to antismoking videos on YouTube with the videos' message characteristics (message sensation value [MSV] and appeals), producer types, and viewer influences (viewer rating and number of viewers). Through multilevel modeling, a content analysis of 7,561 viewer comments on antismoking videos is linked with a content analysis of 87 antismoking videos. Based on a cognitive response approach, viewer comments are classified and coded as message-oriented thought, video feature-relevant thought, and audience-generated thought. The three mixed logit models indicate that videos with a greater number of viewers consistently increased the odds of favorable viewer responses, while those presenting humor appeals decreased the odds of favorable message-oriented and audience-generated thoughts. Some significant interaction effects show that videos produced by laypeople may hinder favorable viewer responses, while a greater number of viewer comments can work jointly with videos presenting threat appeals to predict favorable viewer responses. Also, for a more accurate understanding of audience responses to the messages, nuance cues should be considered together with message features and viewer influences.

  6. Resonances at very low temperature for the reaction D2 + H

    NASA Astrophysics Data System (ADS)

    Simbotin, I.; Côté, R.

    2017-05-01

    We present numerical results for rate coefficients of reaction and vibrational quenching in the collision of H with {{{D}}}2(v,j) at cold and ultracold temperatures. We explore both ortho-D{}2(j=0) and para-D{}2(j=1) for several initial vibrational states (v≤slant 5), and find resonant structures in the energy range 0.01-10 K, which are sensitive to the initial rovibrational state (v, j). We compare the reaction rates for D2 + H with our previously obtained results for the isotopologue reaction H2 + D, and discuss the implications of our detailed study of this benchmark system for ultracold chemistry.

  7. Nuclear Reactions in the Crusts of Accreting Neutron Stars

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

    Lau, Rita; Beard, Mary; Gupta, Sanjib S.

    X-ray observations of transiently accreting neutron stars during quiescence provide information about the structure of neutron star crusts and the properties of dense matter. Interpretation of the observational data requires an understanding of the nuclear reactions that heat and cool the crust during accretion and define its nonequilibrium composition. We identify here in detail the typical nuclear reaction sequences down to a depth in the inner crust where the mass density ismore » $$\\rho =2\\times {10}^{12}\\,{\\rm{g}}\\,{\\mathrm{cm}}^{-3}$$ using a full nuclear reaction network for a range of initial compositions. The reaction sequences differ substantially from previous work. We find a robust reduction of crust impurity at the transition to the inner crust regardless of initial composition, though shell effects can delay the formation of a pure crust somewhat to densities beyond $$\\rho =2\\times {10}^{12}\\,{\\rm{g}}\\,{\\mathrm{cm}}^{-3}$$. This naturally explains the small inner crust impurity inferred from observations of a broad range of systems. The exception are initial compositions with A ≥ 102 nuclei, where the inner crust remains impure with an impurity parameter of Q imp ≈ 20 owing to the N = 82 shell closure. In agreement with previous work, we find that nuclear heating is relatively robust and independent of initial composition, while cooling via nuclear Urca cycles in the outer crust depends strongly on initial composition. As a result, this work forms a basis for future studies of the sensitivity of crust models to nuclear physics and provides profiles of composition for realistic crust models.« less

  8. Nuclear Reactions in the Crusts of Accreting Neutron Stars

    NASA Astrophysics Data System (ADS)

    Lau, R.; Beard, M.; Gupta, S. S.; Schatz, H.; Afanasjev, A. V.; Brown, E. F.; Deibel, A.; Gasques, L. R.; Hitt, G. W.; Hix, W. R.; Keek, L.; Möller, P.; Shternin, P. S.; Steiner, A. W.; Wiescher, M.; Xu, Y.

    2018-05-01

    X-ray observations of transiently accreting neutron stars during quiescence provide information about the structure of neutron star crusts and the properties of dense matter. Interpretation of the observational data requires an understanding of the nuclear reactions that heat and cool the crust during accretion and define its nonequilibrium composition. We identify here in detail the typical nuclear reaction sequences down to a depth in the inner crust where the mass density is ρ =2× {10}12 {{g}} {cm}}-3 using a full nuclear reaction network for a range of initial compositions. The reaction sequences differ substantially from previous work. We find a robust reduction of crust impurity at the transition to the inner crust regardless of initial composition, though shell effects can delay the formation of a pure crust somewhat to densities beyond ρ =2× {10}12 {{g}} {cm}}-3. This naturally explains the small inner crust impurity inferred from observations of a broad range of systems. The exception are initial compositions with A ≥ 102 nuclei, where the inner crust remains impure with an impurity parameter of Q imp ≈ 20 owing to the N = 82 shell closure. In agreement with previous work, we find that nuclear heating is relatively robust and independent of initial composition, while cooling via nuclear Urca cycles in the outer crust depends strongly on initial composition. This work forms a basis for future studies of the sensitivity of crust models to nuclear physics and provides profiles of composition for realistic crust models.

  9. Nuclear Reactions in the Crusts of Accreting Neutron Stars

    DOE PAGES

    Lau, Rita; Beard, Mary; Gupta, Sanjib S.; ...

    2018-05-24

    X-ray observations of transiently accreting neutron stars during quiescence provide information about the structure of neutron star crusts and the properties of dense matter. Interpretation of the observational data requires an understanding of the nuclear reactions that heat and cool the crust during accretion and define its nonequilibrium composition. We identify here in detail the typical nuclear reaction sequences down to a depth in the inner crust where the mass density ismore » $$\\rho =2\\times {10}^{12}\\,{\\rm{g}}\\,{\\mathrm{cm}}^{-3}$$ using a full nuclear reaction network for a range of initial compositions. The reaction sequences differ substantially from previous work. We find a robust reduction of crust impurity at the transition to the inner crust regardless of initial composition, though shell effects can delay the formation of a pure crust somewhat to densities beyond $$\\rho =2\\times {10}^{12}\\,{\\rm{g}}\\,{\\mathrm{cm}}^{-3}$$. This naturally explains the small inner crust impurity inferred from observations of a broad range of systems. The exception are initial compositions with A ≥ 102 nuclei, where the inner crust remains impure with an impurity parameter of Q imp ≈ 20 owing to the N = 82 shell closure. In agreement with previous work, we find that nuclear heating is relatively robust and independent of initial composition, while cooling via nuclear Urca cycles in the outer crust depends strongly on initial composition. As a result, this work forms a basis for future studies of the sensitivity of crust models to nuclear physics and provides profiles of composition for realistic crust models.« less

  10. Glutaredoxin-2 is required to control oxidative phosphorylation in cardiac muscle by mediating deglutathionylation reactions.

    PubMed

    Mailloux, Ryan J; Xuan, Jian Ying; McBride, Skye; Maharsy, Wael; Thorn, Stephanie; Holterman, Chet E; Kennedy, Christopher R J; Rippstein, Peter; deKemp, Robert; da Silva, Jean; Nemer, Mona; Lou, Marjorie; Harper, Mary-Ellen

    2014-05-23

    Glutaredoxin-2 (Grx2) modulates the activity of several mitochondrial proteins in cardiac tissue by catalyzing deglutathionylation reactions. However, it remains uncertain whether Grx2 is required to control mitochondrial ATP output in heart. Here, we report that Grx2 plays a vital role modulating mitochondrial energetics and heart physiology by mediating the deglutathionylation of mitochondrial proteins. Deletion of Grx2 (Grx2(-/-)) decreased ATP production by complex I-linked substrates to half that in wild type (WT) mitochondria. Decreased respiration was associated with increased complex I glutathionylation diminishing its activity. Tissue glucose uptake was concomitantly increased. Mitochondrial ATP output and complex I activity could be recovered by restoring the redox environment to that favoring the deglutathionylated states of proteins. Grx2(-/-) hearts also developed left ventricular hypertrophy and fibrosis, and mice became hypertensive. Mitochondrial energetics from Grx2 heterozygotes (Grx2(+/-)) were also dysfunctional, and hearts were hypertrophic. Intriguingly, Grx2(+/-) mice were far less hypertensive than Grx2(-/-) mice. Thus, Grx2 plays a vital role in modulating mitochondrial metabolism in cardiac muscle, and Grx2 deficiency leads to pathology. As mitochondrial ATP production was restored by the addition of reductants, these findings may be relevant to novel redox-related therapies in cardiac disease. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

  11. Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

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

    Polo-Garzon, Felipe; Yang, Shi-Ze; Fung, Victor

    2017-07-19

    Although perovskites have been widely used in catalysis, tuning their surface terminations to control reaction selectivities has not been well established. In this work, we employ multiple surface sensitive techniques to characterize the surface termination (one aspect of surface reconstruction) of SrTiO 3 (STO) after thermal pretreatment (Sr-enrichment) and chemical etching (Ti-enrichment). We show, using the conversion of 2-propanol as a probe reaction, that the surface termination of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivities in a wide range, which are inaccessible using single metal oxides, either SrO or TiO 2. Densitymore » functional theory (DFT) calculations well explain the selectivity tuning and reaction mechanism on different surface terminations of STO. Similar catalytic tunability is also observed on BaZrO 3, highlighting the generality of the finding from this work.« less

  12. Reaction of iminopropadienones with amines: mechanistic explanations of zwitterionic intermediate, ketene and ketenimine formation.

    PubMed

    Koch, Rainer; Finnerty, Justin J; Bruhn, Torsten; Borget, Fabien; Wentrup, Curt

    2008-09-25

    The complex reaction of thermally generated iminopropadienones with amines in the gas phase and upon matrix deposition and its varying product composition is investigated using density functional theory. In the high energy gas phase addition a single amine molecule reacts readily with iminopropadienone with the decisive step being a 1,3-hydrogen shift and activation barriers of at least 100 kJ/mol. In accordance with the experiment, the formation of ketenes is favored. In the condensed phase of an amine matrix, the utilization of amine dimers both as reagents and as explicit solvents lowers the activation energy required to a feasible 20-30 kJ/mol and predicts ketenimines as the main products, as observed experimentally.

  13. Assignment of EC Numbers to Enzymatic Reactions with Reaction Difference Fingerprints

    PubMed Central

    Hu, Qian-Nan; Zhu, Hui; Li, Xiaobing; Zhang, Manman; Deng, Zhe; Yang, Xiaoyan; Deng, Zixin

    2012-01-01

    The EC numbers represent enzymes and enzyme genes (genomic information), but they are also utilized as identifiers of enzymatic reactions (chemical information). In the present work (ECAssigner), our newly proposed reaction difference fingerprints (RDF) are applied to assign EC numbers to enzymatic reactions. The fingerprints of reactant molecules minus the fingerprints of product molecules will generate reaction difference fingerprints, which are then used to calculate reaction Euclidean distance, a reaction similarity measurement, of two reactions. The EC number of the most similar training reaction will be assigned to an input reaction. For 5120 balanced enzymatic reactions, the RDF with a fingerprint length at 3 obtained at the sub-subclass, subclass, and main class level with cross-validation accuracies of 83.1%, 86.7%, and 92.6% respectively. Compared with three published methods, ECAssigner is the first fully automatic server for EC number assignment. The EC assignment system (ECAssigner) is freely available via: http://cadd.whu.edu.cn/ecassigner/. PMID:23285222

  14. How Parental Reactions Change in Response to Adolescent Suicide Attempt.

    PubMed

    Greene-Palmer, Farrah N; Wagner, Barry M; Neely, Laura L; Cox, Daniel W; Kochanski, Kristen M; Perera, Kanchana U; Ghahramanlou-Holloway, Marjan

    2015-01-01

    This study examined parental reactions to adolescents' suicide attempts and the association of reactions with future suicidal self-directed violence. Participants were 81 mothers and 49 fathers of 85 psychiatric inpatient adolescents. Maternal hostility and paternal anger and arguing predicted future suicide attempts. From pre- to post-attempt, mothers reported feeling increased sadness, caring, anxiety, guilt, fear, and being overwhelmed; fathers reported increased sadness, anxiety, and fear. Findings have clinical implications; improving parent-child relationships post-suicide attempt may serve as a protective factor for suicide.

  15. White House Budget Proposal Favorable Overall for Federal Science Agencies

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    2012-02-01

    President Barack Obama's proposed federal budget of 3.8 trillion for fiscal year (FY) 2013, released on 13 February, provides an overall favorable funding picture for federal science agencies in a tight economic environment. However, there are also a number of proposed decreases, including a sharp cut to NASA's Planetary Science account. Overall, the budget proposal includes 140.8 billion for the federal investment in research and development, a 1.4% increase above the FY 2012 enacted level. Funding for federal basic and applied research would be 64 billion, 3.3% above FY 2012 enacted levels. Funding for defense research and development (R&D) would decrease to 75.9 billion, a drop of 1.5%; nondefense R&D would increase 5% to $64.9 billion.

  16. Rational selection of structurally diverse natural product scaffolds with favorable ADME properties for drug discovery.

    PubMed

    Samiulla, D S; Vaidyanathan, V V; Arun, P C; Balan, G; Blaze, M; Bondre, S; Chandrasekhar, G; Gadakh, A; Kumar, R; Kharvi, G; Kim, H O; Kumar, S; Malikayil, J A; Moger, M; Mone, M K; Nagarjuna, P; Ogbu, C; Pendhalkar, D; Rao, A V S Raja; Rao, G Venkateshwar; Sarma, V K; Shaik, S; Sharma, G V R; Singh, S; Sreedhar, C; Sonawane, R; Timmanna, U; Hardy, L W

    2005-01-01

    Natural product analogs are significant sources for therapeutic agents. To capitalize efficiently on the effective features of naturally occurring substances, a natural product-based library production platform has been devised at Aurigene for drug lead discovery. This approach combines the attractive biological and physicochemical properties of natural product scaffolds, provided by eons of natural selection, with the chemical diversity available from parallel synthetic methods. Virtual property analysis, using computational methods described here, guides the selection of a set of natural product scaffolds that are both structurally diverse and likely to have favorable pharmacokinetic properties. The experimental characterization of several in vitro ADME properties of twenty of these scaffolds, and of a small set of designed congeners based upon one scaffold, is also described. These data confirm that most of the scaffolds and the designed library members have properties favorable to their utilization for creating libraries of lead-like molecules.

  17. Impulsivity, Rejection Sensitivity, and Reactions to Stressors in Borderline Personality Disorder

    PubMed Central

    Berenson, Kathy R.; Gregory, Wesley Ellen; Glaser, Erin; Romirowsky, Aliza; Rafaeli, Eshkol; Yang, Xiao; Downey, Geraldine

    2016-01-01

    This research investigated baseline impulsivity, rejection sensitivity, and reactions to stressors in individuals with borderline personality disorder compared to healthy individuals and those with avoidant personality disorder. The borderline group showed greater impulsivity than the avoidant and healthy groups both in a delay-discounting task with real monetary rewards and in self-reported reactions to stressors; moreover, these findings could not be explained by co-occurring substance use disorders. Distress reactions to stressors were equally elevated in both personality disorder groups (relative to the healthy group). The borderline and avoidant groups also reported more maladaptive reactions to a stressor of an interpersonal vs. non-interpersonal nature, whereas the healthy group did not. Finally, self-reported impulsive reactions to stressors were associated with baseline impulsivity in the delay-discounting task, and greater self-reported reactivity to interpersonal than non-interpersonal stressors was associated with rejection sensitivity. This research highlights distinct vulnerabilities contributing to impulsive behavior in borderline personality disorder. PMID:27616800

  18. Effect of Edaravone on Favorable Outcome in Patients with Acute Cerebral Large Vessel Occlusion: Subanalysis of RESCUE-Japan Registry

    PubMed Central

    MIYAJI, Yuki; YOSHIMURA, Shinichi; SAKAI, Nobuyuki; YAMAGAMI, Hiroshi; EGASHIRA, Yusuke; SHIRAKAWA, Manabu; UCHIDA, Kazutaka; KAGEYAMA, Hirohito; TOMOGANE, Yusuke

    2015-01-01

    The data of the nationwide prospective registry of acute cerebral large vessel occlusion (LVO; RESCUE-Japan Registry) were analyzed to know the effect of edaravone, a free radical scavenger, on clinical outcome at 90 days after onset. In this registry, patients with acute cerebral LVO admitted within 24 h after onset were prospectively registered. The effect of various factors including endovascular treatment (EVT), intravenous recombinant tissue plasminogen activator (IV rt-PA), and other medication including edaravone on favorable outcome (modified Rankin scale 0–1) was analyzed. Of the 1,454 registered patients, 1,442 patients (99.2%) had the information of edaravone were analyzed. In total, edaravone group had more patients with favorable outcome compared to non-edaravone group (22.9% vs. 13.8%, p = 0.0006). Edaravone increased favorable outcome in patients treated with IV rt-PA (29.4% vs. 11.1%, p = 0.0107), but not with EVT (21.2% vs. 13.9%, p = 0.309). Logistic regression analysis revealed that higher National Institutes of Health Stroke Scale (NIHSS) score on admission [odds ratio (OR) 0.875, 95% confidence interval (CI) 0.858–0.894] and advanced age (OR 0.963, 95%CI 0.952–0.975) were significantly related to unfavorable outcome. In contrast, IV rt-PA (OR 2.489, 95%CI 1.867–3.319), EVT (OR 1.375, 95%CI 1.013–1.865), and edaravone (OR 1.483, 95%CI 1.027–2.143) were significantly associated with favorable outcome. This analysis indicated that IV rt-PA, EVT, and edaravone were effective to obtain favorable outcome in patients with acute LVO. Combination IV rt-PA with edaravone was more effective. PMID:25739433

  19. [Reactions to food].

    PubMed

    Halvorsen, R; Eggesb M; Botten, G

    1995-12-10

    Adverse reactions to food occur in about 1-2% of the population, but are reported more frequently by patients. Most reactions to food are not caused by allergy. IgE-mediated food reactions are well known and of major clinical significance owing to their potentially dangerous, even life-threatening character. Adverse reactions to food can also be caused by immunological mechanisms other than IgE-mediated reactions such as, enzyme deficiencies, active pharmacological substances in food and psychological mechanisms. Double-blind provocation is the only way to diagnose a positive reaction to a food item with some certainty. Regretably no objective measures for food reactions exist.

  20. Subcutaneous lymphoid follicular hyperplasia secondary to vaccination: correlation of ultrasound findings with clinical and histological findings.

    PubMed

    Castro Copete, M C; Crespo Martínez, C; Martínez García, C; Calbo Maiques, J

    In recent years, the use of vaccines has been standardized within vaccination programs. Adverse effects at the puncture site are usually mild and transient. Nevertheless, in some cases, persistence subcutaneous nodules can develop; these are often underdiagnosed because they are so rare and because of the long time that can transpire between the vaccination and their appearance. Histologically, they consist of a lymphoid follicular hyperplasia that occurs as a reaction to the aluminum particles usually used as an adjuvant in some vaccines. We were unable to find any reference in the radiological literature to these soft-tissue nodules secondary to vaccination. We report the characteristic ultrasound findings that will enable radiologists to identify or strongly suspect these lesions and thereby avoid unnecessary imaging tests that might lead to confusion and inadequate management of these patients. Copyright © 2016 SERAM. Publicado por Elsevier España, S.L.U. All rights reserved.

  1. Experimental and Quantum Mechanics Investigations of Early Reactions of Monomethylhydrazine with Mixtures of NO2 and N2O4

    DTIC Science & Technology

    2013-02-15

    red fuming nitric acid (RFNA), which is composed of nitric acid (HNO3, 85 wt%) and NO2 (8–15 wt%). Recently the impinging stream vortex engine (ISVE... nitric acid [51]. As a result, growth of the particles is favored over H-abstraction reactions at the low temperatures of our experiments. As the...followed by the proton transfer from NAH bond to NO3 to form nitric acid , as shown in Scheme 3. Although it is very easy to form nitric acid (enthalpic

  2. Free Energy Contribution Analysis Using Response Kernel Approximation: Insights into the Acylation Reaction of a Beta-Lactamase.

    PubMed

    Asada, Toshio; Ando, Kanta; Bandyopadhyay, Pradipta; Koseki, Shiro

    2016-09-08

    A widely applicable free energy contribution analysis (FECA) method based on the quantum mechanical/molecular mechanical (QM/MM) approximation using response kernel approaches has been proposed to investigate the influences of environmental residues and/or atoms in the QM region on the free energy profile. This method can evaluate atomic contributions to the free energy along the reaction path including polarization effects on the QM region within a dramatically reduced computational time. The rate-limiting step in the deactivation of the β-lactam antibiotic cefalotin (CLS) by β-lactamase was studied using this method. The experimentally observed activation barrier was successfully reproduced by free energy perturbation calculations along the optimized reaction path that involved activation by the carboxylate moiety in CLS. It was found that the free energy profile in the QM region was slightly higher than the isolated energy and that two residues, Lys67 and Lys315, as well as water molecules deeply influenced the QM atoms associated with the bond alternation reaction in the acyl-enzyme intermediate. These facts suggested that the surrounding residues are favorable for the reactant complex and prevent the intermediate from being too stabilized to proceed to the following deacylation reaction. We have demonstrated that the free energy contribution analysis should be a useful method to investigate enzyme catalysis and to facilitate intelligent molecular design.

  3. Reactions of Criegee Intermediates with Non-Water Greenhouse Gases: Implications for Metal Free Chemical Fixation of Carbon Dioxide.

    PubMed

    Kumar, Manoj; Francisco, Joseph S

    2017-09-07

    High-level theoretical calculations suggest that a Criegee intermediate preferably interacts with carbon dioxide compared to two other greenhouse gases, nitrous oxide and methane. The results also suggest that the interaction between Criegee intermediates and carbon dioxide involves a cycloaddition reaction, which results in the formation of a cyclic carbonate-type adduct with a barrier of 6.0-14.0 kcal/mol. These results are in contrast to a previous assumption that the reaction occurs barrierlessly. The subsequent decomposition of the cyclic adduct into formic acid and carbon dioxide follows both concerted and stepwise mechanisms. The latter mechanism has been overlooked previously. Under formic acid catalysis, the concerted decomposition of the cyclic carbonate may be favored under tropospheric conditions. Considering that there is a strong nexus between carbon dioxide levels in the atmosphere and global warming, the high reactivity of Criegee intermediates could be utilized for designing efficient carbon capture technologies.

  4. Bradycardia During Targeted Temperature Management: An Early Marker of Lower Mortality and Favorable Neurologic Outcome in Comatose Out-of-Hospital Cardiac Arrest Patients.

    PubMed

    Thomsen, Jakob Hartvig; Nielsen, Niklas; Hassager, Christian; Wanscher, Michael; Pehrson, Steen; Køber, Lars; Bro-Jeppesen, John; Søholm, Helle; Winther-Jensen, Matilde; Pellis, Tommaso; Kuiper, Michael; Erlinge, David; Friberg, Hans; Kjaergaard, Jesper

    2016-02-01

    Bradycardia is common during targeted temperature management, likely being a physiologic response to lower body temperature, and has recently been associated with favorable outcome following out-of-hospital cardiac arrest in smaller observational studies. The present study sought to confirm this finding in a large multicenter cohort of patients treated with targeted temperature management at 33°C and explore the response to targeted temperature management targeting 36°C. Post hoc analysis of a prospective randomized study. Thirty-six ICUs in 10 countries. We studied 447 (targeted temperature management = 33°C) and 430 (targeted temperature management = 36°C) comatose out-of-hospital cardiac arrest patients with available heart rate data, randomly assigned in the targeted temperature management trial from 2010 to 2013. Targeted temperature management at 33°C and 36°C. Endpoints were 180-day mortality and unfavorable neurologic function (cerebral performance category 3-5). Patients were stratified by target temperature and minimum heart rate during targeted temperature management (< 50, 50-59, and ≥ 60 beats/min [reference]) at 12, 20, and 28 hours after randomization. Heart rates less than 50 beats/min and 50-59 beats/min were recorded in 132 (30%) and 131 (29%) of the 33°C group, respectively. Crude 180-day mortality increased with increasing minimum heart rate (< 50 beats/min = 32%, 50-59 beats/min = 43%, and ≥ 60 beats/min = 60%; p(log-rank) < 0.0001). Bradycardia less than 50 beats/min was independently associated with lower 180-day mortality (hazard ratio(adjusted) = 0.50 [0.34-0.74; p < 0.001]) and lower odds of unfavorable neurologic outcome (odds ratio(adjusted) = 0.38 [ 0.21-0.68; p < 0.01]) in models adjusting for potential confounders including age, initial rhythm, time to return of spontaneous circulation, and lactate at admission. Similar, albeit less strong, independent associations of lower heart rates and favorable outcome were found in

  5. Rate coefficients from quantum and quasi-classical cumulative reaction probabilities for the S(1D) + H2 reaction

    NASA Astrophysics Data System (ADS)

    Jambrina, P. G.; Lara, Manuel; Menéndez, M.; Launay, J.-M.; Aoiz, F. J.

    2012-10-01

    Cumulative reaction probabilities (CRPs) at various total angular momenta have been calculated for the barrierless reaction S(1D) + H2 → SH + H at total energies up to 1.2 eV using three different theoretical approaches: time-independent quantum mechanics (QM), quasiclassical trajectories (QCT), and statistical quasiclassical trajectories (SQCT). The calculations have been carried out on the widely used potential energy surface (PES) by Ho et al. [J. Chem. Phys. 116, 4124 (2002), 10.1063/1.1431280] as well as on the recent PES developed by Song et al. [J. Phys. Chem. A 113, 9213 (2009), 10.1021/jp903790h]. The results show that the differences between these two PES are relatively minor and mostly related to the different topologies of the well. In addition, the agreement between the three theoretical methodologies is good, even for the highest total angular momenta and energies. In particular, the good accordance between the CRPs obtained with dynamical methods (QM and QCT) and the statistical model (SQCT) indicates that the reaction can be considered statistical in the whole range of energies in contrast with the findings for other prototypical barrierless reactions. In addition, total CRPs and rate coefficients in the range of 20-1000 K have been calculated using the QCT and SQCT methods and have been found somewhat smaller than the experimental total removal rates of S(1D).

  6. Histopathological findings in immunohistological staining of the granulomatous tissue reaction associated with tuberculosis.

    PubMed

    Karimi, Shirin; Shamaei, Masoud; Pourabdollah, Mihan; Sadr, Makan; Karbasi, Mehrdad; Kiani, Arda; Bahadori, Moslem

    2014-01-01

    Purpose. The histological diagnosis of Mycobacterium tuberculosis (MTB) remains a diagnostic challenge despite different methods. Immunohistochemistry (IHC) not only could confirm granulomatous tissue involvement but also can demonstrate MTB antigen immunolocalization. This study tries to clarify the details of immunohistochemical staining for MTB with pAbBCG. Materials/Methods. Twenty-three confirmed TB granulomatous tissue samples were studied by Ziehl-Neelsen and immunohistochemistry (IHC) staining with pAbBCG. Samples were selected from the archive of the Department of Pathology, National Research Institute of Tuberculosis and Lung Disease, Tehran, Iran. Results. IHC staining was positive in all samples, whereas Ziehl-Neelsen was positive in 9 cases out of 23 (39.1%). Tissue types used were pleural tissue, lymph nodes, and lung tissue. IHC showed positive coarse granular cytoplasmic and round, fragmented bacillary staining. In this study, epithelioid cells clearly showed more positive staining at the periphery of the granuloma rather than the center of granuloma. There is also positive staining in endothelial cells, fibroblasts, plasma cells, lymphocytes, and macrophages outside the granuloma. Conclusion. Considering the criteria of positive immunohistochemical staining of TB granulomatous reactions, this stain not only highlights the presence of mycobacterial antigens for tissue diagnosis, but also could morphologically localize its distribution in different cells.

  7. Histopathological Findings in Immunohistological Staining of the Granulomatous Tissue Reaction Associated with Tuberculosis

    PubMed Central

    Karimi, Shirin; Pourabdollah, Mihan; Sadr, Makan; Karbasi, Mehrdad; Bahadori, Moslem

    2014-01-01

    Purpose. The histological diagnosis of Mycobacterium tuberculosis (MTB) remains a diagnostic challenge despite different methods. Immunohistochemistry (IHC) not only could confirm granulomatous tissue involvement but also can demonstrate MTB antigen immunolocalization. This study tries to clarify the details of immunohistochemical staining for MTB with pAbBCG. Materials/Methods. Twenty-three confirmed TB granulomatous tissue samples were studied by Ziehl-Neelsen and immunohistochemistry (IHC) staining with pAbBCG. Samples were selected from the archive of the Department of Pathology, National Research Institute of Tuberculosis and Lung Disease, Tehran, Iran. Results. IHC staining was positive in all samples, whereas Ziehl-Neelsen was positive in 9 cases out of 23 (39.1%). Tissue types used were pleural tissue, lymph nodes, and lung tissue. IHC showed positive coarse granular cytoplasmic and round, fragmented bacillary staining. In this study, epithelioid cells clearly showed more positive staining at the periphery of the granuloma rather than the center of granuloma. There is also positive staining in endothelial cells, fibroblasts, plasma cells, lymphocytes, and macrophages outside the granuloma. Conclusion. Considering the criteria of positive immunohistochemical staining of TB granulomatous reactions, this stain not only highlights the presence of mycobacterial antigens for tissue diagnosis, but also could morphologically localize its distribution in different cells. PMID:24511393

  8. Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

    DOE PAGES

    Rotavera, Brandon; Zádor, Judit; Welz, Oliver; ...

    2014-09-19

    The product formation from R + O 2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). The interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO 2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O 2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positivemore » dependence on temperature over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Furthermore, quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O 2-addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with β-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.« less

  9. Consistency and Inconsistency in A Level Students' Understandings of a Number of Chemical Reactions.

    ERIC Educational Resources Information Center

    Kwen, Boo Hong

    1996-01-01

    Explores A level students' conceptions of some common chemical reactions. Findings indicate that students apply frameworks consistently across groups of events that they perceive to be similar. What was found to be lacking was the scientists' view of all the reactions being regarded as realizations of the same underlying conceptual model. Contains…

  10. Probing the Structure of {sup 74}Ge Nucleus with Coupled-channels Analysis of {sup 74}Ge+{sup 74}Ge Fusion Reaction

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

    Zamrun F, Muhammad; Jurusan Fisika FMIPA, Universitas Haluoleo, Kendari, Sulawesi Tenggara, 93232; Kasim, Hasan Abu

    2010-12-23

    We study the fusion reaction of the {sup 74}Ge+{sup 74}Ge system in term of the full order coupled-channels formalism. We especially calculated the fusion cross section as well as the fusion barrier distribution of this reaction using transition matrix suggested by recent Coulomb excitation experiment. We compare the results with the one obtained by coupling matrix based on pure vibrational and rotational models. The present coupled-channels calculations for the barrier distributions obtained using experiment coupling matrix is in good agreement with the one obtained with vibrational model, in contrast to the rotational model. This is indicates that {sup 74}Ge nucleusmore » favor a spherical shape than a deformed shape in its ground state. Our results will resolve the debates concerning the structure of this nucleus.« less

  11. Computational study for the circular redox reaction of N2O with CO catalyzed by fullerometallic cations C60Fe+ and C70Fe.

    PubMed

    Anafcheh, Maryam; Naderi, Fereshteh; Khodadadi, Zahra; Ektefa, Fatemeh; Ghafouri, Reza; Zahedi, Mansour

    2017-03-01

    We applied density functional calculations to study the circular redox reaction mechanism of N 2 O with CO catalyzed by fullerometallic cations C 60 Fe + and C 70 Fe + . The on-top sites of six-membered rings (η 6 ) of fullerene cages are the most preferred binding sites for Fe + cation, and the hexagon to pentagon migration of Fe + is unlikely under ambient thermodynamic conditions. The initial ion/molecule reaction, N 2 O rearrangement and N 2 abstraction on the considered fullerometallic cations are easier than those on the bare Fe + cation in the gas phase. Generally, our results indicate that fullerometallic ions, C 60 Fe + and C 70 Fe + , are more favorable substrates for redox reaction of N 2 O with CO in comparison to the other previously studied carbon nanostructures such as graphene and nanotubes. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Cycloaddition Reactions of Cobalt-Complexed Macrocyclic Alkynes: The Transannular Pauson-Khand Reaction.

    PubMed

    Karabiyikoglu, Sedef; Boon, Byron A; Merlic, Craig A

    2017-08-04

    The Pauson-Khand reaction is a powerful tool for the synthesis of cyclopentenones through the efficient [2 + 2 + 1] cycloaddition of dicobalt alkyne complexes with alkenes. While intermolecular and intramolecular variants are widely known, transannular versions of this reaction are unknown and the basis of this study. Macrocyclic enyne and dienyne complexes were readily synthesized by palladium(II)-catalyzed oxidative macrocyclizations of bis(vinyl boronate esters) or ring-closing metathesis reactions followed by complexation with dicobalt octacarbonyl. Several reaction modalities of these macrocyclic complexes were uncovered. In addition to the first successful transannular Pauson-Khand reactions, other intermolecular and transannular cycloaddition reactions included intermolecular Pauson-Khand reactions, transannular [4 + 2] cycloaddition reactions, intermolecular [2 + 2 + 2] cycloaddition reactions, and intermolecular [2 + 2 + 1 + 1] cycloaddition reactions. The structural and reaction requirements for each process are presented.

  13. Extracting Spectroscopic Factors of Argon Isotopes from Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Manfredi, Juan; Lee, J.; Tsang, M. B.; Lynch, W. G.; Barney, J.; Estee, J.; Sweany, S.; Brown, K. W.; Cerizza, G.; Anderson, C.; Setiawan, H.; Loelius, C.; Xu, Z.; Rogers, A. M.; Pruitt, C.; Sobotka, L. G.; Elson, J. M.; Langer, C.; Chajecki, Z.; Chen, G.; Jones, K. L.; Smith, K.; Xiao, Z.; Li, Z.; Winkelbauer, J. R.

    2017-01-01

    A spectroscopic factor (SF) quantifies the single particle occupancy of a given state in a nucleus. For the argon isotopes, there is a discrepancy of the SF between studies that use transfer reactions and knockout reactions. Understanding the SFs of these isotopes, and in particular how the SF changes across the isotopic chain, is important for understanding how single particle structure changes with neutron number. The transfer reactions 34Ar(p,d) and 46Ar(p,d) were measured at the National Superconducting Cyclotron Laboratory (NSCL) using the same beam energy (70 MeV/u) as from the previous knockout measurement. Spectroscopic factors were extracted from measured angular distributions via ADWA calculations. Preliminary findings will be presented. The National Superconducting Cyclotron Laboratory is supported by the NSF (PHY 1102511), and Juan Manfredi is supported by the DOE NNSA Stewardship Science Graduate Fellowship.

  14. Stigmatizing Reactions to Intimate Partner Violence Disclosure and Depression: Examining the Mediating Role of Coping Strategies

    PubMed Central

    Overstreet, Nicole M.; Willie, Tiara C.; Sullivan, Tami P.

    2017-01-01

    Objective Despite increased attention to the relation between negative social reactions to intimate partner violence (IPV) disclosure and poorer mental health outcomes for victims, research has yet to examine whether certain types of negative social reactions are associated with poorer mental health outcomes more so than others. Further, research is scarce on potential mediators of this relationship. To fill these gaps, the current study examines whether stigmatizing reactions to IPV disclosure, such as victim-blaming responses and minimizing experiences of IPV, are a specific type of negative social reaction that exerts greater influence on women’s depressive symptoms than general negative reactions, such as being angry at the perpetrators of IPV. We also examine avoidance coping as a key mediator of this relationship. Methods A cross sectional correlational study was conducted to examine these relationships. Participants were 212 women from an urban northeast community who indicated being physically victimized by their male partner in the past six months. Results Findings from a multiple regression analysis showed that stigmatizing reactions, not general negative reactions, predicted women’s depressive symptoms. In addition, a multiple mediation analysis revealed that avoidance coping strategies, but not approach coping strategies, significantly accounted for the relationship between stigmatizing social reactions and women’s depressive symptoms. Conclusions Findings have implications for improving support from informal and formal sources and subsequently, IPV exposed women’s psychological well-being. PMID:27296052

  15. Proton-conducting Micro-solid Oxide Fuel Cells with Improved Cathode Reactions by a Nanoscale Thin Film Gadolinium-doped Ceria Interlayer

    PubMed Central

    Li, Yong; Wang, Shijie; Su, Pei-Chen

    2016-01-01

    An 8 nm-thick gadolinium-doped ceria (GDC) layer was inserted as a cathodic interlayer between the nanoscale proton-conducting yttrium-doped barium zirconate (BZY) electrolyte and the porous platinum cathode of a micro-solid oxide fuel cell (μ-SOFC), which has effectively improved the cathode reaction kinetics and rendered high cell power density. The addition of the GDC interlayer significantly reduced the cathodic activation loss and increased the peak power density of the μ-SOFC by 33% at 400 °C. The peak power density reached 445 mW/cm2 at 425 °C, which is the highest among the reported μ-SOFCs using proton-conducting electrolytes. The impressive performance was attributed to the mixed protonic and oxygen ionic conducting properties of the nano-granular GDC, and also to the high densities of grain boundaries and lattice defects in GDC interlayer that favored the oxygen incorporation and transportation during the oxygen reduction reaction (ORR) and the water evolution reaction at cathode. PMID:26928192

  16. Prognostic factors of a favorable outcome following a supervised exercise program for soldiers with sub-acute and chronic low back pain.

    PubMed

    Perron, Marc; Gendron, Chantal; Langevin, Pierre; Leblond, Jean; Roos, Marianne; Roy, Jean-Sébastien

    2018-04-02

    Low back pain (LBP) encompasses heterogeneous patients unlikely to respond to a unique treatment. Identifying sub-groups of LBP may help to improve treatment outcomes. This is a hypothesis-setting study designed to create a clinical prediction rule (CPR) that will predict favorable outcomes in soldiers with sub-acute and chronic LBP participating in a multi-station exercise program. Military members with LBP participated in a supervised program comprising 7 stations each consisting of exercises of increasing difficulty. Demographic, impairment and disability data were collected at baseline. The modified Oswestry Disability Index (ODI) was administered at baseline and following the 6-week program. An improvement of 50% in the initial ODI score was considered the reference standard to determine a favorable outcome. Univariate associations with favorable outcome were tested using chi-square or paired t-tests. Variables that showed between-group (favorable/unfavorable) differences were entered into a logistic regression after determining the sampling adequacy. Finally, continuous variables were dichotomized and the sensitivity, specificity and positive and negative likelihood ratios were determined for the model and for each variable. A sample of 85 participants was included in analyses. Five variables contributed to prediction of a favorable outcome: no pain in lying down (p = 0.017), no use of antidepressants (p = 0.061), FABQ work score < 22.5 (p = 0.061), fewer than 5 physiotherapy sessions before entering the program (p = 0.144) and less than 6 months' work restriction (p = 0.161). This model yielded a sensitivity of 0.78, specificity of 0.80, LR+ of 3.88, and LR- of 0.28. A 77.5% probability of favorable outcome can be predicted by the presence of more than three of the five variables, while an 80% probability of unfavorable outcome can be expected if only three or fewer variables are present. The use of prognostic factors may guide

  17. The Association Between Duration of Resuscitation and Favorable Outcome After Out-of-Hospital Cardiac Arrest: Implications for Prolonging or Terminating Resuscitation

    PubMed Central

    Reynolds, Joshua C.; Grunau, Brian E.; Rittenberger, Jon C.; Sawyer, Kelly N.; Kurz, Michael C.; Callaway, Clifton W.

    2016-01-01

    Background Little evidence guides the appropriate duration of resuscitation in out-of-hospital cardiac arrest (OHCA), and case features justifying longer or shorter durations are ill-defined. We estimated the impact of resuscitation duration on the probability of favorable functional outcome in OHCA using a large, multi-center cohort. Methods Secondary analysis of a North American, single blind, multi-center, cluster-randomized clinical trial (ROC-PRIMED) of consecutive adults with non-traumatic, EMS-treated, OHCA. Primary exposure was duration of resuscitation in minutes (onset of professional resuscitation to return of spontaneous circulation [ROSC] or termination of resuscitation). Primary outcome was survival to hospital discharge with favorable outcome (modified Rankin scale [mRS] 0-3). Subjects were additionally classified as survival with unfavorable outcome (mRS 4-5), ROSC without survival (mRS 6), or without ROSC. Subject accrual was plotted as a function of resuscitation duration, and the dynamic probability of favorable outcome at discharge was estimated for the whole cohort and subgroups. Adjusted logistic regression models tested the association between resuscitation duration and survival with favorable outcome. Results The primary cohort included 11,368 subjects (median age 69 years [IQR: 56-81 years]; 7,121 men [62.6%]). Of these, 4,023 (35.4%) achieved ROSC, 1,232 (10.8%) survived to hospital discharge, and 905 (8.0%) had mRS 0-3 at discharge. Distribution of CPR duration differed by outcome (p<0.00001). For CPR duration up to 37.0 minutes (95%CI 34.9-40.9 minutes), 99% with eventual mRS 0-3 at discharge achieved ROSC. Dynamic probability of mRS 0-3 at discharge declined over elapsed resuscitation duration, but subjects with initial shockable cardiac rhythm, witnessed cardiac arrest, and bystander CPR were more likely to survive with favorable outcome after prolonged efforts (30-40 minutes). Adjusting for prehospital (OR 0.93; 95%CI 0.92-0.95) and

  18. A novel thiamine-derived pigment, pyrizepine, formed by the Maillard reaction.

    PubMed

    Igoshi, Asuka; Noda, Kyoko; Murata, Masatsune

    2018-04-26

    To find a Maillard pigment derived from thiamine, a solution containing glucose and thiamine was heated and analyzed with high-performance liquid chromatography equipped with diode-array detection. As a result, a unique peak showing an absorption maximum at 380 nm was detected. This peak was then isolated from a reaction solution containing glucose, lysine and thiamine, and was identified as 1-(2-methyl-6,9-dihydro-5H-pyrimido[4,5-e][1,4]diazepin-7-yl)ethan-1-one using instrumental analyses. This compound, named pyrizepine, was a novel yellow pigment having a fused ring consisting of pyrimidine and diazepine. Pyrizepine was a major low-molecular-weight pigment in the reaction solution. The structure suggests that pyrizepine is formed by condensation reaction between a degradation product of thiamine and a tetrosone derivative formed from glucose by the Maillard reaction.

  19. Toward rational design of amines for CO2 capture: Substituent effect on kinetic process for the reaction of monoethanolamine with CO2.

    PubMed

    Xie, Hongbin; Wang, Pan; He, Ning; Yang, Xianhai; Chen, Jingwen

    2015-11-01

    Amines have been considered as promising candidates for post-combustion CO2 capture. A mechanistic understanding for the chemical processes involved in the capture and release of CO2 is important for the rational design of amines. In this study, the structural effects of amines on the kinetic competition among three typical products (carbamates, carbamic acids and bicarbonate) from amines+CO2 were investigated, in contrast to previous thermodynamic studies to tune the reaction of amines with CO2 based on desirable reaction enthalpy and reaction stoichiometry. We used a quantum chemical method to calculate the activation energies (Ea) for the reactions of a range of substituted monoethanolamines with CO2 covering three pathways to the three products. The results indicate that the formation of carbamates is the most favorable, among the three considered products. In addition, we found that the Ea values for all pathways linearly correlate with pKa of amines, and more importantly, the kinetic competition between carbamate and bicarbonate absorption pathways varies with pKa of the amines, i.e. stronger basicity results in less difference in Ea. These results highlight the importance of the consideration of kinetic competition among different reaction pathways in amine design. Copyright © 2015. Published by Elsevier B.V.

  20. Glutamine supplementation favors weight loss in nondieting obese female patients. A pilot study.

    PubMed

    Laviano, A; Molfino, A; Lacaria, M T; Canelli, A; De Leo, S; Preziosa, I; Rossi Fanelli, F

    2014-11-01

    Glutamine supplementation improves insulin sensitivity in critically ill patients, and prevents obesity in animals fed a high-fat diet. We hypothesized that glutamine supplementation favors weight loss in humans. Obese and overweight female patients (n=6) were enrolled in a pilot, cross-over study. After recording anthropometric (that is, body weight, waist circumference) and metabolic (that is, glycemia, insulinemia, homeostatic model of insulin resistance (HOMA-IR)) characteristics, patients were randomly assigned to 4-week supplementation with glutamine or isonitrogenous protein supplement (0.5 g/KgBW/day). During supplementation, patients did not change their dietary habits nor lifestyle. At the end, anthropometric and metabolic features were assessed, and after 2 weeks of washout, patients were switched to the other supplement for 4 weeks. Body weight and waist circumference significantly declined only after glutamine supplementation (85.0±10.4 Kg vs 82.2±10.1 Kg, and 102.7±2.0 cm vs 98.9±2.9 cm, respectively; P=0.01). Insulinemia and HOMA-IR declined by 20% after glutamine, but not significantly so. This pilot study shows that glutamine is safe and effective in favoring weight loss and possibly enhancing glucose metabolism.

  1. Favorable effect of moderate dose caffeine on the skeletal system in ovariectomized rats.

    PubMed

    Folwarczna, Joanna; Pytlik, Maria; Zych, Maria; Cegieła, Urszula; Kaczmarczyk-Sedlak, Ilona; Nowińska, Barbara; Sliwiński, Leszek

    2013-10-01

    Caffeine, a methylxanthine present in coffee, has been postulated to be responsible for an increased risk of osteoporosis in coffee drinkers; however, the data are inconsistent. The aim of the present study was to investigate the effects of a moderate dose of caffeine on the skeletal system of rats with normal and decreased estrogen level (developing osteoporosis due to estrogen deficiency). The experiments were carried out on mature nonovariectomized and ovariectomized Wistar rats, divided into control rats and rats receiving caffeine once daily, 20 mg/kg p.o., for 4 wk. Serum bone turnover markers, bone mass, mass of bone mineral, calcium and phosphorus content, histomorphometric parameters, and bone mechanical properties were examined. Caffeine favorably affected the skeletal system of ovariectomized rats, slightly inhibiting the development of bone changes induced by estrogen deficiency (increasing bone mineralization, and improving the strength and structure of cancellous bone). Moreover, it favorably affected mechanical properties of compact bone. There were no significant effects of caffeine in rats with normal estrogen levels. In conclusion, results of the present study indicate that low-to-moderate caffeine intake may exert some beneficial effects on the skeletal system of mature organisms. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Selection on Inversion Breakpoints Favors Proximity to Pairing Sensitive Sites in Drosophila melanogaster

    PubMed Central

    Corbett-Detig, Russell B.

    2016-01-01

    Chromosomal inversions are widespread among taxa, and have been implicated in a number of biological processes including adaptation, sex chromosome evolution, and segregation distortion. Consistent with selection favoring linkage between loci, it is well established that length is a selected trait of inversions. However, the factors that affect the distribution of inversion breakpoints remain poorly understood. “Sensitive sites” have been mapped on all euchromatic chromosome arms in Drosophila melanogaster, and may be a source of natural selection on inversion breakpoint positions. Briefly, sensitive sites are genomic regions wherein proximal structural rearrangements result in large reductions in local recombination rates in heterozygotes. Here, I show that breakpoints of common inversions are significantly more likely to lie within a cytological band containing a sensitive site than are breakpoints of rare inversions. Furthermore, common inversions for which neither breakpoint intersects a sensitive site are significantly longer than rare inversions, but common inversions whose breakpoints intersect a sensitive site show no evidence for increased length. I interpret these results to mean that selection favors inversions whose breakpoints disrupt synteny near to sensitive sites, possibly because these inversions suppress recombination in large genomic regions. To my knowledge this is the first evidence consistent with positive selection acting on inversion breakpoint positions. PMID:27343234

  3. Selection on Inversion Breakpoints Favors Proximity to Pairing Sensitive Sites in Drosophila melanogaster.

    PubMed

    Corbett-Detig, Russell B

    2016-09-01

    Chromosomal inversions are widespread among taxa, and have been implicated in a number of biological processes including adaptation, sex chromosome evolution, and segregation distortion. Consistent with selection favoring linkage between loci, it is well established that length is a selected trait of inversions. However, the factors that affect the distribution of inversion breakpoints remain poorly understood. "Sensitive sites" have been mapped on all euchromatic chromosome arms in Drosophila melanogaster, and may be a source of natural selection on inversion breakpoint positions. Briefly, sensitive sites are genomic regions wherein proximal structural rearrangements result in large reductions in local recombination rates in heterozygotes. Here, I show that breakpoints of common inversions are significantly more likely to lie within a cytological band containing a sensitive site than are breakpoints of rare inversions. Furthermore, common inversions for which neither breakpoint intersects a sensitive site are significantly longer than rare inversions, but common inversions whose breakpoints intersect a sensitive site show no evidence for increased length. I interpret these results to mean that selection favors inversions whose breakpoints disrupt synteny near to sensitive sites, possibly because these inversions suppress recombination in large genomic regions. To my knowledge this is the first evidence consistent with positive selection acting on inversion breakpoint positions. Copyright © 2016 by the Genetics Society of America.

  4. Oxygen Reduction Reaction Affected by Sulfate-Reducing Bacteria: Different Roles of Bacterial Cells and Metabolites.

    PubMed

    Wu, Jiajia; Liu, Huaiqun; Wang, Peng; Zhang, Dun; Sun, Yan; Li, Ee

    2017-09-01

    Sulfate-reducing bacteria (SRB) were found to be capable of tolerating a certain amount of oxygen (O 2 ), but how they affect oxygen reduction reaction (ORR) has not been clear. The present work investigated the impact of SRB on ORR in 3.5 wt% sodium chloride solution with the cyclic voltammetry method. The addition of SRB culture solution hampered both the reduction of O 2 to superoxide (O 2 ·- ) and hydrogen peroxide (H 2 O 2 ) to water (H 2 O), and the influence of SRB metabolites was much larger than that of bacterial cells. Sulfide and extracellular polymeric substances (EPS), typical inorganic and organic metabolic products, had great impact on ORR. Sulfide played an important role in the decrease of cathodic current for H 2 O 2 reduction due to its hydrolysis and chemical reaction activity with H 2 O 2 . EPS were sticky, easy to adsorb on the electrode surface and abundant in functional groups, which hindered the transformation of O 2 into O 2 ·- and favored the reduction of H 2 O 2 to H 2 O.

  5. Synthesis of branched cores by poly-O-alkylation reaction under phase transfer conditions. A systematic study

    NASA Astrophysics Data System (ADS)

    Landeros, José M.; Silvestre, Hugo A.; Guadarrama, Patricia

    2013-04-01

    In the present paper is described a systematic study of poly-O-alkylation reactions of pentaerythritol (PE) and 1,1,1-tris(hydroxymethyl)ethane (TME) by 1,4 Michael addition, under phase transfer catalysis (PTC), considering the effect of: (1) the organophilicity of PTC (three different catalysts were tested), (2) PTC concentration (from catalytic to equimolar conditions), and (3) the regime of addition of reactants coexisting in the aqueous phase of the heterogeneous reaction system. The less organophilic transfer agent showed the best performance on these reactions. In our case, benzyltriethylammonium chloride (TEBAC) gathers the best features. The presence of NaOH as base, promotes the interfacial mechanism and not the bulk one. Out of the optimal range of concentration of NaOH (35-40%), competition between nucleophiles can occur, due to the saturation of the medium. Regarding the regime of addition of reactants, the scenario where NaOH and TEBAC are less time in contact, favors the formation of the desired products. Finally, the deprotection of tert-butyl groups of the poly-O-alkylated compounds is described, to get branched cores with terminal carboxylic acid groups in good yields (90-94%). Spectroscopic properties, such as IR, 1H and 13C NMR, of the synthesized compounds are also described.

  6. Combination of cascade chemical reactions with graphene-DNA interaction to develop new strategy for biosensor fabrication.

    PubMed

    Zhu, Xiaoli; Sun, Liya; Chen, Yangyang; Ye, Zonghuang; Shen, Zhongming; Li, Genxi

    2013-09-15

    Graphene, a single atom thick and two dimensional carbon nano-material, has been proven to possess many unique properties, one of which is the recent discovery that it can interact with single-stranded DNA through noncovalent π-π stacking. In this work, we demonstrate that a new strategy to fabricate many kinds of biosensors can be developed by combining this property with cascade chemical reactions. Taking the fabrication of glucose sensor as an example, while the detection target, glucose, may regulate the graphene-DNA interaction through three cascade chemical reactions, electrochemical techniques are employed to detect the target-regulated graphene-DNA interaction. Experimental results show that in a range from 5μM to 20mM, the glucose concentration is in a natural logarithm with the logarithm of the amperometric response, suggesting a best detection limit and detection range. The proposed biosensor also shows favorable selectivity, and it has the advantage of no need for labeling. What is more, by controlling the cascade chemical reactions, detection of a variety of other targets may be achieved, thus the strategy proposed in this work may have a wide application potential in the future. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Negative reactions to monitoring: Do they undermine the ability of monitoring to protect adolescents?

    PubMed

    Laird, Robert D; Zeringue, Megan M; Lambert, Emily S

    2018-02-01

    This study focused on adolescents' negative reactions to parental monitoring to determine whether parents should avoid excessive monitoring because adolescents find monitoring behaviors to be over-controlling and privacy invasive. Adolescents (n = 242, M age = 15.4 years; 51% female) reported monitoring, negative reactions, warmth, antisocial behavior, depressive symptoms, and disclosure. Adolescents additionally reported antisocial behavior, depressive symptoms, and disclosure one to two years later. In cross-sectional analyses, less monitoring but more negative reactions were linked with less disclosure, suggesting that negative reactions can undermine parents' ability to obtain information. Although monitoring behaviors were not related to depressive symptoms, more negative reactions were linked with more depressive symptoms, suggesting that negative reactions also may increase depressive symptoms as a side effect of monitoring behavior. Negative reactions were not linked to antisocial behavior. There were no longitudinal links between negative reactions and changes in disclosure, antisocial behavior, or depressive symptoms. Copyright © 2017. Published by Elsevier Ltd.

  8. Interaction Heterogeneity can Favorably Impact Colloidal Crystal Nucleation

    NASA Astrophysics Data System (ADS)

    Jenkins, Ian C.; Crocker, John C.; Sinno, Talid

    2017-10-01

    Colloidal particles with short-ranged attractions, e.g., micron-scale spheres functionalized with single-stranded DNA oligomers, are susceptible to becoming trapped in disordered configurations even when a crystalline arrangement is the ground state. Moreover, for reasons that are not well understood, seemingly minor variations in the particle formulation can lead to dramatic changes in the crystallization outcome. We demonstrate, using a combination of equilibrium and nonequilibrium computer simulations, that interaction heterogeneity—variations in the energetic interactions among different particle pairs in the population—may favorably impact crystal nucleation. Specifically, interaction heterogeneity is found to lower the free energy barrier to nucleation via the formation of clusters comprised preferentially of strong-binding particle pairs. Moreover, gelation is inhibited by "spreading out over time" the nucleation process, resulting in a reduced density of stable nuclei, allowing each to grow unhindered and larger. Our results suggest a simple and robust approach for enhancing colloidal crystallization near the "sticky sphere" limit, and support the notion that differing extents of interaction heterogeneity arising from various particle functionalization protocols may contribute to the otherwise unexplained variations in crystallization outcomes reported in the literature.

  9. Structures of Neural Correlation and How They Favor Coding

    PubMed Central

    Franke, Felix; Fiscella, Michele; Sevelev, Maksim; Roska, Botond; Hierlemann, Andreas; da Silveira, Rava Azeredo

    2017-01-01

    Summary The neural representation of information suffers from “noise”—the trial-to-trial variability in the response of neurons. The impact of correlated noise upon population coding has been debated, but a direct connection between theory and experiment remains tenuous. Here, we substantiate this connection and propose a refined theoretical picture. Using simultaneous recordings from a population of direction-selective retinal ganglion cells, we demonstrate that coding benefits from noise correlations. The effect is appreciable already in small populations, yet it is a collective phenomenon. Furthermore, the stimulus-dependent structure of correlation is key. We develop simple functional models that capture the stimulus-dependent statistics. We then use them to quantify the performance of population coding, which depends upon interplays of feature sensitivities and noise correlations in the population. Because favorable structures of correlation emerge robustly in circuits with noisy, nonlinear elements, they will arise and benefit coding beyond the confines of retina. PMID:26796692

  10. Preliminary report of the uranium favorability of shear zones in the crystalline rocks of the southern Appalachians

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

    Penley, H.M.; Schot, E.H.; Sewell, J.M.

    1978-11-01

    Three sheared areas in the crystalline Piedmont and Blue Ridge provinces, from which uranium occurrences or anomalous radioactivity have been reported, were studied to determine their favorability for uranium mineralization. The study, which involved a literature review, geologic reconnaissance, ground radiometric surveys, and sampling of rock outcrops for petrographic and chemical analyses, indicates that more-detailed investigations of these and similar areas are warranted. In each area, surface leaching and deep residual cover make it difficult to assess the potential for uranium mineralization on the basis of results from chemical analyses for U/sub 3/O/sub 8/ and the radiometric surveys. Although anomalousmore » radioactivity and anomalous chemical uranium values were noted in only a few rock exposures and samples from the shear zones, the potential for uranium mineralization at depth could be much greater than indicated by these surface data. The study indicates that shear zones within Precambiran granitic basement complexes (such as the Wilson Creek Gneiss of western North Carolina, the Cranberry Gneiss of eastern Tennessee, and the Toxaway Gneiss of western South Carolina) are favorable as hosts for uranium and may contain subsurface deposits. Mylonitized graphitic schists immediately north of the Towaliga fault in Alabama and Georgia may be favorable host rocks for uranium.« less

  11. Competing E2 and SN2 Mechanisms for the F- + CH3CH2I Reaction.

    PubMed

    Yang, Li; Zhang, Jiaxu; Xie, Jing; Ma, Xinyou; Zhang, Linyao; Zhao, Chenyang; Hase, William L

    2017-02-09

    Anti-E2, syn-E2, inv-, and ret-S N 2 reaction channels for the gas-phase reaction of F - + CH 3 CH 2 I were characterized with a variety of electronic structure calculations. Geometrical analysis confirmed synchronous E2-type transition states for the elimination of the current reaction, instead of nonconcerted processes through E1cb-like and E1-like mechanisms. Importantly, the controversy concerning the reactant complex for anti-E2 and inv-S N 2 paths has been clarified in the present work. A positive barrier of +19.2 kcal/mol for ret-S N 2 shows the least feasibility to occur at room temperature. Negative activation energies (-16.9, -16.0, and -4.9 kcal/mol, respectively) for inv-S N 2, anti-E2, and syn-E2 indicate that inv-S N 2 and anti-E2 mechanisms significantly prevail over the eclipsed elimination. Varying the leaving group for a series of reactions F - + CH 3 CH 2 Y (Y = F, Cl, Br, and I) leads to monotonically decreasing barriers, which relates to the gradually looser TS structures following the order F > Cl > Br > I. The reactivity of each channel nearly holds unchanged except for the perturbation between anti-E2 and inv-S N 2. RRKM calculation reveals that the reaction of the fluorine ion with ethyl iodide occurs predominately via anti-E2 elimination, and the inv-S N 2 pathway is suppressed, although it is energetically favored. This phenomenon indicates that, in evaluating the competition between E2 and S N 2 processes, the kinetic or dynamical factors may play a significant role. By comparison with benchmark CCSD(T) energies, MP2, CAM-B3LYP, and M06 methods are recommended to perform dynamics simulations of the title reaction.

  12. Reaction of gas phase OH with unsaturated self-assembled monolayers and relevance to atmospheric organic oxidations.

    PubMed

    Moussa, Samar G; Finlayson-Pitts, Barbara J

    2010-08-28

    The kinetics and mechanisms of the reaction of gas phase OH radicals with organics on surfaces are of fundamental chemical interest, as well as relevant to understanding the degradation of organics on tropospheric surfaces or when they are components of airborne particles. We report here studies of the oxidation of a terminal alkene self-assembled monolayer (7-octenyltrichlorosilane, C8= SAM) on a germanium attenuated total reflectance crystal by OH radicals at a concentration of 2.1 x 10(5) cm(-3) at 1 atm total pressure and 298 K in air. Loss of the reactant SAM and the formation of surface products were followed in real time using infrared spectroscopy. From the rate of loss of the C=C bond, a reaction probability within experimental error of unity was derived. The products formed on the surface include organic nitrates and carbonyl compounds, with yields of 10 +/- 4% and < or = 7 +/- 4%, respectively, and there is evidence for the formation of organic products with C-O bonds such as alcohols, ethers and/or alkyl peroxides and possibly peroxynitrates. The yield of organic nitrates relative to carbonyl compounds is higher than expected based on analogous gas phase mechanisms, suggesting that the branching ratio for the RO(2) + NO reaction is shifted to favor the formation of organic nitrates when the reaction occurs on a surface. Water uptake onto the surface was only slightly enhanced upon oxidation, suggesting that oxidation per se cannot be taken as a predictor of increased hydrophilicity of atmospheric organics. These experiments indicate that the mechanisms for the surface reactions are different from gas phase reactions, but the OH oxidation of surface species will still be a significant contributor to determining their lifetimes in air.

  13. Origin of Enhanced Reactivity of a Microsolvated Nucleophile in Ion Pair SN2 Reactions: The Cases of Sodium p-Nitrophenoxide with Halomethanes in Acetone.

    PubMed

    Li, Qiang-Gen; Xu, Ke; Ren, Yi

    2015-04-30

    In a kinetic experiment on the SN2 reaction of sodium p-nitrophenoxide with iodomethane in acetone-water mixed solvent, Humeres et al. (J. Org. Chem. 2001, 66, 1163) found that the reaction depends strongly on the medium, and the fastest rate constant was observed in pure acetone. The present work tries to explore why acetone can enhance the reactivity of the title reactions. Accordingly, we make a mechanistic study on the reactions of sodium p-nitrophenoxide with halomethanes (CH3X, X = Cl, Br, I) in acetone by using a supramolecular/continuum model at the PCM-MP2/6-311+G(d,p)//B3LYP/6-311+G(d,p) level, in which the ion pair nucleophile is microsolvated by one to three acetone molecules. We compared the reactivity of the microsolvated ion pair nucleophiles with solvent-free ion pair and anionic ones. Our results clearly reveal that the microsolvated ion pair nucleophile is favorable for the SN2 reactions; meanwhile, the origin of the enhanced reactivity induced by microsolvation of the nucleophile is discussed in terms of the geometries of transition state (TS) structures and activation strain model, suggesting that lower deformation energies and stronger interaction energies between the deformed reactants in the TS lead to the lower overall reaction barriers for the SN2 reaction of microsolvated sodium p-nitrophenoxide toward halomethanes in acetone.

  14. Notch3 signaling is associated with MUC5AC expression and favorable prognosis in patients with small intestinal adenocarcinomas.

    PubMed

    Eom, Dae-Woon; Hong, Seung-Mo; Kim, Jihun; Kim, Gwangil; Bae, Young Kyung; Jang, Kee-Taek; Yu, Eunsil

    2014-08-01

    Notch signaling plays diverse roles not only in physiologic processes, including development and differentiation but also in tumorigenesis, either as a tumor promoter or suppressor depending on the cellular context, level of expression and cross-talk with other signaling pathways. In this study we investigated the expression of Notch3 and MUC proteins and their clinicopathological significance in small intestinal adenocarcinoma (SIAC). Surgically resected 191 SIACs and their clinical data were collected. Immunohistochemistry for Notch3, MUC2, MUC5AC, and MUC6 using tissue microarrays from formalin-fixed paraffin-embedded normal and matched tumor tissues was performed. Notch3 expression was found in 52 (29.9%) cases of the tumors. MUC2, MUC5AC, and MUC6 were expressed in 52 (27.5%), 51 (31.9%), and 42 (22.0%) cases of the tumor, respectively. Notch3 expression was correlated with the absence of lymphovascular invasion (p=0.009), lower T stage (p=0.038), and histological subtype of tubular adenocarcinoma (p=0.01), respectively. MUC2 was correlated with large tumor size (p=0.013) and mucinous and signet ring cell adenocarcinomas (p=0.01). MUC5A was correlated with proximal tumor location (p<0.0001) and tumor differentiation (p=0.027). MUC6 was correlated with proximal tumor location (p<0.0001) and lower pT stage (p=0.009), and absence of lymphovascular invasion, respectively. A significant correlation was noted between Notch3 and MUC5AC expression (p=0.019). Notch3 expression was a relatively favorable prognostic factor in SIACs by univariate (p=0.05) and multivariate analysis (p=0.08, Cox Hazard ratio 0.841). Our findings indicate that Notch3 signaling, associated with MUC5AC expression, could be a more favorable prognostic factor in SIACs. Copyright © 2014 Elsevier GmbH. All rights reserved.

  15. Procedures for Decomposing a Redox Reaction into Half-Reaction

    ERIC Educational Resources Information Center

    Fishtik, Ilie; Berka, Ladislav H.

    2005-01-01

    A simple algorithm for a complete enumeration of the possible ways a redox reaction (RR) might be uniquely decomposed into half-reactions (HRs) using the response reactions (RERs) formalism is presented. A complete enumeration of the possible ways a RR may be decomposed into HRs is equivalent to a complete enumeration of stoichiometrically…

  16. Finding the K best synthesis plans.

    PubMed

    Fagerberg, Rolf; Flamm, Christoph; Kianian, Rojin; Merkle, Daniel; Stadler, Peter F

    2018-04-05

    In synthesis planning, the goal is to synthesize a target molecule from available starting materials, possibly optimizing costs such as price or environmental impact of the process. Current algorithmic approaches to synthesis planning are usually based on selecting a bond set and finding a single good plan among those induced by it. We demonstrate that synthesis planning can be phrased as a combinatorial optimization problem on hypergraphs by modeling individual synthesis plans as directed hyperpaths embedded in a hypergraph of reactions (HoR) representing the chemistry of interest. As a consequence, a polynomial time algorithm to find the K shortest hyperpaths can be used to compute the K best synthesis plans for a given target molecule. Having K good plans to choose from has many benefits: it makes the synthesis planning process much more robust when in later stages adding further chemical detail, it allows one to combine several notions of cost, and it provides a way to deal with imprecise yield estimates. A bond set gives rise to a HoR in a natural way. However, our modeling is not restricted to bond set based approaches-any set of known reactions and starting materials can be used to define a HoR. We also discuss classical quality measures for synthesis plans, such as overall yield and convergency, and demonstrate that convergency has a built-in inconsistency which could render its use in synthesis planning questionable. Decalin is used as an illustrative example of the use and implications of our results.

  17. Erratum: Correction to: The sTOF, a Favorable Geometry for a Time-of-Flight Analyzer

    NASA Astrophysics Data System (ADS)

    Murphy, Daniel M.

    2018-05-01

    In the article "The sTOF, a Favorable Geometry for a Time-of-Flight Analyzer", the electric sectors in the prototype analyzer used to generate the data in Figure 4 were mistakenly listed as having a radius of 165 mm. The correct size is a diameter of 165 mm.

  18. Finding Direction in the Search for Selection.

    PubMed

    Thiltgen, Grant; Dos Reis, Mario; Goldstein, Richard A

    2017-01-01

    Tests for positive selection have mostly been developed to look for diversifying selection where change away from the current amino acid is often favorable. However, in many cases we are interested in directional selection where there is a shift toward specific amino acids, resulting in increased fitness in the species. Recently, a few methods have been developed to detect and characterize directional selection on a molecular level. Using the results of evolutionary simulations as well as HIV drug resistance data as models of directional selection, we compare two such methods with each other, as well as against a standard method for detecting diversifying selection. We find that the method to detect diversifying selection also detects directional selection under certain conditions. One method developed for detecting directional selection is powerful and accurate for a wide range of conditions, while the other can generate an excessive number of false positives.

  19. Design of N-Coordinated Dual-Metal Sites: A Stable and Active Pt-Free Catalyst for Acidic Oxygen Reduction Reaction.

    PubMed

    Wang, Jing; Huang, Zhengqing; Liu, Wei; Chang, Chunran; Tang, Haolin; Li, Zhijun; Chen, Wenxing; Jia, Chunjiang; Yao, Tao; Wei, Shiqiang; Wu, Yuen; Li, Yadong

    2017-12-06

    We develop a host-guest strategy to construct an electrocatalyst with Fe-Co dual sites embedded on N-doped porous carbon and demonstrate its activity for oxygen reduction reaction in acidic electrolyte. Our catalyst exhibits superior oxygen reduction reaction performance, with comparable onset potential (E onset , 1.06 vs 1.03 V) and half-wave potential (E 1/2 , 0.863 vs 0.858 V) than commercial Pt/C. The fuel cell test reveals (Fe,Co)/N-C outperforms most reported Pt-free catalysts in H 2 /O 2 and H 2 /air. In addition, this cathode catalyst with dual metal sites is stable in a long-term operation with 50 000 cycles for electrode measurement and 100 h for H 2 /air single cell operation. Density functional theory calculations reveal the dual sites is favored for activation of O-O, crucial for four-electron oxygen reduction.

  20. Increasing insect reactions in Alaska: is this related to changing climate?

    PubMed

    Demain, Jeffrey G; Gessner, Bradford D; McLaughlin, Joseph B; Sikes, Derek S; Foote, J Timothy

    2009-01-01

    In 2006, Fairbanks, AK, reported its first cases of fatal anaphylaxis as a result of Hymenoptera stings concurrent with an increase in insect reactions observed throughout the state. This study was designed to determine whether Alaska medical visits for insect reactions have increased. We conducted a retrospective review of three independent patient databases in Alaska to identify trends of patients seeking medical care for adverse reactions after insect-related events. For each database, an insect reaction was defined as a claim for the International Classification of Diseases, Ninth Edition (ICD-9), codes E9053, E906.4, and 989.5. Increases in insect reactions in each region were compared with temperature changes in the same region. Each database revealed a statistically significant trend in patients seeking care for insect reactions. Fairbanks Memorial Hospital Emergency Department reported a fourfold increase in patients in 2006 compared with previous years (1992-2005). The Allergy, Asthma, and Immunology Center of Alaska reported a threefold increase in patients from 1999 to 2002 to 2003 to 2007. A retrospective review of the Alaska Medicaid database from 1999 to 2006 showed increases in medical claims for insect reactions among all regions, with the largest percentage of increases occurring in the most northern areas. Increases in insect reactions in Alaska have occurred after increases in annual and winter temperatures, and these findings may be causally related.

  1. Atmospheric chemical reactions of alternatives of polybrominated diphenyl ethers initiated by OH: A case study on triphenyl phosphate.

    PubMed

    Yu, Qi; Xie, Hong-Bin; Chen, Jingwen

    2016-11-15

    Many studies have been performed to evaluate the environmental risk caused by alternative flame retardants (AFRs) of polybrominated diphenyl ethers due to their ubiquitous occurrence in the environment. However, as an indispensable component of the environmental risk assessment, the information on atmospheric fate of AFRs is limited although some AFRs have been frequently and highly detected in the atmosphere. Here, a combined quantum chemical method and kinetics modeling were used to investigate atmospheric transformation mechanism and kinetics of AFRs initiated by OH in the presence of O2, taking triphenyl phosphate (TPhP) as a case. Results show that the pathway involving initial OH addition to phenyl of TPhP to form TPhP-OH adduct, and subsequent reaction of the TPhP-OH adduct with O2 to finally form phenol phosphate, is the most favorable for the titled reaction. The calculated overall reaction rate constant is 1.6×10(-12)cm(3) molecule(-1)s(-1), translating 7.6days atmospheric lifetime of TPhP. This clarifies that gaseous TPhP has atmospheric persistence. In addition, it was found that ice surface, as a case of ubiquitous water in the atmosphere, has little effect on the kinetics of the rate-determining step in the OH-initiated TPhP reaction. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Explaining financial and prosocial biases in favor of attractive people: Interdisciplinary perspectives from economics, social psychology, and evolutionary psychology.

    PubMed

    Maestripieri, Dario; Henry, Andrea; Nickels, Nora

    2017-01-01

    Financial and prosocial biases in favor of attractive adults have been documented in the labor market, in social transactions in everyday life, and in studies involving experimental economic games. According to the taste-based discrimination model developed by economists, attractiveness-related financial and prosocial biases are the result of preferences or prejudices similar to those displayed toward members of a particular sex, racial, ethnic, or religious group. Other explanations proposed by economists and social psychologists maintain that attractiveness is a marker of personality, intelligence, trustworthiness, professional competence, or productivity. Evolutionary psychologists have argued that attractive adults are favored because they are preferred sexual partners. Evidence that stereotypes about attractive people are causally related to financial or prosocial biases toward them is weak or nonexistent. Consistent with evolutionary explanations, biases in favor of attractive women appear to be more consistent or stronger than those in favor of attractive men, and biases are more consistently reported in interactions between opposite-sex than same-sex individuals. Evolutionary explanations also account for increased prosocial behavior in situations in which attractive individuals are simply bystanders. Finally, evolutionary explanations are consistent with the psychological, physiological, and behavioral changes that occur when individuals are exposed to potential mates, which facilitate the expression of courtship behavior and increase the probability of occurrence of mating. Therefore, multiple lines of evidence suggest that mating motives play a more important role in driving financial and prosocial biases toward attractive adults than previously recognized.

  3. Search for an explanation for neutralization rates of atomic ion-ion reactions

    NASA Astrophysics Data System (ADS)

    Miller, Thomas M.; Wiens, Justin P.; Shuman, Nicholas S.; Viggiano, Albert A.

    2016-09-01

    We have measured well over a hundred rate coefficients k for cation-anion mutual neutralization reactions at thermal energies. For molecular ions, the k at 300 K tend not to vary more than a factor of two or three, presumably because a great many neutral states cross the incoming Coulombic potential energy curve. Atomic-atomic systems, for which there are few favorable curve crossings between the neutral and Coulombic curves, show variation of at least a factor of 60 in the measured k values at 300 K. For reactions involving the noble-gas cations, we assume that the final state is the lowest excited state of the neutral, plus the ground state of the neutralized anion, because otherwise the crossing distance R is so small that the curve-crossing probability is nil. We plotted measured k values (in cm3/s) vs the distance R (in bohr) at which the neutral and Coulombic curves cross, the found that the data are fairly well fit by a power law for k, 10-4R - 2 . 8 . The question is, is there a physical explanation for the observed dependence on R? We will discuss the data and the expectations of Landau-Zener theory. Supported by Air Force Office of Scientific Research (AFOSR-2303EP).

  4. Effect of micro-stirring on enzymatic reaction kinetics inside a biomimetic container

    NASA Astrophysics Data System (ADS)

    Gozen, Irep; Horowitz, Viva; Chambers, Zachary; Manoharan, Vinothan

    The intracellular environment is dynamic, influenced by the motion of active machinery such as cytoskeleton filaments and molecular motors. To understand whether and how such activity affects the rates of diffusion-limited reactions, we construct a model system consisting of a phospholipid vesicle encapsulating a small number of micro- or nanoparticles, the active motion of which can be induced by chemical or magnetic cues. We aim to determine a relation between active motion of particles and rates of enzymatic reactions in the confined volume. Our findings might illuminate how active motion influences cytoplasmic reaction dynamics, or may have played a role in protocell genetics.

  5. Reactions of religious fundamentalists to taboo images and words.

    PubMed

    Bates, Larry W; Hudiburg, Richard A; Lauderdale, Elizabeth P; Castillo, Joseph R

    2013-08-01

    Some view religious fundamentalism as inclusive of fear of the world as a dangerous place. Fundamentalists are known to have extensive taboo lists, but research concerning their reactions to taboo stimuli is sparse. If fear is a basic component of fundamentalism, then reactions to taboo stimuli should be somewhat similar to common fear reactions, including subjective appraisal of discomfort, psychophysiological arousal, cognitive interference, and behavioral avoidance. The current research addressed some of these questions with three studies to examine subjective discomfort to religiously-taboo and religiously-neutral words and photographs (N = 160), physiological arousal to these same photographs (N = 129), and attentional bias on a modified Stroop test of these same words (N = 182). Although subjective appraisals of discomfort to taboo words and photographs among fundamentalists were confirmed, this research did not find that physiological responses or cognitive interference to taboo stimuli were elevated in those scoring high in religious fundamentalism.

  6. Retrosynthetic Reaction Prediction Using Neural Sequence-to-Sequence Models

    PubMed Central

    2017-01-01

    We describe a fully data driven model that learns to perform a retrosynthetic reaction prediction task, which is treated as a sequence-to-sequence mapping problem. The end-to-end trained model has an encoder–decoder architecture that consists of two recurrent neural networks, which has previously shown great success in solving other sequence-to-sequence prediction tasks such as machine translation. The model is trained on 50,000 experimental reaction examples from the United States patent literature, which span 10 broad reaction types that are commonly used by medicinal chemists. We find that our model performs comparably with a rule-based expert system baseline model, and also overcomes certain limitations associated with rule-based expert systems and with any machine learning approach that contains a rule-based expert system component. Our model provides an important first step toward solving the challenging problem of computational retrosynthetic analysis. PMID:29104927

  7. Experimental evidence of quantum radiation reaction in aligned crystals.

    PubMed

    Wistisen, Tobias N; Di Piazza, Antonino; Knudsen, Helge V; Uggerhøj, Ulrik I

    2018-02-23

    Quantum radiation reaction is the influence of multiple photon emissions from a charged particle on the particle's dynamics, characterized by a significant energy-momentum loss per emission. Here we report experimental radiation emission spectra from ultrarelativistic positrons in silicon in a regime where quantum radiation reaction effects dominate the positron's dynamics. Our analysis shows that while the widely used quantum approach is overall the best model, it does not completely describe all the data in this regime. Thus, these experimental findings may prompt seeking more generally valid methods to describe quantum radiation reaction. This experiment is a fundamental test of quantum electrodynamics in a regime where the dynamics of charged particles is strongly influenced not only by the external electromagnetic fields but also by the radiation field generated by the charges themselves and where each photon emission may significantly reduce the energy of the charge.

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

    NASA Astrophysics Data System (ADS)

    Rolih, Biljana; Ozolins, Vidvuds; Ozolins Team

    2013-03-01

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

  9. Ruthenium-catalyzed metathesis reactions of ortho- and meta-dialkenyl-carboranes: efficient ring-closing and acyclic diene polymerization reactions.

    PubMed

    Guron, Marta; Wei, Xiaolan; Carroll, Patrick J; Sneddon, Larry G

    2010-07-05

    The ruthenium-catalyzed metathesis reactions of dialkenyl-substituted ortho- and meta-carboranes provide excellent routes to both cyclic-substituted o-carboranes and new types of main-chain m-carborane polymers. The adjacent positions of the two olefins in the 1,2-(alkenyl)(2)-o-carboranes strongly favor the formation of ring-closed (RCM) products with the reactions of 1,2-(CH(2)=CHCH(2))(2)-1,2-C(2)B(10)H(10) (1), 1,2-(CH(2)=CH(CH(2))(3)CH(2))(2)-1,2-C(2)B(10)H(10) (2), 1,2-(CH(2)=CHSiMe(2))(2)-1,2-C(2)B(10)H(10) (3), 1,2-(CH(2)=CHCH(2)SiMe(2))(2)-1,2-C(2)B(10)H(10) (4), and 1,2-[CH(2)=CH(CH(2))(4)SiMe(2)](2)-1,2-C(2)B(10)H(10) (5) affording 1,2-(-CH(2)CH=CHCH(2)-)-C(2)B(10)H(10) (10), 1,2-[-CH(2)(CH(2))(3)CH=CH(CH(2))(3)CH(2)-]-1,2-C(2)B(10)H(10) (11), 1,2-[-SiMe(2)CH=CHSiMe(2)-]-1,2-C(2)B(10)H(10) (12), 1,2-[-SiMe(2)CH(2)CH=CHCH(2)SMe(2)-]-C(2)B(10)H(10) (13), and 1,2-[-SiMe(2)(CH(2))(4)CH=CH(CH(2))(4)SiMe(2)-]-C(2)B(10)H(10) (14), respectively, in 72-97% yields. On the other hand, the reaction of 1,2-(CH(2)-CHCH(2)OC(=O))(2)-1,2-C(2)B(10)H(10) (6) gave cyclo-[1,2-(1',8'-C(=O)OCH(2)CH=CHCH(2)OC(=O))-1,2-C(2)B(10)H(10)](2) (15a) and polymer 15b resulting from intermolecular metathesis reactions. The nonadjacent positions of the alkenyl groups in the 1,7-(alkenyl)(2)-m-carboranes, 1,7-(CH(2)=CHCH(2))(2)-1,7-C(2)B(10)H(10) (7), 1,7-(CH(2)=CH(CH(2))(3)CH(2))(2)-1,7-C(2)B(10)H(10) (8), and 1,7-(CH(2)=CHCH(2)SiMe(2))(2)-1,7-C(2)B(10)H(10) (9), disfavor the formation of RCM products, and in these cases, acyclic diene metathesis polymerizations (ADMET) produced new types of main chain m-carborane polymers. The structures of 3, 9, 11, 12, 13, and 15a were crystallographically confirmed.

  10. Association Between Duration of Resuscitation and Favorable Outcome After Out-of-Hospital Cardiac Arrest: Implications for Prolonging or Terminating Resuscitation.

    PubMed

    Reynolds, Joshua C; Grunau, Brian E; Rittenberger, Jon C; Sawyer, Kelly N; Kurz, Michael C; Callaway, Clifton W

    2016-12-20

    Little evidence guides the appropriate duration of resuscitation in out-of-hospital cardiac arrest, and case features justifying longer or shorter durations are ill defined. We estimated the impact of resuscitation duration on the probability of favorable functional outcome in out-of-hospital cardiac arrest using a large, multicenter cohort. This was a secondary analysis of a North American, single-blind, multicenter, cluster-randomized, clinical trial (ROC-PRIMED [Resuscitation Outcomes Consortium Prehospital Resuscitation Using an Impedance Valve and Early Versus Delayed]) of consecutive adults with nontraumatic, emergency medical services-treated out-of-hospital cardiac arrest. Primary exposure was duration of resuscitation in minutes (onset of professional resuscitation to return of spontaneous circulation [ROSC] or termination of resuscitation). Primary outcome was survival to hospital discharge with favorable outcome (modified Rankin scale [mRS] score of 0-3). Subjects were additionally classified as survival with unfavorable outcome (mRS score of 4-5), ROSC without survival (mRS score of 6), or without ROSC. Subject accrual was plotted as a function of resuscitation duration, and the dynamic probability of favorable outcome at discharge was estimated for the whole cohort and subgroups. Adjusted logistic regression models tested the association between resuscitation duration and survival with favorable outcome. The primary cohort included 11 368 subjects (median age, 69 years [interquartile range, 56-81 years]; 7121 men [62.6%]). Of these, 4023 (35.4%) achieved ROSC, 1232 (10.8%) survived to hospital discharge, and 905 (8.0%) had an mRS score of 0 to 3 at discharge. Distribution of cardiopulmonary resuscitation duration differed by outcome (P<0.00001). For cardiopulmonary resuscitation duration up to 37.0 minutes (95% confidence interval, 34.9-40.9 minutes), 99% with an eventual mRS score of 0 to 3 at discharge achieved ROSC. The dynamic probability of an m

  11. Mechanism of chimera formation during the Multiple Displacement Amplification reaction.

    PubMed

    Lasken, Roger S; Stockwell, Timothy B

    2007-04-12

    Multiple Displacement Amplification (MDA) is a method used for amplifying limiting DNA sources. The high molecular weight amplified DNA is ideal for DNA library construction. While this has enabled genomic sequencing from one or a few cells of unculturable microorganisms, the process is complicated by the tendency of MDA to generate chimeric DNA rearrangements in the amplified DNA. Determining the source of the DNA rearrangements would be an important step towards reducing or eliminating them. Here, we characterize the major types of chimeras formed by carrying out an MDA whole genome amplification from a single E. coli cell and sequencing by the 454 Life Sciences method. Analysis of 475 chimeras revealed the predominant reaction mechanisms that create the DNA rearrangements. The highly branched DNA synthesized in MDA can assume many alternative secondary structures. DNA strands extended on an initial template can be displaced becoming available to prime on a second template creating the chimeras. Evidence supports a model in which branch migration can displace 3'-ends freeing them to prime on the new templates. More than 85% of the resulting DNA rearrangements were inverted sequences with intervening deletions that the model predicts. Intramolecular rearrangements were favored, with displaced 3'-ends reannealing to single stranded 5'-strands contained within the same branched DNA molecule. In over 70% of the chimeric junctions, the 3' termini had initiated priming at complimentary sequences of 2-21 nucleotides (nts) in the new templates. Formation of chimeras is an important limitation to the MDA method, particularly for whole genome sequencing. Identification of the mechanism for chimera formation provides new insight into the MDA reaction and suggests methods to reduce chimeras. The 454 sequencing approach used here will provide a rapid method to assess the utility of reaction modifications.

  12. Mechanism of chimera formation during the Multiple Displacement Amplification reaction

    PubMed Central

    Lasken, Roger S; Stockwell, Timothy B

    2007-01-01

    Background Multiple Displacement Amplification (MDA) is a method used for amplifying limiting DNA sources. The high molecular weight amplified DNA is ideal for DNA library construction. While this has enabled genomic sequencing from one or a few cells of unculturable microorganisms, the process is complicated by the tendency of MDA to generate chimeric DNA rearrangements in the amplified DNA. Determining the source of the DNA rearrangements would be an important step towards reducing or eliminating them. Results Here, we characterize the major types of chimeras formed by carrying out an MDA whole genome amplification from a single E. coli cell and sequencing by the 454 Life Sciences method. Analysis of 475 chimeras revealed the predominant reaction mechanisms that create the DNA rearrangements. The highly branched DNA synthesized in MDA can assume many alternative secondary structures. DNA strands extended on an initial template can be displaced becoming available to prime on a second template creating the chimeras. Evidence supports a model in which branch migration can displace 3'-ends freeing them to prime on the new templates. More than 85% of the resulting DNA rearrangements were inverted sequences with intervening deletions that the model predicts. Intramolecular rearrangements were favored, with displaced 3'-ends reannealing to single stranded 5'-strands contained within the same branched DNA molecule. In over 70% of the chimeric junctions, the 3' termini had initiated priming at complimentary sequences of 2–21 nucleotides (nts) in the new templates. Conclusion Formation of chimeras is an important limitation to the MDA method, particularly for whole genome sequencing. Identification of the mechanism for chimera formation provides new insight into the MDA reaction and suggests methods to reduce chimeras. The 454 sequencing approach used here will provide a rapid method to assess the utility of reaction modifications. PMID:17430586

  13. The Impact of Nuclear Reaction Rate Uncertainties on the Evolution of Core-collapse Supernova Progenitors

    NASA Astrophysics Data System (ADS)

    Fields, C. E.; Timmes, F. X.; Farmer, R.; Petermann, I.; Wolf, William M.; Couch, S. M.

    2018-02-01

    We explore properties of core-collapse supernova progenitors with respect to the composite uncertainties in the thermonuclear reaction rates by coupling the probability density functions of the reaction rates provided by the STARLIB reaction rate library with MESA stellar models. We evolve 1000 models of 15{M}ȯ from the pre-main sequence to core O-depletion at solar and subsolar metallicities for a total of 2000 Monte Carlo stellar models. For each stellar model, we independently and simultaneously sample 665 thermonuclear reaction rates and use them in a MESA in situ reaction network that follows 127 isotopes from 1H to 64Zn. With this framework we survey the core mass, burning lifetime, composition, and structural properties at five different evolutionary epochs. At each epoch we measure the probability distribution function of the variations of each property and calculate Spearman rank-order correlation coefficients for each sampled reaction rate to identify which reaction rate has the largest impact on the variations on each property. We find that uncertainties in the reaction rates of {}14{{N}}{({{p}},γ )}15{{O}}, triple-α, {}12{{C}}{(α ,γ )}16{{O}}, 12C(12C,p)23Na, 12C(16O, p)27Al, 16O(16O,n)31S, 16O(16O, p)31P, and 16O(16O,α)28Si dominate the variations of the properties surveyed. We find that variations induced by uncertainties in nuclear reaction rates grow with each passing phase of evolution, and at core H-, He-depletion they are of comparable magnitude to the variations induced by choices of mass resolution and network resolution. However, at core C-, Ne-, and O-depletion, the reaction rate uncertainties can dominate the variation, causing uncertainty in various properties of the stellar model in the evolution toward iron core-collapse.

  14. Cross-reactions to desoximetasone and mometasone furoate in a patient with multiple topical corticosteroid allergies.

    PubMed

    Donovan, Jeffrey C H; Dekoven, Joel G

    2006-09-01

    A 60-year-old man developed a bullous contact dermatitis after topical corticosteroid treatment of dermatitis on his lower leg. Subsequent patch testing showed cross-reactions to numerous group B and group D corticosteroids as well as cross-reactions to group C desoximetasone and group D1 mometasone furoate. His patch-test result was negative for the group A corticosteroids hydrocortisone and tixocortol pivalate. We discuss the uncommon finding of cross-reactions to desoximetasone and mometasone furoate.

  15. The effect of iconicity of visual displays on statistical reasoning: evidence in favor of the null hypothesis.

    PubMed

    Sirota, Miroslav; Kostovičová, Lenka; Juanchich, Marie

    2014-08-01

    Knowing which properties of visual displays facilitate statistical reasoning bears practical and theoretical implications. Therefore, we studied the effect of one property of visual diplays - iconicity (i.e., the resemblance of a visual sign to its referent) - on Bayesian reasoning. Two main accounts of statistical reasoning predict different effect of iconicity on Bayesian reasoning. The ecological-rationality account predicts a positive iconicity effect, because more highly iconic signs resemble more individuated objects, which tap better into an evolutionary-designed frequency-coding mechanism that, in turn, facilitates Bayesian reasoning. The nested-sets account predicts a null iconicity effect, because iconicity does not affect the salience of a nested-sets structure-the factor facilitating Bayesian reasoning processed by a general reasoning mechanism. In two well-powered experiments (N = 577), we found no support for a positive iconicity effect across different iconicity levels that were manipulated in different visual displays (meta-analytical overall effect: log OR = -0.13, 95% CI [-0.53, 0.28]). A Bayes factor analysis provided strong evidence in favor of the null hypothesis-the null iconicity effect. Thus, these findings corroborate the nested-sets rather than the ecological-rationality account of statistical reasoning.

  16. Favorable locations for piezo actuators in plates with good control effectiveness and minimal change in system dynamics

    NASA Astrophysics Data System (ADS)

    Dhuri, K. D.; Seshu, P.

    2007-12-01

    Placement and sizing of piezo actuators is normally based on control effectiveness. However, retrofitting of piezoelectric actuators alters the inherent stiffness/mass properties of the parent structure. In rotating structures, the additional mass due to piezo patches contributes to the centrifugal stiffening force. The parent structure is originally designed to have a certain natural frequency spectrum in relation to the disturbance excitation. In the event of failure of the active system, the dynamics of the structure with piezos (now rendered passive) will therefore become significant. Thus it will be helpful to determine locations for mounting piezo patches based on minimal natural frequency change yet with good control authority. In this study, a finite element based procedure for plate structures is presented. Favorable locations for mounting piezos based on minimal natural frequency changes are iteratively evolved from an initial configuration wherein the whole plate is covered with piezos. A modal controllability approach has been used for finding piezo mounting locations from a good controllability perspective. The procedure is demonstrated for simply supported square, swept-back, circular and rotating rectangular plates considering the first four modes.

  17. Determination of Plasma Screening Effects for Thermonuclear Reactions in Laser-generated Plasmas

    NASA Astrophysics Data System (ADS)

    Wu, Yuanbin; Pálffy, Adriana

    2017-03-01

    Due to screening effects, nuclear reactions in astrophysical plasmas may behave differently than in the laboratory. The possibility to determine the magnitude of these screening effects in colliding laser-generated plasmas is investigated theoretically, having as a starting point a proposed experimental setup with two laser beams at the Extreme Light Infrastructure facility. A laser pulse interacting with a solid target produces a plasma through the Target Normal Sheath Acceleration scheme, and this rapidly streaming plasma (ion flow) impacts a secondary plasma created by the interaction of a second laser pulse on a gas jet target. We model this scenario here and calculate the reaction events for the astrophysically relevant reaction 13C(4He, n)16O. We find that it should be experimentally possible to determine the plasma screening enhancement factor for fusion reactions by detecting the difference in reaction events between two scenarios of ion flow interacting with the plasma target and a simple gas target. This provides a way to evaluate nuclear reaction cross-sections in stellar environments and can significantly advance the field of nuclear astrophysics.

  18. Reaction rates for mesoscopic reaction-diffusion kinetics

    DOE PAGES

    Hellander, Stefan; Hellander, Andreas; Petzold, Linda

    2015-02-23

    The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In thismore » paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. Finally, we show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results.« less

  19. Reaction rates for mesoscopic reaction-diffusion kinetics

    PubMed Central

    Hellander, Stefan; Hellander, Andreas; Petzold, Linda

    2016-01-01

    The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. We show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results. PMID:25768640

  20. A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

    PubMed

    Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

    2015-10-14

    While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7(+), and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.

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