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Sample records for physical realism stereochemistry

  1. Improving physical realism, stereochemistry and side-chain accuracy in homology modeling: four approaches that performed well in CASP8

    PubMed Central

    Krieger, Elmar; Joo, Keehyoung; Lee, Jinwoo; Lee, Jooyoung; Raman, Srivatsan; Thompson, James; Tyka, Mike; Baker, David; Karplus, Kevin

    2009-01-01

    A correct alignment is an essential requirement in homology modeling. Yet in order to bridge the structural gap between template and target, which may not only involve loop rearrangements, but also shifts of secondary structure elements and repacking of core residues, high-resolution refinement methods with full atomic details are needed. Here we describe four approaches that address this ‘last mile of the protein folding problem’ and have performed well during CASP8, yielding physically realistic models: YASARA, which runs molecular dynamics simulations of models in explicit solvent, using a new partly knowledge-based all atom force field derived from Amber, whose parameters have been optimized to minimize the damage done to protein crystal structures. The LEE-SERVER, which makes extensive use of conformational space annealing to create alignments, to help Modeller build physically realistic models while satisfying input restraints from templates and CHARMM stereochemistry, and to remodel the side-chains. ROSETTA, whose high resolution refinement protocol combines a physically realistic all atom force field with Monte Carlo minimization to allow the large conformational space to be sampled quickly. And finally UNDERTAKER, which creates a pool of candidate models from various templates and then optimizes them with an adaptive genetic algorithm, using a primarily empirical cost function that does not include bond angle, bond length, or other physics-like terms. PMID:19768677

  2. Explorations in metalloporphyrin stereochemistry, physical properties and beyond

    PubMed Central

    Scheidt, W. Robert

    2010-01-01

    A review of selected portions of our work in the area of porphyrin structure and physical characterization is presented. Topics covered include early work on periodic trends in first row transtion metalloporphyrins, a survey of electronic structure of iron derivatives including spin-state trends, ligand orientation effects and the elucidtion of unusual low-spin states for iron(II). A discussion of the different tlypes of high-spin iron(II) complexes and the effects of hydrogen bonding is given. A survey of nitric oxide (NO) derivatives is presented as well as a brief introduction into the use of nuclear resonance vibrational spectroscopy for the study of iron porphyrins and heme proteins. PMID:20198111

  3. Does Quantum Physics Refute Realism, Materialism and Determinism?

    NASA Astrophysics Data System (ADS)

    Bunge, Mario

    2012-10-01

    It is argued that the correct answer to the three questions in the title is "no": that the theses being denied derive from traditional philosophy, not from the way the quantum theories are used. For example, the calculation of the energy spectrum of an atom assumes the autonomous existence of the atom, rather than its dependence upon the observer. However, it is also suggested that the problem has been unnecessarily complicated by a careless use of the terms `realism', `materialism', and `determinism'. Precise definitions of these words are proposed.

  4. For or against structural realism? A verdict from high energy physics

    NASA Astrophysics Data System (ADS)

    Nounou, Antigone M.

    2015-02-01

    When it comes to supporting the main ontic structural realist thesis, that we are better off with a metaphysics purged of objects, its proponents have to meet several challenges, three of which are to ensure that objects can be recast in terms of structure alone at both the level of theory and the level of ontology, to justify on physical grounds that structure exists in the world in a way that affects the goings-on in it, and to show that the relation between objects and structure is non-reciprocal, so that structure is ontologically prior to objects but not the converse. Assuming-tacitly or explicitly-that the objects of physics can be thus recast using symmetry group structure, supporters of the thesis have, therefore, to meet the remaining challenges. The present paper discusses and contests two such attempts, which typify arguments in favor of ontic structural realism from high-energy physics.

  5. When realism made a difference: The constitution of matter and its conceptual enigmas in late 19th century physics

    NASA Astrophysics Data System (ADS)

    Wilholt, Torsten

    2008-01-01

    The late 19th century debate among German-speaking physicists about theoretical entities is often regarded as foreshadowing the scientific realism debate. This paper brings out differences between them by concentrating on the part of the earlier debate that was concerned with the conceptual consistency of the competing conceptions of matter-mainly, but not exclusively, of atomism. Philosophical antinomies of atomism were taken up by Emil Du Bois-Reymond in an influential lecture in 1872. Such challenges to the consistency of atomism had repercussions within the physics community, as can be shown for the examples of Heinrich Hertz and Ludwig Boltzmann. The latter developed a series of counter-arguments, culminating in an ingenious attempt to turn the tables on the critics of atomism and prove the inconsistency of non-atomistic conceptions of nature. Underlying this controversy is a disagreement over specific goals of physical research which was considered crucially relevant to the further course of physical inquiry. It thereby exemplifies an attitude towards the realism issue that can be contrasted with a different, more neutral attitude of construing the realism issue as merely philosophical and indifferent with respect to concrete research programs in physics, which one also occasionally finds expressed in the 19th century controversy and which may be seen as the prevailing attitude of the 20th century debate.

  6. Realism vs. Constructivism in Contemporary Physics: The Impact of the Debate on the Understanding of Quantum Theory and Its Instructional Process

    ERIC Educational Resources Information Center

    Karakostas, Vassilios; Hadzidaki, Pandora

    2005-01-01

    In the present study we attempt to incorporate the philosophical dialogue about physical reality into the instructional process of quantum mechanics. Taking into account that both scientific realism and constructivism represent, on the basis of a rather broad spectrum, prevalent philosophical currents in the domain of science education, the…

  7. Color realism and color science.

    PubMed

    Byrne, Alex; Hilbert, David R

    2003-02-01

    The target article is an attempt to make some progress on the problem of color realism. Are objects colored? And what is the nature of the color properties? We defend the view that physical objects (for instance, tomatoes, radishes, and rubies) are colored, and that colors are physical properties, specifically, types of reflectance. This is probably a minority opinion, at least among color scientists. Textbooks frequently claim that physical objects are not colored, and that the colors are "subjective" or "in the mind." The article has two other purposes: First, to introduce an interdisciplinary audience to some distinctively philosophical tools that are useful in tackling the problem of color realism and, second, to clarify the various positions and central arguments in the debate. The first part explains the problem of color realism and makes some useful distinctions. These distinctions are then used to expose various confusions that often prevent people from seeing that the issues are genuine and difficult, and that the problem of color realism ought to be of interest to anyone working in the field of color science. The second part explains the various leading answers to the problem of color realism, and (briefly) argues that all views other than our own have serious difficulties or are unmotivated. The third part explains and motivates our own view, that colors are types of reflectances and defends it against objections made in the recent literature that are often taken as fatal. PMID:14598439

  8. Atmospheric Heterogeneous Stereochemistry

    NASA Astrophysics Data System (ADS)

    Stokes, G. Y.; Buchbinder, A. M.; Geiger, F. M.

    2009-12-01

    This paper addresses the timescale and mechanism of heterogeneous interactions of laboratory models of organic-coated mineral dust and ozone. We are particularly interested in investigating the role of stereochemistry in heterogeneous oxidation reactions involving chiral biogenic VOCs. Using the surface-specific nonlinear optical spectroscopy, sum frequency generation, we tracked terpene diastereomers during exposure to 10^11 to 10^13 molecules of ozone per cm^3 in 1 atm helium to model ozone-limited and ozone-rich tropospheric conditions. Our kinetic data indicate that the diastereomers which orient their reactive C=C double bonds towards the gas phase exhibit heterogeneous ozonolysis rate constants that are two times faster than diastereomers that orient their C=C double bonds away from the gas phase. Insofar as our laboratory model studies are representative of real world environments, our studies suggest that the propensity of aerosol particles coated with chiral semivolatile organic compounds to react with ozone may depend on stereochemistry. Implications of these results for chiral markers that would allow for source appointment of anthropogenic versus biogenic carbon emissions will be discussed.

  9. Mario Bunge's Scientific Realism

    NASA Astrophysics Data System (ADS)

    Cordero, Alberto

    2012-10-01

    This paper presents and comments on Mario Bunge's scientific realism. After a brief introduction in Sects. 1 and 2 outlines Bunge's conception of realism. Focusing on the case of quantum mechanics, Sect. 3 explores how his approach plays out for problematic theories. Section 4 comments on Bunge's project against the background of the current debate on realism in contemporary analytic philosophy.

  10. Mario Bunge's Scientific Realism

    ERIC Educational Resources Information Center

    Cordero, Alberto

    2012-01-01

    This paper presents and comments on Mario Bunge's scientific realism. After a brief introduction in Sects. 1 and 2 outlines Bunge's conception of realism. Focusing on the case of quantum mechanics, Sect. 3 explores how his approach plays out for problematic theories. Section 4 comments on Bunge's project against the background of the current…

  11. Realism in Research.

    ERIC Educational Resources Information Center

    House, Ernest R.

    1991-01-01

    The incorrect Humean notion of causation in the standard view of science has had devastating effects on social science research. Alternatively, scientific realism, as illustrated in R. Bhaskar's work, provides a scientific framework for research, incorporates the perceptions and intentions of participants, and advances critical values (i.e.,…

  12. Child witnesses' metamemory realism.

    PubMed

    Allwood, Carl Martin; Granhag, Pär Anders; Jonsson, Anna-Carin

    2006-12-01

    This study investigated the degree of realism in the confidence judgments of 11 to 12-year-olds (41 girls and 40 boys) of their answers to questions relating to a short film clip showing a kidnapping event. Four different confidence scales were used: a numeric scale, a picture scale, a line scale and a written scale. The results demonstrated that the children showed a high level of overconfidence in their memories. However, no significant differences between the four confidence scales were found. Weak gender differences were found in that the girls were slightly, but significantly, better calibrated than the boys. In addition, although both boys and girls overestimated the total number of memory questions they had answered correctly, the boys gave higher estimates compared with the girls. In brief, the results indicate that, at least in the context investigated, 11-12 year-old children's confidence in and estimations of their own event memory show poor realism (overconfidence and overestimation). A comparison with previous research on adults indicates that 11 to 12-year-old children show noticeably poorer realism. PMID:17107494

  13. Psychology Needs Realism, Not Instrumentalism

    ERIC Educational Resources Information Center

    Haig, Brian D.

    2005-01-01

    In this article, the author presents his comments on "Realism, Instrumentalism, and Scientific Symbiosis: Psychological Theory as a Search for Truth and the Discovery of Solutions" by John T. Cacioppo, Gun R. Semin and Gary G. Berntson. In the original article, the authors recommended the combined use of the philosophies of scientific realism and…

  14. Introducing Stereochemistry to Non-science Majors

    NASA Astrophysics Data System (ADS)

    Luján-Upton, Hannia

    2001-04-01

    Stereochemistry is often a difficult topic for both science and non-science majors to learn. The topics covered in most undergraduate textbooks, although fundamental, seem very abstract to most students. This manuscript describes two simple exercises that can be used to introduce concepts associated with stereochemistry such as "sameness", superimposability, chirality, enantiomers, optical activity, polarimetry, and racemic mixtures. One exercise compares chirality in hands with the achiral nature of two textbooks. The other exercise involves a murder mystery, the solution of which hinges upon understanding the concept of optical activity, specifically in natural products such as toxins from poisonous mushrooms.

  15. Preoperational Graphic Representation: From Intellectual Realism to Visual Realism in Draw a House-Tree Task.

    ERIC Educational Resources Information Center

    Kalyan-Masih, Violet

    In a pilot study of children's drawings of "a house with a tree behind it," Piagetian sequence (scribbling, fortuitous realism, failed realism, intellectual realism, and visual realism) was tentatively supported. Children's strategies in decentering from intellectual to visual realism were noted. The study reported in this paper was undertaken to…

  16. Local Realism of Macroscopic Correlations

    NASA Astrophysics Data System (ADS)

    Ramanathan, R.; Paterek, T.; Kay, A.; Kurzyński, P.; Kaszlikowski, D.

    2011-08-01

    We identify conditions under which correlations resulting from quantum measurements performed on macroscopic systems (systems composed of a number of particles of the order of the Avogadro number) can be described by local realism. We argue that the emergence of local realism at the macroscopic level is caused by an interplay between the monogamous nature of quantum correlations and the fact that macroscopic measurements do not reveal properties of individual particles.

  17. Orbital State Uncertainty Realism

    NASA Astrophysics Data System (ADS)

    Horwood, J.; Poore, A. B.

    2012-09-01

    Fundamental to the success of the space situational awareness (SSA) mission is the rigorous inclusion of uncertainty in the space surveillance network. The *proper characterization of uncertainty* in the orbital state of a space object is a common requirement to many SSA functions including tracking and data association, resolution of uncorrelated tracks (UCTs), conjunction analysis and probability of collision, sensor resource management, and anomaly detection. While tracking environments, such as air and missile defense, make extensive use of Gaussian and local linearity assumptions within algorithms for uncertainty management, space surveillance is inherently different due to long time gaps between updates, high misdetection rates, nonlinear and non-conservative dynamics, and non-Gaussian phenomena. The latter implies that "covariance realism" is not always sufficient. SSA also requires "uncertainty realism"; the proper characterization of both the state and covariance and all non-zero higher-order cumulants. In other words, a proper characterization of a space object's full state *probability density function (PDF)* is required. In order to provide a more statistically rigorous treatment of uncertainty in the space surveillance tracking environment and to better support the aforementioned SSA functions, a new class of multivariate PDFs are formulated which more accurately characterize the uncertainty of a space object's state or orbit. The new distribution contains a parameter set controlling the higher-order cumulants which gives the level sets a distinctive "banana" or "boomerang" shape and degenerates to a Gaussian in a suitable limit. Using the new class of PDFs within the general Bayesian nonlinear filter, the resulting filter prediction step (i.e., uncertainty propagation) is shown to have the *same computational cost as the traditional unscented Kalman filter* with the former able to maintain a proper characterization of the uncertainty for up to *ten

  18. Earth Observing System Covariance Realism

    NASA Technical Reports Server (NTRS)

    Zaidi, Waqar H.; Hejduk, Matthew D.

    2016-01-01

    The purpose of covariance realism is to properly size a primary object's covariance in order to add validity to the calculation of the probability of collision. The covariance realism technique in this paper consists of three parts: collection/calculation of definitive state estimates through orbit determination, calculation of covariance realism test statistics at each covariance propagation point, and proper assessment of those test statistics. An empirical cumulative distribution function (ECDF) Goodness-of-Fit (GOF) method is employed to determine if a covariance is properly sized by comparing the empirical distribution of Mahalanobis distance calculations to the hypothesized parent 3-DoF chi-squared distribution. To realistically size a covariance for collision probability calculations, this study uses a state noise compensation algorithm that adds process noise to the definitive epoch covariance to account for uncertainty in the force model. Process noise is added until the GOF tests pass a group significance level threshold. The results of this study indicate that when outliers attributed to persistently high or extreme levels of solar activity are removed, the aforementioned covariance realism compensation method produces a tuned covariance with up to 80 to 90% of the covariance propagation timespan passing (against a 60% minimum passing threshold) the GOF tests-a quite satisfactory and useful result.

  19. Realism, positivism, instrumentalism, and quantum geometry

    NASA Astrophysics Data System (ADS)

    Prugovečki, Eduard

    1992-02-01

    The roles of classical realism, logical positivism, and pragmatic instrumentalism in the shaping of fundamental ideas in quantum physics are examined in the light of some recent historical and sociological studies of the factors that influenced their development. It is shown that those studies indicate that the conventionalistic form of instrumentalism that has dominated all the major post-World War II developments in quantum physics is not an outgrowth of the Copenhagen school, and that despite the “schism” in twentieth century physics created by the Bohr-Einstein “disagreements” on foundational issues in quantum theory, both their philosophical stands were very much opposed to those of conventionalistic instrumentalism. Quotations from the writings of Dirac, Heisenberg, Popper, Russell, and other influential thinkers, are provided, illustrating the fact that, despite the various divergencies in their opinions, they all either opposed the instrumentalist concept of “truth” in general, or its conventionalistic version in post-World War II quantum physics in particular. The basic epistemic ideas of a quantum geometry approach to quantum physics are reviewed and discussed from the point of view of a quantum realism that seeks to reconcile Bohr's “positivism” with Einstein's “realism” by emphasizing the existence of an underlying quantum reality, in which they both believed. This quantum geometry framework seeks to introduce geometro-stochastic concepts that are specifically designed for the systematic description of that underlying quantum reality, by developing the conceptual and mathematical tools that are most appropriate for such a use.

  20. The Stereochemistry of Biochemical Molecules: A Subject to Revisit

    ERIC Educational Resources Information Center

    Centelles, Josep J.; Imperial, Santiago

    2005-01-01

    Although Fischer's convention for stereoisomers is useful for simple molecules, the stereochemistry of complex biochemical molecules is often poorly indicated in textbooks. This article reports on errors in stereochemistry of complex hydrosoluble vitamin B12 molecule. Twenty-five popular biochemistry textbooks were examined for their treatment of…

  1. Stereochemistry in subcomponent self-assembly.

    PubMed

    Castilla, Ana M; Ramsay, William J; Nitschke, Jonathan R

    2014-07-15

    CONSPECTUS: As Pasteur noted more than 150 years ago, asymmetry exists in matter at all organization levels. Biopolymers such as proteins or DNA adopt one-handed conformations, as a result of the chirality of their constituent building blocks. Even at the level of elementary particles, asymmetry exists due to parity violation in the weak nuclear force. While the origin of homochirality in living systems remains obscure, as does the possibility of its connection with broken symmetries at larger or smaller length scales, its centrality to biomolecular structure is clear: the single-handed forms of bio(macro)molecules interlock in ways that depend upon their handednesses. Dynamic artificial systems, such as helical polymers and other supramolecular structures, have provided a means to study the mechanisms of transmission and amplification of stereochemical information, which are key processes to understand in the context of the origins and functions of biological homochirality. Control over stereochemical information transfer in self-assembled systems will also be crucial for the development of new applications in chiral recognition and separation, asymmetric catalysis, and molecular devices. In this Account, we explore different aspects of stereochemistry encountered during the use of subcomponent self-assembly, whereby complex structures are prepared through the simultaneous formation of dynamic coordinative (N → metal) and covalent (N═C) bonds. This technique provides a useful method to study stereochemical information transfer processes within metal-organic assemblies, which may contain different combinations of fixed (carbon) and labile (metal) stereocenters. We start by discussing how simple subcomponents with fixed stereogenic centers can be incorporated in the organic ligands of mononuclear coordination complexes and communicate stereochemical information to the metal center, resulting in diastereomeric enrichment. Enantiopure subcomponents were then

  2. The evolution of offensive realism.

    PubMed

    Johnson, Dominic D P; Phil, D; Thayer, Bradley A

    2016-01-01

    Offensive realism, a theory of international relations, holds that states are disposed to competition and conflict because they are self-interested, power maximizing, and fearful of other states. Moreover, it argues that states are obliged to behave this way because doing so favors survival in the international system. Debate continues as to whether modern states actually do, or should, behave in this way, but we are struck by a different question. In this article, we ask whether the three core assumptions about behavior in offensive realism-self-help, power maximization, and outgroup fear-have any basis in scientific knowledge about human behavioral evolution. We find that these precise traits are not only evolutionarily adaptive but also empirically common across the animal kingdom, especially in primate and human societies. Based on these findings, we hypothesize that states behave as offensive realists predict not just because of anarchy in the modern international system but also because of the legacy of our evolution. In short, offensive realism may really be describing the nature of the human species more than the nature of the international system. If our hypothesis is correct, then evolutionary theory offers the following: (1) a novel ultimate cause of offensive realist behavior; (2) an extension of offensive realism to any domain in which humans compete for power; and (3) an explanation for why individual leaders themselves, and not just states, seek power. However, a key insight from evolution is that the primacy of self-help, power maximization, and outgroup fear does not necessarily condemn individuals or groups to competition and conflict; rather, these traits can in themselves give rise to cooperation and alliances. PMID:27378020

  3. Critical realism and the dialectic.

    PubMed

    Roberts, J M

    2001-12-01

    A prominent strand within both sociological and social theory has been concerned to develop a 'systems approach' with which to explore social life. One of the most original contributions to a systems approach has arisen within critical realism. In particular critical realism demonstrates that it is possible to abstract the causal powers of different objects of analysis to examine their interaction within concrete and contingent 'open systems'. The recent dialectical turn of critical realism develops this systems approach in a much more rigorous manner. However, in this paper I argue that the (dialectical) critical realist mode of abstraction ultimately fails to embed concepts and categories internally within the specific ideological and historical forms of social relations. Or rather, critical realists do not seek to develop concepts that reflect the self-movement of a historical and contradictory essence. This self-movement is what I prefer to call a 'system'. Consequently critical realists are led to separate method from system in theory construction and such a separation leads to a problematic dualist mode of theorizing. I make these observations from a Hegelian-Marxist position. PMID:11853063

  4. Nosology, ontology and promiscuous realism.

    PubMed

    Binney, Nicholas

    2015-06-01

    Medics may consider worrying about their metaphysics and ontology to be a waste of time. I will argue here that this is not the case. Promiscuous realism is a metaphysical position which holds that multiple, equally valid, classification schemes should be applied to objects (such as patients) to capture different aspects of their complex and heterogeneous nature. As medics at the bedside may need to capture different aspects of their patients' problems, they may need to use multiple classification schemes (multiple nosologies), and thus consider adopting a different metaphysics to the one commonly in use. PMID:25389077

  5. Ethical Realism: A Guide to Action?

    ERIC Educational Resources Information Center

    Matkin, Gary

    2008-01-01

    This article presents the author's response to Gary Miller's essay entitled "Ethical Realism and Continuing Education." In his essay, Dr. Miller has provided a valuable opportunity to reflect on the practice of continuing education (CE) leadership. Dr. Miller reviews six principles that are encapsulated in the concept of ethical realism, but are…

  6. Realism, Deweyan Pragmatism, and Educational Research.

    ERIC Educational Resources Information Center

    Garrison, Jim

    1994-01-01

    To the debate between the Rortyan pragmatic model of scientific research advocated by Cleo Cherryholmes and the scientific realism espoused by Ernest R. House is added another model for educational research based on the realism of John Dewey's pragmatism. Constructivist and behaviorist aspects of Dewey's philosophy are explored. (SLD)

  7. Hardy's test for local realism

    NASA Astrophysics Data System (ADS)

    Nguyen, Quynh; Dregli, Aurelio

    2014-03-01

    We demonstrated the violation of Bell inequality using entangled photons produced by spontaneous parametric down-conversion. The experiment is based on a local realism test originally proposed by Lucien Hardy. Polarized entangled photons is produced in down-conversion through a pair of beta barium borate crystals. Polarization is adjusted by half wave plates and quartz plates. Single photons travel down two separate paths, each pass through a half-wave plate and a broad band polarizing beam splitter. Light from the beam splitter is collected by lens and focused into optic fibers that direct light into a single photon counting module. Coincidence counting is done using time-to-amplitude converter/single-channel-analyzer units. The probabilities in Bell-Clauser-Horne inequality is calculated by the ratio of the measured coincidence counts on the transmitted laser beams to the total number of coincidence. The counting is done by a LabVIEW program. We find the data to violate local realism by 30 standard deviation. The experiment is based on straight forward quantum mechanical calculations and experimental techniques more accessible to undergraduate students than other methods of testing Bell inequalities.

  8. Critical realism in nursing: an emerging approach.

    PubMed

    Schiller, Catharine J

    2016-04-01

    Critical realism, a philosophical framework originally developed by Roy Bhaskar in the 1970s, represents a relatively new approach to research generally and to nursing research in particular. This article explores the ontological and epistemological tenets of critical realism and examines the application of critical realist principles to nursing research and practice through a review of the literature. It is evident that few published nursing research studies have, as of yet, utilized critical realism as their paradigm of choice. Both the strengths and limitations of the presentation and use of critical realism in these studies are discussed in this article. Given the varying degrees of success of the authors in explicating critical realism as a philosophical framework, the value of critical realism to the research study, and the ways in which usage of the critical realist framework influenced development of the study and interpretation of findings, it is evident that the quality of future publications espousing the use of critical realism must continue to be strengthened significantly. PMID:26608357

  9. Familiar faces rendered strange: Why inconsistent realism drives characters into the uncanny valley.

    PubMed

    Chattopadhyay, Debaleena; MacDorman, Karl F

    2016-09-01

    Computer-modeled characters resembling real people sometimes elicit cold, eerie feelings. This effect, called the uncanny valley, has been attributed to uncertainty about whether the character is human or living or real. Uncertainty, however, neither explains why anthropomorphic characters lie in the uncanny valley nor their characteristic eeriness. We propose that realism inconsistency causes anthropomorphic characters to appear unfamiliar, despite their physical similarity to real people, owing to perceptual narrowing. We further propose that their unfamiliar, fake appearance elicits cold, eerie feelings, motivating threat avoidance. In our experiment, 365 participants categorized and rated objects, animals, and humans whose realism was manipulated along consistency-reduced and control transitions. These data were used to quantify a Bayesian model of categorical perception. In hypothesis testing, we found reducing realism consistency did not make objects appear less familiar, but only animals and humans, thereby eliciting cold, eerie feelings. Next, structural equation models elucidated the relation among realism inconsistency (measured objectively in a two-dimensional Morlet wavelet domain inspired by the primary visual cortex), realism, familiarity, eeriness, and warmth. The fact that reducing realism consistency only elicited cold, eerie feelings toward anthropomorphic characters, and only when it lessened familiarity, indicates the role of perceptual narrowing in the uncanny valley. PMID:27611063

  10. The methodological defense of realism scrutinized.

    PubMed

    Wray, K Brad

    2015-12-01

    I revisit an older defense of scientific realism, the methodological defense, a defense developed by both Popper and Feyerabend. The methodological defense of realism concerns the attitude of scientists, not philosophers of science. The methodological defense is as follows: a commitment to realism leads scientists to pursue the truth, which in turn is apt to put them in a better position to get at the truth. In contrast, anti-realists lack the tenacity required to develop a theory to its fullest. As a consequence, they are less likely to get at the truth. My aim is to show that the methodological defense is flawed. I argue that a commitment to realism does not always benefit science, and that there is reason to believe that a research community with both realists and anti-realists in it may be better suited to advancing science. A case study of the Copernican Revolution in astronomy supports this claim. PMID:26568089

  11. Cosmology and the Demise of Color Realism

    NASA Astrophysics Data System (ADS)

    Hockey, Thomas

    2011-04-01

    Scientific realism is a bulwark of modern metaphysics, especially entity realism. Scientists expect there to be real objects in nature that may be enumerated and measured using objective properties. (Rest mass is an example.) Is color one of these properties? The question, "What is the color of the Universe?" unexpectedly leads to the conclusion that it is not. Astronomers use the concept of color at their ontological peril.

  12. Investigating Realism in the Arts: Can Elements of Realism Be Identified in "Enter Achilles" (Lloyd Newson)?

    ERIC Educational Resources Information Center

    Wall, Mellina

    2006-01-01

    This paper investigates realism both as an artistic attitude within the arts, and more specifically in relation to Lloyd Newson's "Enter Achilles". There is initially a discussion of realism, focusing on the theories of Lukacs and Brecht in relation to art, and an attempt to relate these ideas more specifically to dance. Discussion of "Enter…

  13. Prediction of Stereochemistry using Q2MM.

    PubMed

    Hansen, Eric; Rosales, Anthony R; Tutkowski, Brandon; Norrby, Per-Ola; Wiest, Olaf

    2016-05-17

    transition metal-catalyzed reactions that are important from both an industrial and an academic perspective. In this Account, we provide an overview of the continued improvement of the prediction of stereochemistry using Q2MM-derived TSFFs using four examples from different stages of development: (i) Pd-catalyzed allylation, (ii) OsO4-catalyzed asymmetric dihydroxylation (AD) of alkenes, (iii) Rh-catalyzed hydrogenation of enamides, and (iv) Ru-catalyzed hydrogenation of ketones. In the current form, correlation coefficients of 0.8-0.9 between calculated and experimental ee values are typical for a wide range of substrate-ligand combinations, and suitable ligands can be predicted for a given substrate with ∼80% accuracy. Although the generation of a TSFF requires an initial effort and will therefore be most useful for widely used reactions that require frequent screening campaigns, the method allows for a rapid virtual screen of large ligand libraries to focus experimental efforts on the most promising substrate-ligand combinations. PMID:27064579

  14. Prediction of Stereochemistry using Q2MM

    PubMed Central

    2016-01-01

    screens on a range of transition metal-catalyzed reactions that are important from both an industrial and an academic perspective. In this Account, we provide an overview of the continued improvement of the prediction of stereochemistry using Q2MM-derived TSFFs using four examples from different stages of development: (i) Pd-catalyzed allylation, (ii) OsO4-catalyzed asymmetric dihydroxylation (AD) of alkenes, (iii) Rh-catalyzed hydrogenation of enamides, and (iv) Ru-catalyzed hydrogenation of ketones. In the current form, correlation coefficients of 0.8–0.9 between calculated and experimental ee values are typical for a wide range of substrate–ligand combinations, and suitable ligands can be predicted for a given substrate with ∼80% accuracy. Although the generation of a TSFF requires an initial effort and will therefore be most useful for widely used reactions that require frequent screening campaigns, the method allows for a rapid virtual screen of large ligand libraries to focus experimental efforts on the most promising substrate–ligand combinations. PMID:27064579

  15. Realism Assessment of Sonic Boom Simulators

    NASA Technical Reports Server (NTRS)

    Sullivan, Brenda M.; Davies, Patrica; Hodgdon, Kthleen K.; Salamone, Joseph A., III; Pilon, Anthony

    2008-01-01

    Developments in small supersonic aircraft design are predicted to result in low-intensity sonic booms. Booms generated by current aircraft are similar to those that led to the ban on commercial supersonic fli ght over the US, so are unsuitable for parametric studies of psychoac oustic response to low-intensity booms. Therefore, simulators have be en used to study the impact of predicted low-intensity sonic booms. H owever, simulators have been criticized because, when simulating conv entional-level booms, the sounds were observed to be unrealistic by p eople experienced in listening to sonic booms. Thus, two studies were conducted to measure the perceived realism of three sonic boom simul ators. Experienced listeners rated the realism of conventional sonic boom signatures when played in these simulators. The effects on percei ved realism of factors such as duration of post-boom noise, exclusion of very low frequency components, inclusion of ground reflections, a nd type of simulator were examined. Duration of post-boom noise was f ound to have a strong effect on perceived realism, while type of simu lator had a weak effect. It was determined that post-boom noise had t o be at least 1.5 seconds long for the sound to be rated very realist ic. Loudness level did not affect realism for the range of sounds pla yed in the tests (80-93 dB ASEL).

  16. Stereochemistry of Consabatine from Convolvulus sabatius Viv. (Convolvulaceae).

    PubMed

    Ott, Sonja Christina; Jenett-Siems, Kristina; Eich, Eckart

    2013-03-01

    The stereochemistry of consabatine, which was isolated from the roots of Convolvulus sabatius Viv. as a novel natural compound, has now been determined by the synthesis of its Mosher esters. Consabatine was found to be 1'R-configurated. PMID:23641342

  17. Stereochemistry of Consabatine from Convolvulus sabatius Viv. (Convolvulaceae)

    PubMed Central

    Ott, Sonja Christina; Jenett-Siems, Kristina; Eich, Eckart

    2013-01-01

    The stereochemistry of consabatine, which was isolated from the roots of Convolvulus sabatius Viv. as a novel natural compound, has now been determined by the synthesis of its Mosher esters. Consabatine was found to be 1′R-configurated. PMID:23641342

  18. Dynamic Stereochemistry: A Simple Approach to Delineating Relative Configuration

    ERIC Educational Resources Information Center

    Mandal, Dipak K.

    2007-01-01

    A simple approach for delineating the stereochemistry of the products relative to that of the reactants in reactions involving stereogenic centers is addressed. The reaction at the tetrahedral center involves the cleavage of a bond to one of the ligands in the reactant and the resulting new ligand in the product is labeled by affixing prime to the…

  19. 48 CFR 1515.404-475 - Cost realism.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 48 Federal Acquisition Regulations System 6 2013-10-01 2013-10-01 false Cost realism. 1515.404-475... METHODS AND CONTRACT TYPES CONTRACTING BY NEGOTIATION Contract Pricing 1515.404-475 Cost realism. The EPA structured approach is not required when the contracting officer is evaluating cost realism in a...

  20. Critical Realism and Statistical Methods--A Response to Nash

    ERIC Educational Resources Information Center

    Scott, David

    2007-01-01

    This article offers a defence of critical realism in the face of objections Nash (2005) makes to it in a recent edition of this journal. It is argued that critical and scientific realisms are closely related and that both are opposed to statistical positivism. However, the suggestion is made that scientific realism retains (from statistical…

  1. Inspirational Realism: Chesley Bonestell and Astronomical Art

    NASA Astrophysics Data System (ADS)

    Perkowitz, S.

    2013-04-01

    At the very beginning of the space age, some sixty years ago, the American artist and illustrator Chesley Bonestell portrayed planets, stars, and spacecraft with stunning, near-photographic realism. Collaborating with experts like rocket pioneer Wernher von Braun, Bonestell's renditions combined the best scientific and engineering knowledge of the time, and scientific exactness, with artistic imagination.

  2. Reinvestigation of the Branimycin Stereochemistry at Position 17-C.

    PubMed

    Čikoš, Ana; Triballeau, Nicolas; Hubbard, Paul A; Žiher, Dinko; Stouten, Pieter F W; Doyon, Julien G P-O; Deschrijver, Tiny; Wouters, Johan; Lépine, Renaud H M; Saniere, Laurent

    2016-02-19

    A conformational study of branimycin was performed using single-crystal X-ray crystallography to characterize the solid-state form, while a combination of NMR spectroscopy and molecular modeling was employed to gain information about the solution structure. Comparison of the crystal structure with its solution counterpart showed no significant differences in conformation, confirming the relative rigidity of the tricyclic system. However, these experiments revealed that the formerly proposed stereochemistry of branimycin at 17-C should be revised. PMID:26849068

  3. Assignment of absolute stereochemistry by computation of optical rotation angles

    NASA Astrophysics Data System (ADS)

    Kondru, Rama Krishna

    We have developed simple wire and molecular orbital models to qualitatively and quantitatively understand optical rotation angles of molecules. We reported the first ab initio theoretical approach to determine the absolute stereochemistry of a complex natural product by calculating molar rotation angles, [M]D. We applied this method for an unambiguous assignment of the absolute stereochemistry of the hennoxazole A. A protocol analogous to population analysis was devised to analyze atomic contributions to the rotation angles for oxiranes, orthoesters, and other organic compounds. The molar rotations for an indoline, an indonone, menthol and menthone were calculated using ab inito methods and compared with experimental values. We reported the first prediction of the absolute configuration of a natural product, i.e. an a priori assignment of the relative and absolute stereochemistry of pitiamide A. Furthermore, we described a strategy that may help to establish structure-function relations for rotation angles by visualizing the electric and magnetic-field perturbations to a molecule's molecular orbitals.

  4. Must Metaethical Realism Make a Semantic Claim?

    PubMed Central

    Kahane, Guy

    2012-01-01

    Mackie drew attention to the distinct semantic and metaphysical claims made by meta ethical realists, arguing that although our evaluative discourse is cognitive and objective, there are no objective evaluative facts. This distinction, however, also opens up a reverse possibility: that our evaluative discourse is antirealist, yet objective values do exist. I suggest that this seemingly far-fetched possibility merits serious attention; realism seems com mitted to its intelligibility, and, despite appearances, it isn’t incoherent, ineffable, inherently implausible or impossible to defend. I argue that reflection on this possibility should lead us to revise our understanding of the debate between realists and antirealists. It is not only that the realist’s semantic claim is insufficient for realism to be true, as Mackie argued; it’s not even necessary. Robust metaethical realism is best understood as making a purely metaphysical claim. It is thus not enough for antirealists to show that our discourse is antirealist. They must directly attack the realist’s metaphysical claim. PMID:23525148

  5. Must Metaethical Realism Make a Semantic Claim?

    PubMed

    Kahane, Guy

    2013-02-01

    Mackie drew attention to the distinct semantic and metaphysical claims made by meta ethical realists, arguing that although our evaluative discourse is cognitive and objective, there are no objective evaluative facts. This distinction, however, also opens up a reverse possibility: that our evaluative discourse is antirealist, yet objective values do exist. I suggest that this seemingly far-fetched possibility merits serious attention; realism seems com mitted to its intelligibility, and, despite appearances, it isn't incoherent, ineffable, inherently implausible or impossible to defend. I argue that reflection on this possibility should lead us to revise our understanding of the debate between realists and antirealists. It is not only that the realist's semantic claim is insufficient for realism to be true, as Mackie argued; it's not even necessary. Robust metaethical realism is best understood as making a purely metaphysical claim. It is thus not enough for antirealists to show that our discourse is antirealist. They must directly attack the realist's metaphysical claim. PMID:23525148

  6. Stereochemistry of enzymatic water addition to C=C bonds.

    PubMed

    Chen, Bi-Shuang; Otten, Linda G; Hanefeld, Ulf

    2015-01-01

    Water addition to carbon-carbon double bonds using hydratases is attracting great interest in biochemistry. Most of the known hydratases are involved in primary metabolism and to a lesser extent in secondary metabolism. New hydratases have recently been added to the toolbox, both from natural sources or artificial metalloenzymes. In order to comprehensively understand how the hydratases are able to catalyse the water addition to carbon-carbon double bonds, this review will highlight the mechanistic and stereochemical studies of the enzymatic water addition to carbon-carbon double bonds, focusing on the syn/anti-addition and stereochemistry of the reaction. PMID:25640045

  7. Development of a Web-Based, Student-Centered Stereochemistry Tutorial

    ERIC Educational Resources Information Center

    Burrmann, Nicola J.; Moore, John W.

    2013-01-01

    A Web-based stereochemistry tutorial is described that details the core definitions and structural representations of stereochemistry in an organic chemistry course. The Cahn-Ingold-Prelog rules and their application for assigning "R" and "S" orientations to stereocenters and "E" and "Z" orientations to…

  8. A Simple and Novel Approach to Delineating Stereochemistry of Electrocyclic Reactions

    ERIC Educational Resources Information Center

    Mandal, Dipak K.

    2012-01-01

    The dynamic stereochemistry of electrocyclic reactions (a class of pericyclic reactions) stems from the operation of either conrotatory (con) or disrotatory (dis) mode of ring-closing and ring-opening processes. Difficulty is often encountered in depicting product stereochemistry resulting from such movements of substituents. A novel, simple,…

  9. An Engaging Illustration of the Physical Differences among Menthol Stereoisomers

    ERIC Educational Resources Information Center

    Treadwell, Edward M.; Black, T. Howard

    2005-01-01

    An experiment illustrating stereochemical principles, like different physical properties in achiral environments, assignment of absolute stereochemistry, and the stereoisomeric relationships to differences in absolute stereochemistry is devised. A demonstration of how enantiomers have the same physical properties until placed in chiral…

  10. Emergent Paradigm: Critical Realism and Transformative Research in Educational Administration

    ERIC Educational Resources Information Center

    Egbo, Benedicta

    2005-01-01

    This paper explores the prospects of using critical realism as a guiding philosophy for critical inquiry in the field of educational administration. A relatively recent philosophy in the social sciences, critical realism offers an alternative framework for researchers engaged in empirical work that is aimed at transforming undesirable social…

  11. Comparison of Linear Microinstability Calculations of Varying Input Realism

    SciTech Connect

    G. Rewoldt

    2003-09-08

    The effect of varying ''input realism'' or varying completeness of the input data for linear microinstability calculations, in particular on the critical value of the ion temperature gradient for the ion temperature gradient mode, is investigated using gyrokinetic and gyrofluid approaches. The calculations show that varying input realism can have a substantial quantitative effect on the results.

  12. Earth Observation System Flight Dynamics System Covariance Realism

    NASA Technical Reports Server (NTRS)

    Zaidi, Waqar H.; Tracewell, David

    2016-01-01

    This presentation applies a covariance realism technique to the National Aeronautics and Space Administration (NASA) Earth Observation System (EOS) Aqua and Aura spacecraft based on inferential statistics. The technique consists of three parts: collection calculation of definitive state estimates through orbit determination, calculation of covariance realism test statistics at each covariance propagation point, and proper assessment of those test statistics.

  13. Response: Critical Realism--Response to Longhofer and Floersch

    ERIC Educational Resources Information Center

    Briar-Lawson, Katharine

    2012-01-01

    This article addresses key challenges posed by critical realism, proposed by Longhofer and Floersch, as a philosophical underpinning for a science of social work. As a response to Longhofer and Floersch, it is argued that critical realism may be instructive in debates about structural conditions that dictate more inclusive interventions and…

  14. Exorcising the Racism Phantasm: Racial Realism in Educational Research

    ERIC Educational Resources Information Center

    Blaisdell, Benjamin

    2016-01-01

    Based on a 3-year ethnographic project at a public elementary school in North Carolina, this article discusses how the concept of racial realism can be useful to researchers trying to live up to the goals of critical race studies in school-based research. Racial realism maintains that racism is a permanent aspect of U.S. society and schools. A…

  15. 48 CFR 1515.404-475 - Cost realism.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 48 Federal Acquisition Regulations System 6 2014-10-01 2014-10-01 false Cost realism. 1515.404-475 Section 1515.404-475 Federal Acquisition Regulations System ENVIRONMENTAL PROTECTION AGENCY CONTRACTING METHODS AND CONTRACT TYPES CONTRACTING BY NEGOTIATION Contract Pricing 1515.404-475 Cost realism. The EPA structured approach is not...

  16. 48 CFR 1515.404-475 - Cost realism.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 48 Federal Acquisition Regulations System 6 2012-10-01 2012-10-01 false Cost realism. 1515.404-475 Section 1515.404-475 Federal Acquisition Regulations System ENVIRONMENTAL PROTECTION AGENCY CONTRACTING METHODS AND CONTRACT TYPES CONTRACTING BY NEGOTIATION Contract Pricing 1515.404-475 Cost realism. The EPA structured approach is not...

  17. The Interaction of Color Realism and Pictorial Recall Memory.

    ERIC Educational Resources Information Center

    Berry, Louis H.

    This study investigated the interaction of variations in color realism on pictorial recall memory in order to better understand the effects of variations in color realism, and to draw comparisons between visual recall memory and visual recognition memory in terms of color information processing. Stimulus materials used were three sets of slides,…

  18. Energy-time entanglement, elements of reality, and local realism

    NASA Astrophysics Data System (ADS)

    Jogenfors, Jonathan; Larsson, Jan-Åke

    2014-10-01

    The Franson interferometer, proposed in 1989 (Franson 1989 Phys. Rev. Lett. 62 2205-08), beautifully shows the counter-intuitive nature of light. The quantum description predicts sinusoidal interference for specific outcomes of the experiment, and these predictions can be verified in experiment. In the spirit of Einstein, Podolsky, and Rosen it is possible to ask if the quantum-mechanical description (of this setup) can be considered complete. This question will be answered in detail in this paper, by delineating the quite complicated relation between energy-time entanglement experiments and Einstein-Podolsky-Rosen (EPR) elements of reality. The mentioned sinusoidal interference pattern is the same as that giving a violation in the usual Bell experiment. Even so, depending on the precise requirements made on the local realist model, this can imply (a) no violation, (b) smaller violation than usual, or (c) full violation of the appropriate statistical bound. Alternatives include (a) using only the measurement outcomes as EPR elements of reality, (b) using the emission time as EPR element of reality, (c) using path realism, or (d) using a modified setup. This paper discusses the nature of these alternatives and how to choose between them. The subtleties of this discussion needs to be taken into account when designing and setting up experiments intended to test local realism. Furthermore, these considerations are also important for quantum communication, for example in Bell-inequality-based quantum cryptography, especially when aiming for device independence. This article is part of a special issue of Journal of Physics A: Mathematical and Theoretical devoted to ‘50 years of Bell’s theorem’.

  19. Unified Synthesis of 10-Oxygenated Lycopodium Alkaloids: Impact of C10-Stereochemistry on Reactivity.

    PubMed

    Saha, Mrinmoy; Li, Xin; Collett, Nathan D; Carter, Rich G

    2016-07-15

    The pronounced impact of the C10 stereochemistry on the successful construction of a polycyclic Lycopodium alkaloid scaffold has been explored. A wide range of reaction conditions and functionality were investigated to control a keto sulfone Michael addition to construct the C7-C12 linkage. An unexpected, overriding impact of the C10 stereochemistry in stereoselectivity and reaction rate in the Michael addition was observed. Furthermore, divergent reactivity of a conformationally accelerated, intramolecular Mannich cyclization based on the C10 stereochemistry was discovered. The successful execution of this synthetic route resulted in the total synthesis of all three known 10-oxygenated Lycopodium alkaloids: 10-hydroxylycopodine, paniculine, and deacetylpaniculine. PMID:27353498

  20. Julio Cortázar quotes on normal and abnormal movements: magical realism or reality?

    PubMed

    Merello, Marcelo

    2006-08-01

    Together with Mario Vargas Llosa and Gabriel García Márquez, Julio Cortázar was one of the most representative authors of the Latin American magical realism genre. Within his extensive body of work, many descriptions of characters suffering physical disabilities, as well as situations suggesting such medical conditions, can be extracted. In this review, two short stories by Cortázar are presented. In the first one, the main character could easily be a man suffering from corticobasal degeneration; in the second, an old woman with symptoms suggestive of progressive supranuclear palsy is clearly depicted. Despite the fact that one of the main ingredients in Cortázar's magical realism is fiction, cases described here fit real medical conditions quite well, making it hard to believe that they represent purely fantastic descriptions rather than the product of Cortázar's inquisitive observation and the description of real patients. PMID:16685680

  1. Improving the physiological realism of experimental models.

    PubMed

    Vinnakota, Kalyan C; Cha, Chae Y; Rorsman, Patrik; Balaban, Robert S; La Gerche, Andre; Wade-Martins, Richard; Beard, Daniel A; Jeneson, Jeroen A L

    2016-04-01

    The Virtual Physiological Human (VPH) project aims to develop integrative, explanatory and predictive computational models (C-Models) as numerical investigational tools to study disease, identify and design effective therapies and provide an in silico platform for drug screening. Ultimately, these models rely on the analysis and integration of experimental data. As such, the success of VPH depends on the availability of physiologically realistic experimental models (E-Models) of human organ function that can be parametrized to test the numerical models. Here, the current state of suitable E-models, ranging from in vitro non-human cell organelles to in vivo human organ systems, is discussed. Specifically, challenges and recent progress in improving the physiological realism of E-models that may benefit the VPH project are highlighted and discussed using examples from the field of research on cardiovascular disease, musculoskeletal disorders, diabetes and Parkinson's disease. PMID:27051507

  2. Happiness, Psychology, and Degrees of Realism

    PubMed Central

    Lavazza, Andrea

    2016-01-01

    The recent emphasis on a realist ontology that cannot be overshadowed by subjectivist or relativist perspectives seems to have a number of consequences for psychology as well. My attempt here is to analyse the relationship between happiness as a state of the individual and the states of the external world and the brain events related to (or, in some hypotheses, causally responsible for) its occurrence. It can be maintained that different degrees of realism are suitable to describe the states of happiness and this fact might have relevant psychological implications, namely for the so-called positive psychology. This is especially true now that there are methods available to induce subjective states of happiness unrelated to the external conditions usually taken to be linked to such states. PMID:27536261

  3. Happiness, Psychology, and Degrees of Realism.

    PubMed

    Lavazza, Andrea

    2016-01-01

    The recent emphasis on a realist ontology that cannot be overshadowed by subjectivist or relativist perspectives seems to have a number of consequences for psychology as well. My attempt here is to analyse the relationship between happiness as a state of the individual and the states of the external world and the brain events related to (or, in some hypotheses, causally responsible for) its occurrence. It can be maintained that different degrees of realism are suitable to describe the states of happiness and this fact might have relevant psychological implications, namely for the so-called positive psychology. This is especially true now that there are methods available to induce subjective states of happiness unrelated to the external conditions usually taken to be linked to such states. PMID:27536261

  4. Determination of the Absolute Stereochemistry of Secondary Alcohols: An Advanced Organic Chemistry Experiment for Undergraduate Students.

    ERIC Educational Resources Information Center

    Bandaranayake, Wickramasinghe M.

    1980-01-01

    Describes experiments which can be completed in five four-hour laboratory sessions, including two synthesis (alpha-phenylbutyric and alpha-phenylbutyric acid anhydride) and determining the absolute stereochemistry of secondary alcohols using the synthetic products. (JN)

  5. Stereochemistry of 10-sulfoxidation catalyzed by a soluble delta9 desaturase

    SciTech Connect

    Tremblay, A.E.; Shanklin, J.; Tan, N.; Whittle, E.; Hodgson, D. J.; Dawson, B.; Buist, P. H.

    2010-03-21

    The stereochemistry of castor stearoyl-ACP 9 desaturase-mediated 10-sulfoxidation has been determined. This was accomplished by 19F NMR analysis of a fluorine-tagged product, 18-fluoro-10-thiastearoyl ACP S-oxide, in combination with a chiral solvating agent, (R)-AMA. Sulfoxidation proceeds with the same stereoselectivity as hydrogen removal from the parent stearoyl substrate. These data validate the use of thia probes to determine the stereochemistry and cryptoregiochemistry of desaturase-mediated oxidations.

  6. Asymmetric total synthesis of (-)-lundurine B and determination of its absolute stereochemistry.

    PubMed

    Nakajima, Masaya; Arai, Shigeru; Nishida, Atsushi

    2015-04-01

    A total synthesis of the Kopsia tenuis alkaloid (-)-lundurine B has been achieved. A quaternary chiral carbon has been created by an asymmetric deprotonation using a symmetric spiro cyclohexanone intermediate with a chiral lithium amide. The hexacyclic skeleton was sequentially constructed through metal-mediated reactions. The absolute stereochemistry of intermediate 5 has been unambiguously established by X-ray crystallographic analysis. This is the first description of the absolute stereochemistry of Kopsia tenuis alkaloids based on chemical synthesis. PMID:25601233

  7. Accurate stereochemistry for two related 22,26-epiminocholestene derivatives

    SciTech Connect

    Vega-Baez, José Luis; Sandoval-Ramírez, Jesús; Meza-Reyes, Socorro; Montiel-Smith, Sara; Gómez-Calvario, Victor; Bernès, Sylvain

    2008-04-01

    Regioselective opening of ring E of solasodine under various conditions afforded (25R)-22,26-epimino@@cholesta-5,22(N)-di@@ene-3β,16β-diyl diacetate (previously known as 3,16-diacetyl pseudosolasodine B), C{sub 31}H{sub 47}NO{sub 4}, or (22S,25R)-16β-hydr@@oxy-22,26-epimino@@cholesta-5-en-3β-yl acetate (a derivative of the naturally occurring alkaloid oblonginine), C{sub 29}H{sub 47}NO{sub 3}. In both cases, the reactions are carried out with retention of chirality at the C16, C20 and C25 stereogenic centers, which are found to be S, S and R, respectively. Although pseudosolasodine was synthesized 50 years ago, these accurate assignments clarify some controversial points about the actual stereochemistry for these alkaloids. This is of particular importance in the case of oblonginine, since this compound is currently under consideration for the treatment of aphasia arising from apoplexy; the present study defines a diastereoisomerically pure compound for pharmacological studies.

  8. Costs and benefits of realism and optimism

    PubMed Central

    Bortolotti, Lisa; Antrobus, Magdalena

    2015-01-01

    Purpose of review What is the relationship between rationality and mental health? By considering the psychological literature on depressive realism and unrealistic optimism, it was hypothesized that, in the context of judgments about the self, accurate cognitions are psychologically maladaptive and inaccurate cognitions are psychologically adaptive. Recent studies recommend being cautious in drawing any general conclusion about the style of thinking and mental health. Recent findings Recent investigations suggest that people with depressive symptoms are more accurate than controls in tasks involving time perception and estimates of personal circumstances, but not in other tasks. Unrealistic optimism remains a robust phenomenon across a variety of tasks and domains, and researchers are starting to explore its neural bases. However, the challenge is to determine to what extent and in what way unrealistic optimism is beneficial. Summary We should revisit the hypothesis that optimistic cognitions are psychologically adaptive, whereas realistic thinking is not. Realistic beliefs and expectations can be conducive to wellbeing and good functioning, and wildly optimistic cognitions have considerable psychological costs. PMID:25594418

  9. Looking for treasure in stereochemistry-land. A path marked by curiosity, obstinacy, and serendipity.

    PubMed

    Juaristi, Eusebio

    2012-06-01

    Over the past 40 years, much of my research has evolved around various topics of conformational analysis and asymmetric synthesis. This Perspective describes some of my salient contributions in eight different areas of organic stereochemistry: (1) conformational analysis of six-membered rings, (2) evaluation of stereoelectronic interactions in (1)J(C-H) one-bond coupling constants in six-membered rings, (3) eclipsed conformation in cis-2-tert-butyl-5-(tert-butylsulfonyl)-1,3-dioxane, (4) determination of enthalpic and entropic contributions to ΔG°(CH(2)Ph) and ΔG°(t-Bu), (5) study of the "attractive gauche effect" in O-C-C-O segments, (6) examination of salt effects on conformational equilibria, (7) asymmetric synthesis of β-amino acids, and (8) asymmetric organocatalysis and "Green" chemistry. It will be appreciated that a basic understanding of the principles of physical organic chemistry has been essential in all projects. Furthermore, curiosity, enthusiasm, obstinacy, and paying attention to unexpected observations will lead to many new (stereo)chemical discoveries. PMID:22439876

  10. An Essay for Educators: Epistemological Realism Really is Common Sense

    NASA Astrophysics Data System (ADS)

    Cobern, William W.; Loving, Cathleen C.

    2008-04-01

    “What is truth?” Pontius Pilot asked Jesus of Nazareth. For many educators today this question seems quaintly passé. Rejection of “truth” goes hand-in-hand with the rejection of epistemological realism. Educational thought over the last decade has instead been dominated by empiricist, anti-realist, instrumentalist epistemologies of two types: first by psychological constructivism and later by social constructivism. Social constructivism subsequently has been pressed to its logical conclusion in the form of relativistic multiculturalism. Proponents of both psychological constructivism and social constructivism value knowledge for its utility and eschew as irrelevant speculation any notion that knowledge is actually about reality. The arguments are largely grounded in the discourse of science and science education where science is “western” science; neither universal nor about what is really real. The authors defended the notion of science as universal in a previous article. The present purpose is to offer a commonsense argument in defense of critical realism as an epistemology and the epistemically distinguished position of science (rather than privileged) within a framework of epistemological pluralism. The paper begins with a brief cultural survey of events during the thirty-year period from 1960-1990 that brought many educators to break with epistemological realism and concludes with comments on the pedagogical importance of realism. Understanding the cultural milieu of the past forty years is critical to understanding why traditional philosophical attacks on social constructivist ideas have proved impotent defenders of scientific realism.

  11. Efficient quantification of experimental evidence against local realism

    NASA Astrophysics Data System (ADS)

    Zhang, Yanbao; Glancy, Scott; Knill, Emanuel

    2013-11-01

    Tests of local realism and their applications aim for very high confidence in their results even in the presence of potentially adversarial effects. For this purpose, one can measure a quantity that reflects the amount of violation of local realism and determine a bound on the probability, according to local realism, of obtaining a violation at least that observed. In general, it is difficult to obtain sufficiently robust and small bounds. Here we describe an efficient protocol for computing such bounds from any set of Bell inequalities for any number of parties, measurement settings, or outcomes. The protocol can be applied to tests of other properties (such as entanglement or dimensionality) that are witnessed by linear inequalities.

  12. Does mood influence the realism of confidence judgments?

    PubMed

    Allwood, Carl Martin; Granhag, Pär Anders; Jonsson, Anna-Carin

    2002-07-01

    Previous research has shown that mood affects cognition, but the extent to which mood affects meta-cognitive judgments is a relatively over-looked issue. In the current study we investigated how mood influences the degree of realism in participants' confidence judgments (based on an episodic memory task). Using music and film in combination, we successfully induced an elated mood in half of the participants, but failed to induce a sad mood in the other half. In line with previous research, the participants in both conditions were overconfident in their judgments. However, and contrary to our prediction, our data indicated that there was no difference in the realism of the confidence between the conditions. When relating this result to previous research, our conclusion is that there is no, or very little, influence of mood of moderate intensity on the realism of confidence judgments. PMID:12184480

  13. A new paradigm for nursing: the potential of realism.

    PubMed

    Wainwright, S P

    1997-12-01

    Realism has been the dominant approach in the philosophy of science for the last 20 years. Realist philosophy has also been widely employed across a range of social sciences. Unfortunately, these powerful intellectual currents have not reached the shores of nursing which appears trapped in a time-warped debate about 'qualitative' (constructivist) and 'quantitative' (positivist) approaches. This paper argues that both positivism and constructionism are seriously flawed as philosophies of social and natural science. This is in marked contrast with realism which is a philosophy of both the natural and social sciences. I therefore propose that realism should be adopted as a radically different new paradigm for a unified biopsychosocial nursing. PMID:9429979

  14. Piloting Augmented Reality Technology to Enhance Realism in Clinical Simulation.

    PubMed

    Vaughn, Jacqueline; Lister, Michael; Shaw, Ryan J

    2016-09-01

    We describe a pilot study that incorporated an innovative hybrid simulation designed to increase the perception of realism in a high-fidelity simulation. Prelicensure students (N = 12) cared for a manikin in a simulation lab scenario wearing Google Glass, a wearable head device that projected video into the students' field of vision. Students reported that the simulation gave them confidence that they were developing skills and knowledge to perform necessary tasks in a clinical setting and that they met the learning objectives of the simulation. The video combined visual images and cues seen in a real patient and created a sense of realism the manikin alone could not provide. PMID:27258807

  15. Eight-coordinate stereochemistries of U(IV) catecholate and aquo complexes

    SciTech Connect

    Hay, Benjamin P.; Uddin, Jamal; Firman, Timothy K.

    2004-01-01

    An extended MM3 model has been used to identify all low energy configurations for U(IV) complexes with catecholate and aquo ligands. Both stochastic and systematic conformational analyses of[U(cat)n(OH2)8-n]4-2n complexes, n= 1 - 4, establish that 20 of the 67 possible stereochemistries are minima on the MM3 potential surface. The stable stereochemistries are reported for each stoichiometry and, where possible, the results are compared with experimental data and with the predictions from prior repulsion energy calculations.

  16. Host-Guest Assembly of a Molecular Reporter with Chiral Cyanohydrins for Assignment of Absolute Stereochemistry.

    PubMed

    Gholami, Hadi; Anyika, Mercy; Zhang, Jun; Vasileiou, Chrysoula; Borhan, Babak

    2016-06-27

    The absolute stereochemistry of cyanohydrins, derived from ketones and aldehydes, is obtained routinely, in a microscale and derivatization-free manner, upon their complexation with Zn-MAPOL, a zincated porphyrin host with a binding pocket comprised of a biphenol core. The host-guest complex leads to observable exciton-coupled circular dichroism (ECCD), the sign of which is easily correlated to the absolute stereochemistry of the bound cyanohydrin. A working model, based on the ECCD signal of cyanohydrins with known configuration, is proposed. PMID:27258557

  17. Real Gardens with Real Toads: A New Sort of Realism in Poetry.

    ERIC Educational Resources Information Center

    Livingston, Myra Cohn

    1995-01-01

    Discusses realism in children's poetry and a New Realism which dates from the 1960s. Suggests that the denial of realism occupies much of the efforts of Mother Goose reformers, who have carried on "for eons" over the violence, mayhem, and cruelty in the old nursery rhymes. (RS)

  18. Scientific Symbiosis Represents the Mutual Benefit of Iteratively Adopting the Perspective of Realism and Instrumentalism

    ERIC Educational Resources Information Center

    Cacioppo, John T.; Berntson, Gary G.; Semin, Gu R.

    2005-01-01

    This article presents comments on "Psychology Needs Realism not Instrumentalism" by B. Haig, "Ontological and Epistemic Claims of Realism and Instrumentalism" by Lau and "The Scientific Denial of the Real and the Dialectic of Scientism and Humanism" by Ramey and Chrysikou which were all comments on the original article "Realism, Instrumentalism,…

  19. Does Quantum Physics Refute Realism, Materialism and Determinism?

    ERIC Educational Resources Information Center

    Bunge, Mario

    2012-01-01

    It is argued that the correct answer to the three questions in the title is "no": that the theses being denied derive from traditional philosophy, not from the way the quantum theories are used. For example, the calculation of the energy spectrum of an atom assumes the autonomous existence of the atom, rather than its dependence upon the observer.…

  20. The JPL Cost Risk Analysis Approach that Incorporates Engineering Realism

    NASA Technical Reports Server (NTRS)

    Harmon, Corey C.; Warfield, Keith R.; Rosenberg, Leigh S.

    2006-01-01

    This paper discusses the JPL Cost Engineering Group (CEG) cost risk analysis approach that accounts for all three types of cost risk. It will also describe the evaluation of historical cost data upon which this method is based. This investigation is essential in developing a method that is rooted in engineering realism and produces credible, dependable results to aid decision makers.

  1. An Exploration of Adolescents' Perceptions of Videogame Realism

    ERIC Educational Resources Information Center

    Malliet, Steven

    2006-01-01

    An attempt is made to translate the concept of perceived realism from the domain of general media studies to the domain of videogame studies. In order to make such a translation, a thorough knowledge and integration is required of the simulation aspects that distinguish videogames from older media such as film or television. The different meanings…

  2. A Quest to Explain the Extreme Realism in Newbery Books

    ERIC Educational Resources Information Center

    Miguez, Betsy Bryan; Goetting, Denise

    2006-01-01

    The quest to explain the extreme realism found in some Newbery Award books led the authors to discover that there is no unified view of childhood affecting children's literature today. While some adults feel that children must be protected against the evil surrounding them, others feel that they must be prepared to face the world in which they…

  3. Ontological and Epistemic Claims of Realism and Instrumentalism

    ERIC Educational Resources Information Center

    Lau, Michael Y.

    2005-01-01

    This article presents comments on "Realism, Instrumentalism, and Scientific Symbiosis: Psychological Theory as a Search for Truth and the Discovery of Solutions" by John T. Cacioppo, Gun R. Semin and Gary G. Berntson. While Lau admires the authors efforts to negotiate symbiosis with seemingly incommensurate realist and instrumentalist positions in…

  4. Young People: Victims of Realism in Books and in Life

    ERIC Educational Resources Information Center

    Jordan, June

    1973-01-01

    The author's credo is not to write anything unless it is usable, good news, or usable information to interdict and humanely supersede the reality of some particular bad news. She urges librarians and publishers to desist their perpetuation of the status quo under the mantle of realism. (Author/SJ)

  5. An Essay for Educators: Epistemological Realism Really is Common Sense

    ERIC Educational Resources Information Center

    Cobern, William W.; Loving, Cathleen C.

    2008-01-01

    "What is truth?" Pontius Pilot asked Jesus of Nazareth. For many educators today this question seems quaintly passe. Rejection of "truth" goes hand-in-hand with the rejection of epistemological realism. Educational thought over the last decade has instead been dominated by empiricist, anti-realist, instrumentalist epistemologies of two types:…

  6. Response to "Notes on Pragmatism and Scientific Realism."

    ERIC Educational Resources Information Center

    House, Ernest R.

    1992-01-01

    The main differences between pragmatism and scientific realism seem to focus on the certainty of knowledge. Pragmatists contend that one can never be entirely certain of one's beliefs, whereas scientific realists argue that progress has been, and can be, made in explaining things about the world. (SLD)

  7. Realism and Romance: The Study of Media Effects.

    ERIC Educational Resources Information Center

    Tuchman, Gaye

    1993-01-01

    Compares and contrasts two studies representing diametrical approaches (Romanticism versus Realism) toward the issue of agency and media effects: P. Willis's "Common Culture" and W. A. Gamson's "Talking Politics." Argues that both studies find that people make their own uses of media. (SR)

  8. Implementation and Student Testing of a Web-Based, Student-Centered Stereochemistry Tutorial

    ERIC Educational Resources Information Center

    Burrmann, Nicola J.; Moore, John W.

    2015-01-01

    The implementation of a web-based stereochemistry tutorial, which allows students to select their preferred structural representation and method for making stereochemical comparisons between molecules, is discussed. The tutorial was evaluated by students in three different introductory organic chemistry courses at a large midwestern university.…

  9. A Wet-Lab Approach to Stereochemistry Using [superscript 31]P NMR Spectroscopy

    ERIC Educational Resources Information Center

    Fenton, Owen S.; Sculimbrene, Bianca R.

    2011-01-01

    Understanding stereochemistry is an important and difficult task for students to master in organic chemistry. In both introductory and advanced courses, students are encouraged to explore the spatial relationships between molecules, but this exploration is often limited either to the lecture hall or the confines of the library. As such, we sought…

  10. Reinvestigation of the stereochemistry of the C-glycosidic ellagitannins, vescalagin and castalagin.

    PubMed

    Matsuo, Yosuke; Wakamatsu, Hatsumi; Omar, Mohamed; Tanaka, Takashi

    2015-01-01

    The stereochemistry of the C-glycosidic ellagitannins, vescalagin and castalagin, has been reinvestigated using computational methods. DFT calculations of their (1)H and (13)C NMR spectra, as well as TDDFT calculations of the ECD spectra of their des-hexahydroxydiphenoyl analogues, revealed that the structure of the triphenoyl moiety of vescalagin and castalagin should be revised. PMID:25496565

  11. Using NMR to Probe the Regio- and Stereochemistry of the Hydration of 1-Hexene

    ERIC Educational Resources Information Center

    Saba, Shahrokh; Clarke, Donald D.; Iwanoski, Christa; Lobasso, Thomas

    2010-01-01

    This undergraduate organic laboratory experiment complements previously described and popular experiments on hydration of 1-hexene where students experimentally establish the Markovnikov regioselectivity of alkene hydration. In this experiment, students explore not only the regiochemistry but also the stereochemistry of 1-hexene hydration and…

  12. [Dispositional optimism, pessimism and realism in technological potential entrepreneurs].

    PubMed

    López Puga, Jorge; García García, Juan

    2011-11-01

    Optimism has been classically considered a key trait in entrepreneurs' personality but it has been studied from a psychological point of view only in recent years. The main aim of this research is to study the relationship between dispositional optimism, pessimism and realism as a function of the tendency to create technology-based businesses. A sample of undergraduate students (n= 205) filled in an electronic questionnaire containing the Life Orientation Test-Revised after they were classified as potential technological entrepreneurs, potential general entrepreneurs and non-potential entrepreneurs. Our results show that technology-based entrepreneurs are more optimistic than non-potential entrepreneurs, whereas there were no statistical differences in pessimism and realism. The results are interpreted theoretically to define the potential entrepreneur and, from an applied perspective, to design training programmes to support future technological entrepreneurs. PMID:22047847

  13. Strong Loophole-Free Test of Local Realism.

    PubMed

    Shalm, Lynden K; Meyer-Scott, Evan; Christensen, Bradley G; Bierhorst, Peter; Wayne, Michael A; Stevens, Martin J; Gerrits, Thomas; Glancy, Scott; Hamel, Deny R; Allman, Michael S; Coakley, Kevin J; Dyer, Shellee D; Hodge, Carson; Lita, Adriana E; Verma, Varun B; Lambrocco, Camilla; Tortorici, Edward; Migdall, Alan L; Zhang, Yanbao; Kumor, Daniel R; Farr, William H; Marsili, Francesco; Shaw, Matthew D; Stern, Jeffrey A; Abellán, Carlos; Amaya, Waldimar; Pruneri, Valerio; Jennewein, Thomas; Mitchell, Morgan W; Kwiat, Paul G; Bienfang, Joshua C; Mirin, Richard P; Knill, Emanuel; Nam, Sae Woo

    2015-12-18

    We present a loophole-free violation of local realism using entangled photon pairs. We ensure that all relevant events in our Bell test are spacelike separated by placing the parties far enough apart and by using fast random number generators and high-speed polarization measurements. A high-quality polarization-entangled source of photons, combined with high-efficiency, low-noise, single-photon detectors, allows us to make measurements without requiring any fair-sampling assumptions. Using a hypothesis test, we compute p values as small as 5.9×10^{-9} for our Bell violation while maintaining the spacelike separation of our events. We estimate the degree to which a local realistic system could predict our measurement choices. Accounting for this predictability, our smallest adjusted p value is 2.3×10^{-7}. We therefore reject the hypothesis that local realism governs our experiment. PMID:26722906

  14. Asymptotically optimal data analysis for rejecting local realism

    NASA Astrophysics Data System (ADS)

    Zhang, Yanbao; Glancy, Scott; Knill, Emanuel

    2011-12-01

    Reliable experimental demonstrations of violations of local realism are highly desirable for fundamental tests of quantum mechanics. One can quantify the violation witnessed by an experiment in terms of a statistical p value, which can be defined as the maximum probability according to local realism of a violation at least as high as that witnessed. Thus, high violation corresponds to small p value. We propose a prediction-based-ratio (PBR) analysis protocol whose p values are valid even if the prepared quantum state varies arbitrarily and local realistic models can depend on previous measurement settings and outcomes. It is therefore not subject to the memory loophole [J. Barrett , Phys. Rev. APLRAAN1050-294710.1103/PhysRevA.66.042111 66, 042111 (2002)]. If the prepared state does not vary in time, the p values are asymptotically optimal. For comparison, we consider protocols derived from the number of standard deviations of violation of a Bell inequality and from martingale theory [R. Gill, e-print arXiv:quant-ph/0110137]. We find that the p values of the former can be too small and are therefore not statistically valid, while those derived from the latter are suboptimal. PBR p values do not require a predetermined Bell inequality and can be used to compare results from different tests of local realism independent of experimental details.

  15. Predicting the ungauged basin: Model validation and realism assessment

    NASA Astrophysics Data System (ADS)

    van Emmerik, Tim; Mulder, Gert; Eilander, Dirk; Piet, Marijn; Savenije, Hubert

    2015-10-01

    The hydrological decade on Predictions in Ungauged Basins (PUB) led to many new insights in model development, calibration strategies, data acquisition and uncertainty analysis. Due to a limited amount of published studies on genuinely ungauged basins, model validation and realism assessment of model outcome has not been discussed to a great extent. With this paper we aim to contribute to the discussion on how one can determine the value and validity of a hydrological model developed for an ungauged basin. As in many cases no local, or even regional, data are available, alternative methods should be applied. Using a PUB case study in a genuinely ungauged basin in southern Cambodia, we give several examples of how one can use different types of soft data to improve model design, calibrate and validate the model, and assess the realism of the model output. A rainfall-runoff model was coupled to an irrigation reservoir, allowing the use of additional and unconventional data. The model was mainly forced with remote sensing data, and local knowledge was used to constrain the parameters. Model realism assessment was done using data from surveys. This resulted in a successful reconstruction of the reservoir dynamics, and revealed the different hydrological characteristics of the two topographical classes. This paper does not present a generic approach that can be transferred to other ungauged catchments, but it aims to show how clever model design and alternative data acquisition can result in a valuable hydrological model for an ungauged catchment.

  16. Asymptotically optimal data analysis for rejecting local realism

    SciTech Connect

    Zhang, Yanbao; Glancy, Scott; Knill, Emanuel

    2011-12-15

    Reliable experimental demonstrations of violations of local realism are highly desirable for fundamental tests of quantum mechanics. One can quantify the violation witnessed by an experiment in terms of a statistical p value, which can be defined as the maximum probability according to local realism of a violation at least as high as that witnessed. Thus, high violation corresponds to small p value. We propose a prediction-based-ratio (PBR) analysis protocol whose p values are valid even if the prepared quantum state varies arbitrarily and local realistic models can depend on previous measurement settings and outcomes. It is therefore not subject to the memory loophole [J. Barrett et al., Phys. Rev. A 66, 042111 (2002)]. If the prepared state does not vary in time, the p values are asymptotically optimal. For comparison, we consider protocols derived from the number of standard deviations of violation of a Bell inequality and from martingale theory [R. Gill, e-print arXiv:quant-ph/0110137]. We find that the p values of the former can be too small and are therefore not statistically valid, while those derived from the latter are suboptimal. PBR p values do not require a predetermined Bell inequality and can be used to compare results from different tests of local realism independent of experimental details.

  17. Relative Stereochemistry and Absolute Configuration of Farinosin, a Eudesmanolide From Encelia farinosa.

    PubMed

    Ortega, Alfredo R; Sánchez-Castellanos, Mariano; Pérez-Hernández, Nury; Robles-Zepeda, Ramón E; Joseph-Nathan, Pedro; Quijano, Leovigildo

    2016-05-01

    The naturally occurring eudesmanolide farinosin () is now fully characterized for the first time despite its original isolation almost half a century ago. The early assumed relative stereochemistry and absolute configuration were confirmed by vibrational circular dichroism together with evaluation of the Hooft X-ray parameters. The molecular conformation is very similar in the gas stage and in the solid state. Chirality 28:415-419, 2016. © 2016 Wiley Periodicals, Inc. PMID:27027742

  18. The German VR Simulation Realism Scale--psychometric construction for virtual reality applications with virtual humans.

    PubMed

    Poeschl, Sandra; Doering, Nicola

    2013-01-01

    Virtual training applications with high levels of immersion or fidelity (for example for social phobia treatment) produce high levels of presence and therefore belong to the most successful Virtual Reality developments. Whereas display and interaction fidelity (as sub-dimensions of immersion) and their influence on presence are well researched, realism of the displayed simulation depends on the specific application and is therefore difficult to measure. We propose to measure simulation realism by using a self-report questionnaire. The German VR Simulation Realism Scale for VR training applications was developed based on a translation of scene realism items from the Witmer-Singer-Presence Questionnaire. Items for realism of virtual humans (for example for social phobia training applications) were supplemented. A sample of N = 151 students rated simulation realism of a Fear of Public Speaking application. Four factors were derived by item- and principle component analysis (Varimax rotation), representing Scene Realism, Audience Behavior, Audience Appearance and Sound Realism. The scale developed can be used as a starting point for future research and measurement of simulation realism for applications including virtual humans. PMID:23792838

  19. ADDING REALISM TO NUCLEAR MATERIAL DISSOLVING ANALYSIS

    SciTech Connect

    Williamson, B.

    2011-08-15

    Two new criticality modeling approaches have greatly increased the efficiency of dissolver operations in H-Canyon. The first new approach takes credit for the linear, physical distribution of the mass throughout the entire length of the fuel assembly. This distribution of mass is referred to as the linear density. Crediting the linear density of the fuel bundles results in using lower fissile concentrations, which allows higher masses to be charged to the dissolver. Also, this approach takes credit for the fact that only part of the fissile mass is wetted at a time. There are multiple assemblies stacked on top of each other in a bundle. On average, only 50-75% of the mass (the bottom two or three assemblies) is wetted at a time. This means that only 50-75% (depending on operating level) of the mass is moderated and is contributing to the reactivity of the system. The second new approach takes credit for the progression of the dissolving process. Previously, dissolving analysis looked at a snapshot in time where the same fissile material existed both in the wells and in the bulk solution at the same time. The second new approach models multiple consecutive phases that simulate the fissile material moving from a high concentration in the wells to a low concentration in the bulk solution. This approach is more realistic and allows higher fissile masses to be charged to the dissolver.

  20. Improving Realism in Reduced Gravity Simulators

    NASA Technical Reports Server (NTRS)

    Cowley, Matthew; Harvil, Lauren; Clowers, Kurt; Clark, Timothy; Rajulu, Sudhakar

    2010-01-01

    Since man was first determined to walk on the moon, simulating the lunar environment became a priority. Providing an accurate reduced gravity environment is crucial for astronaut training and hardware testing. This presentation will follow the development of reduced gravity simulators to a final comparison of environments between the currently used systems. During the Apollo program era, multiple systems were built and tested, with several NASA centers having their own unique device. These systems ranged from marionette-like suspension devices where the subject laid on his side, to pneumatically driven offloading harnesses, to parabolic flights. However, only token comparisons, if any, were made between systems. Parabolic flight allows the entire body to fall at the same rate, giving an excellent simulation of reduced gravity as far as the biomechanics and physical perceptions are concerned. While the effects are accurate, there is limited workspace, limited time, and high cost associated with these tests. With all mechanical offload systems only the parts of the body that are actively offloaded feel any reduced gravity effects. The rest of the body still feels the full effect of gravity. The Partial Gravity System (Pogo) is the current ground-based offload system used to training and testing at the NASA Johnson Space Center. The Pogo is a pneumatic type system that allows for offloaded motion in the z-axis and free movement in the x-axis, but has limited motion in the y-axis. The pneumatic system itself is limited by cylinder stroke length and response time. The Active Response Gravity Offload System (ARGOS) is a next generation groundbased offload system, currently in development, that is based on modern robotic manufacturing lines. This system is projected to provide more z-axis travel and full freedom in both the x and y-axes. Current characterization tests are underway to determine how the ground-based offloading systems perform, how they compare to parabolic

  1. Predicting the ungauged basin: model validation and realism assessment

    NASA Astrophysics Data System (ADS)

    van Emmerik, Tim; Mulder, Gert; Eilander, Dirk; Piet, Marijn; Savenije, Hubert

    2016-04-01

    The hydrological decade on Predictions in Ungauged Basins (PUB) [1] led to many new insights in model development, calibration strategies, data acquisition and uncertainty analysis. Due to a limited amount of published studies on genuinely ungauged basins, model validation and realism assessment of model outcome has not been discussed to a great extent. With this study [2] we aim to contribute to the discussion on how one can determine the value and validity of a hydrological model developed for an ungauged basin. As in many cases no local, or even regional, data are available, alternative methods should be applied. Using a PUB case study in a genuinely ungauged basin in southern Cambodia, we give several examples of how one can use different types of soft data to improve model design, calibrate and validate the model, and assess the realism of the model output. A rainfall-runoff model was coupled to an irrigation reservoir, allowing the use of additional and unconventional data. The model was mainly forced with remote sensing data, and local knowledge was used to constrain the parameters. Model realism assessment was done using data from surveys. This resulted in a successful reconstruction of the reservoir dynamics, and revealed the different hydrological characteristics of the two topographical classes. We do not present a generic approach that can be transferred to other ungauged catchments, but we aim to show how clever model design and alternative data acquisition can result in a valuable hydrological model for ungauged catchments. [1] Sivapalan, M., Takeuchi, K., Franks, S., Gupta, V., Karambiri, H., Lakshmi, V., et al. (2003). IAHS decade on predictions in ungauged basins (PUB), 2003-2012: shaping an exciting future for the hydrological sciences. Hydrol. Sci. J. 48, 857-880. doi: 10.1623/hysj.48.6.857.51421 [2] van Emmerik, T., Mulder, G., Eilander, D., Piet, M. and Savenije, H. (2015). Predicting the ungauged basin: model validation and realism assessment

  2. Magical realism: a cultural intervention for traumatized Hispanic children.

    PubMed

    De Rios, M D

    1997-01-01

    A case study is presented of two Spanish-speaking immigrant children who were run over in an automobile accident and hospitalized, to describe a culturally congruent play-therapy technique. Drawing on the work of Pynoos and Nader, the author argues for an anthropological approach in play therapy to create hyperaroused states for the traumatized child and to use cultural super heroes-what is termed "magical realism." Such an approach can be used with Latin American traumatized children as well as with children from other Third World countries to provide a culturally appropriate intervention to treat the psychological sequelae of trauma. PMID:9277017

  3. Extreme Violation of Local Realism in Quantum Hypergraph States

    NASA Astrophysics Data System (ADS)

    Gachechiladze, Mariami; Budroni, Costantino; Gühne, Otfried

    2016-02-01

    Hypergraph states form a family of multiparticle quantum states that generalizes the well-known concept of Greenberger-Horne-Zeilinger states, cluster states, and more broadly graph states. We study the nonlocal properties of quantum hypergraph states. We demonstrate that the correlations in hypergraph states can be used to derive various types of nonlocality proofs, including Hardy-type arguments and Bell inequalities for genuine multiparticle nonlocality. Moreover, we show that hypergraph states allow for an exponentially increasing violation of local realism which is robust against loss of particles. Our results suggest that certain classes of hypergraph states are novel resources for quantum metrology and measurement-based quantum computation.

  4. Faithful test of nonlocal realism with entangled coherent states

    SciTech Connect

    Lee, Chang-Woo; Jeong, Hyunseok; Paternostro, Mauro

    2011-02-15

    We investigate the violation of Leggett's inequality for nonlocal realism using entangled coherent states and various types of local measurements. We prove mathematically the relation between the violation of the Clauser-Horne-Shimony-Holt form of Bell's inequality and Leggett's one when tested by the same resources. For Leggett inequalities, we generalize the nonlocal realistic bound to systems in Hilbert spaces larger than bidimensional ones and introduce an optimization technique that allows one to achieve larger degrees of violation by adjusting the local measurement settings. Our work describes the steps that should be performed to produce a self-consistent generalization of Leggett's original arguments to continuous-variable states.

  5. Efficiency of ultrasound training simulators: method for assessing image realism.

    PubMed

    Bø, Lars Eirik; Gjerald, Sjur Urdson; Brekken, Reidar; Tangen, Geir Arne; Hernes, Toril A Nagelhus

    2010-04-01

    Although ultrasound has become an important imaging modality within several medical professions, the benefit of ultrasound depends to some degree on the skills of the person operating the probe and interpreting the image. For some applications, the possibility to educate operators in a clinical setting is limited, and the use of training simulators is considered an alternative approach for learning basic skills. To ensure the quality of simulator-based training, it is important to produce simulated ultrasound images that resemble true images to a sufficient degree. This article describes a method that allows corresponding true and simulated ultrasound images to be generated and displayed side by side in real time, thus facilitating an interactive evaluation of ultrasound simulators in terms of image resemblance, real-time characteristics and man-machine interaction. The proposed method could be used to study the realism of ultrasound simulators and how this realism affects the quality of training, as well as being a valuable tool in the development of simulation algorithms. PMID:20337541

  6. Enhancing Realism of Wet Surfaces in Temporal Bone Surgical Simulation

    PubMed Central

    Kerwin, Thomas; Shen, Han-Wei; Stredney, Don

    2009-01-01

    We present techniques to improve visual realism in an interactive surgical simulation application: a mastoidectomy simulator that offers a training environment for medical residents as a complement to using a cadaver. As well as displaying the mastoid bone through volume rendering, the simulation allows users to experience haptic feedback and appropriate sound cues while controlling a virtual bone drill and suction/irrigation device. The techniques employed to improve realism consist of a fluid simulator and a shading model. The former allows for deformable boundaries based on volumetric bone data, while the latter gives a wet look to the rendered bone to emulate more closely the appearance of the bone in a surgical environment. The fluid rendering includes bleeding effects, meniscus rendering, and refraction. We incorporate a planar computational fluid dynamics simulation into our three-dimensional rendering to effect realistic blood diffusion. Maintaining real-time performance while drilling away bone in the simulation is critical for engagement with the system. PMID:19590102

  7. Sesquiterpene lactone stereochemistry influences herbivore resistance and plant fitness in the field

    PubMed Central

    Ahern, Jeffrey R.; Whitney, Kenneth D.

    2014-01-01

    Background and Aims Stereochemical variation is widely known to influence the bioactivity of compounds in the context of pharmacology and pesticide science, but our understanding of its importance in mediating plant–herbivore interactions is limited, particularly in field settings. Similarly, sesquiterpene lactones are a broadly distributed class of putative defensive compounds, but little is known about their activities in the field. Methods Natural variation in sesquiterpene lactones of the common cocklebur, Xanthium strumarium (Asteraceae), was used in conjunction with a series of common garden experiments to examine relationships between stereochemical variation, herbivore damage and plant fitness. Key Results The stereochemistry of sesquiterpene lactone ring junctions helped to explain variation in plant herbivore resistance. Plants producing cis-fused sesquiterpene lactones experienced significantly higher damage than plants producing trans-fused sesquiterpene lactones. Experiments manipulating herbivore damage above and below ambient levels found that herbivore damage was negatively correlated with plant fitness. This pattern translated into significant fitness differences between chemotypes under ambient levels of herbivore attack, but not when attack was experimentally reduced via pesticide. Conclusions To our knowledge, this work represents only the second study to examine sesquiterpene lactones as defensive compounds in the field, the first to document herbivore-mediated natural selection on sesquiterpene lactone variation and the first to investigate the ecological significance of the stereochemistry of the lactone ring junction. The results indicate that subtle differences in stereochemistry may be a major determinant of the protective role of secondary metabolites and thus of plant fitness. As stereochemical variation is widespread in many groups of secondary metabolites, these findings suggest the possibility of dynamic evolutionary histories

  8. Through-space (19) F-(15) N couplings for the assignment of stereochemistry in flubenzimine.

    PubMed

    Ghiviriga, Ion; Rubinski, Miles A; Dolbier, William R

    2016-07-01

    Through-space (19) F-(15) N couplings revealed the configuration of flubenzimine, with the CF3 group on N4 pointing towards the lone pair of N5. The (19) F-(15) N coupling constants were measured at natural abundance using a spin-state selective indirect-detection pulse sequence. As (15) N-labelled proteins are routinely synthesized for NMR studies, through-space (19) F-(15) N couplings have the potential to probe the stereochemistry of these proteins by (19) F labelling of some amino acids or can reveal the site of docking of fluorine-containing drugs. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27059012

  9. Antiviral activities of isometric dideoxynucleosides of D- and L-related stereochemistry.

    PubMed Central

    Nair, V; Jahnke, T S

    1995-01-01

    In summary, many isomeric analogs of ddNs of both D-related and L-related absolute stereochemistries have been synthesized and evaluated in vitro for their antiviral activities. A few of these compounds exhibit potent antiviral activity and, interestingly, belong to both the D and L families. The synthetic methodologies developed will allow accessibility to many more novel modified nucleosides. While some structure-activity relationships are emerging from this work, it is clear that these chiral isomeric nucleosides have opened a new chapter in the field of antiviral nucleosides. PMID:7625783

  10. The Stereochemistry of Amino Acids In Carbonaceous Meteorites: Implications For Life's Origin

    NASA Astrophysics Data System (ADS)

    Engel, M. H.; Andrusevich, V. E.; Macko, S. A.

    Numerous processes have been proposed for the abiotic synthesis of organic com- pounds deemed essential for life's origin. However, none of these pathways for abiotic synthesis on Earth result in the stereochemistry that is observed for all life on Earth. All experiments utilizing abiotic syntheses for amino acids have produced racemic mixtures. Amino acid constituents of proteins in all living organisms are, however, al- most exclusively levorotary (L). We report the occurrence of L-amino acid enantiomer excesses in the hydrolyzed water extracts of two carbonaceous meteorites. Acid ex- tractions of the meteorite powders subsequent to water extraction resulted in the re- covery of even higher percentages of L-enantiomers relative to D-enantiomers. Amino acid distributions and stable isotope compositions support an extraterrestrial origin for these compounds rather than biological input subsequent to impact. Several common protein amino acids are entirely absent in the meteorite extracts and those that are present have stable isotope compositions outside of the range commonly observed for ancient and modern organic matter of biological origin on Earth. It is suggested that impact events during the Earth's early history may have provided organic compounds with the correct stereochemistry for life's origin.

  11. Stereochemistry and spectroscopic analysis of bis-Betti base derivatives of 2,3-dihydroxynaphthalene.

    PubMed

    Zamani, Mehdi; Shafiee, Mehdi; Keshavarz, Mohammad Hossein

    2016-04-01

    Density functional theory (DFT) was used to study the stereochemistry, thermodynamic stability, and spectra of recently synthesized bis-Betti base derivatives of 2,3-dihydroxynaphthalene obtained through multicomponent reactions of 2,3-dihydroxynaphthalene with aminoisoxazole and benzaldehyde derivatives. The stereochemistry of the products was investigated by theoretically calculating the infrared (IR) and proton nuclear magnetic resonance ((1)H NMR) spectra of the diastereomers and comparing them to the corresponding experimental data. The thermochemical properties of the reactions, including the enthalpy, internal energy, entropy, and Gibbs free energy, were also calculated. The diastereoselectivity of the reactions was estimated from the equilibrium distribution of diastereomers. According to the results, the synthesis of bis-Betti bases is exothermic and accompanied by a decrease in entropy. The energy difference between the diastereomers is quite small, but the Gibbs free energy change for the equilibrium syn <−> anti favors the anti over syn configuration. These results are in good agreement with experimental observations. PMID:26994020

  12. Carbohydrate Stereochemistry.

    ERIC Educational Resources Information Center

    Shallenberger, Robert S.; Wienen, Wanda J.

    1989-01-01

    Treats the development of general stereochemical principles in historical fashion. Discusses work by Pasteur, van't Hoff, and Le Bel. Considers sugars by configuration, anomeric forms, ring forms, and conformational isomers. Presents numerous diagrams and thorough explanations. (MVL)

  13. A Measure of Psychological Realism on a Visual Simulator

    NASA Technical Reports Server (NTRS)

    Palmer, Everett; Petitt, John

    1977-01-01

    A FUNDAMENTAL question of simulation technology is how to determine if an aircraft simulation is creating the proper psychological space necessary to assess manned-system performance. The standard approach to this problem for visual simulators is to measure how well pilots can make approaches and landings on the simulator. Experiments of this type generally show that simulator performance is worse than actual landing performance and that there is an excessive amount of training required to reach acceptable performance. Unfortunately, in these experiments it is difficult to sort out the inadequacies of the visual subsystem from possible inadequacies in other simulator subsystems, such as the motion subsystem. This synoptic presents the results from one of a series of five experiments which attempted to provide direct measures of the psychological realism on a computer graphics night visual flight attachment. These experiments used experimental procedures and methodologies that psychologists have developed in their attempts to determine how people perceived visual space in the real world.

  14. Processing Digital Imagery to Enhance Perceptions of Realism

    NASA Technical Reports Server (NTRS)

    Woodell, Glenn A.; Jobson, Daniel J.; Rahman, Zia-ur

    2003-01-01

    Multi-scale retinex with color restoration (MSRCR) is a method of processing digital image data based on Edwin Land s retinex (retina + cortex) theory of human color vision. An outgrowth of basic scientific research and its application to NASA s remote-sensing mission, MSRCR is embodied in a general-purpose algorithm that greatly improves the perception of visual realism and the quantity and quality of perceived information in a digitized image. In addition, the MSRCR algorithm includes provisions for automatic corrections to accelerate and facilitate what could otherwise be a tedious image-editing process. The MSRCR algorithm has been, and is expected to continue to be, the basis for development of commercial image-enhancement software designed to extend and refine its capabilities for diverse applications.

  15. Relative reactivities in the O-methylation of glucomannans: the influence of stereochemistry at C-2 and the solvent effect.

    PubMed

    Zhang, Yujia; Li, Jiebing; Lindström, Mikael E; Mischnick, Petra

    2015-01-30

    The main hemicellulose in softwood, glucomannan (GM), structurally resembles cellulose but has quite different physical and chemical properties. In addition to branching and original acetylation, the only other difference between these two β-1,4-linked glycans is the configuration at C-2 in approximately 80% of the sugar residues. In contrast to glucose, the 2-OH in mannose has an axial orientation. The influence of this stereochemistry on the relative reactivities of glucosyl compared to mannosyl units in methylation reactions are studied in this work. Glucomannan isolated from spruce (SGM) and commercially available konjac glucomannan (KGM) was methylated in DMSO/Li-dimsyl/MeI and water/NaOH/MeI system, respectively. In the early stage of the reaction, the glucose part of the SGM achieved slightly higher DS values than the mannose residues, but the overall relative rate constants were close to 1:1. The order of reactivities in glucose was k2>k3>k6 and k3>k2>k6 for mannose (in DMSO/Li-dimsyl/MeI). The rate constants did not remain constant, but k3 decreased when k2 increased for both epimeric sugars. In water/NaOH/MeI, the methylation of the primary 6-OH was much more pronounced with an order of reactivity of O-6>O-2>O-3 for mannose and O-2>O-6>O-3 for glucose. The results are discussed with respect to the OH-acidity and the stereoelectronic, sterical, and solvent effects. PMID:25498017

  16. Structures, Reactions, and Mechanisms: Stereochemistry in the Broadest Sense at the 51st Bürgenstock Conference.

    PubMed

    Fleischer, Ivana

    2016-07-18

    Tradition and innovation: The 51st Bürgenstock Conference on Stereochemistry took place from May 1-6, 2016 and offered its usual mixture of impressive science and superb discussions in a wonderful atmosphere. In the Meeting Review, Ivana Fleischer outlines the program. PMID:27337168

  17. Type 2 local realism is alive and well in the quantum world

    NASA Astrophysics Data System (ADS)

    Boyd, Jeffrey

    2012-02-01

    It is often, but incorrectly said, that there is no local realism in the quantum world. This is wrong because there is a second type of local realism. Type two local realism is drastically different than how most people think of their world, including Einstein. It starts with the idea that we are immersed in a sea of invisible elementary waves, traveling in all directions, at all wavelengths. Whenever a photon or other particle moves, it follows one of these waves in the reverse direction. Although this may sound preposterous, this theory can explain several quantum experiments: Jacques (2007) Wheeler thought experiment with delayed choice, Kim (1999), Quantum eraser experiment with delayed choice, all the Bell test experiments with delayed choice, and the double slit experiment. Using the Theory of Elementary Waves (TEW), all these experiments can, surprisingly, be explained using this unconventional type of local realism, with time going forward.

  18. Structure-activity relationships in aminosterol antibiotics: the effect of stereochemistry at the 7-OH group.

    PubMed

    Tessema, Tsemre-Dingel; Gassler, Frank; Shu, Youheng; Jones, Stephen; Selinsky, Barry S

    2013-06-01

    Squalamine and three aminosterol analogs have been shown to inhibit bacterial cell growth and induce lysis of large unilamellar phospholipid vesicles. The analogs differ in the identity of the polyamine attached at C3 of the sterol, and the stereochemistry of a hydroxyl substituent at C7. Analogs with a tetraammonium spermine polyamine are somewhat more active than analogs with a shorter trisammonium spermidine polyamine, and analogs with an axial (α) hydroxyl substituent at C7 are more active than analogs with the corresponding equatorial (β) hydroxyl group. There is some variability noted; the 7β-OH spermine analog is the most active compound against Escherichia coli, but the least effective against Pseudomonas aeruginosa. Lytic activity correlates well with antimicrobial activity of the compounds, but the lytic activity varies with the phospholipid composition of the vesicles. PMID:23618624

  19. Bacterial Sugar 3,4-Ketoisomerases: Structural Insight into Product Stereochemistry.

    PubMed

    Thoden, James B; Vinogradov, Evgeny; Gilbert, Michel; Salinger, Ari J; Holden, Hazel M

    2015-07-28

    3-Acetamido-3,6-dideoxy-d-galactose (Fuc3NAc) and 3-acetamido-3,6-dideoxy-d-glucose (Qui3NAc) are unusual sugars found on the lipopolysaccharides of Gram-negative bacteria and on the S-layers of Gram-positive bacteria. The 3,4-ketoisomerases, referred to as FdtA and QdtA, catalyze the third steps in the respective biosynthetic pathways for these sugars. Whereas both enzymes utilize the same substrate, the stereochemistries of their products are different. Specifically, the hydroxyl groups at the hexose C-4' positions assume the "galactose" and "glucose" configurations in the FdtA and QdtA products, respectively. In 2007 we reported the structure of the apoform of FdtA from Aneurinibacillus thermoaerophilus, which was followed in 2014 by the X-ray analysis of QdtA from Thermoanaerobacterium thermosaccharolyticum as a binary complex. Both of these enzymes belong to the cupin superfamily. Here we report a combined structural and enzymological study to explore the manner in which these enzymes control the stereochemistry of their products. Various site-directed mutant proteins of each enzyme were constructed, and their dTDP-sugar products were analyzed by NMR spectroscopy. In addition, the kinetic parameters for these protein variants were measured, and the structure of one, namely, the QdtA Y17R/R97H double mutant form, was determined to 2.3-Å resolution. Finally, in an attempt to obtain a model of FdtA with a bound dTDP-linked sugar, the 3,4-ketoisomerase domain of a bifunctional enzyme from Shewanella denitrificans was cloned, purified, and crystallized in the presence of a dTDP-linked sugar analogue. Taken together, the results from this investigation demonstrate that it is possible to convert a "galacto" enzyme into a "gluco" enzyme and vice versa. PMID:26125548

  20. 'Diverse epistemologies', truth and archaeology: in defence of realism.

    PubMed

    Horsthemke, Kai

    2011-06-01

    In a recent journal article, as well as in a recent book chapter, in which she critiques my position on 'indigenous knowledge', Lesley Green of the Department of Social Anthropology at the University of Cape Town argues that 'diverse epistemologies ought to be evaluated not on their capacity to express a strict realism but on their ability to advance understanding'. In order to examine the implications of Green's arguments, and of Nelson Goodman and Catherine Elgin's work in this regard, I apply them to a well-known controversy between Native American (or First Nations) creationism and archaeology. I argue that issues in social justice should be distinguished from issues in epistemology. Moreover, in tightening in this paper the link between knowledge and truth, I attempt to defend science as a 'privileged way of seeing the world'. The analysis of truth, and of related concepts like reality and 'the way the world is', will assume a central role here. I contend that, ultimately, the only coherent and consistent position is a realist view of the pertinent issues and ideas. PMID:20091357

  1. A bacterial tyrosine aminomutase proceeds through retention or inversion of stereochemistry to catalyze its isomerization reaction.

    PubMed

    Wanninayake, Udayanga; Walker, Kevin D

    2013-07-31

    β-Amino acids are biologically active compounds of interest in medicinal chemistry. A class I lyase-like family of aminomutases isomerizes (S)-α-arylalanines to the corresponding β-amino acids by exchange of the NH2/H pair. This family uses a 3,5-dihydro-5-methylidene-4H-imidazol-4-one (MIO) group within the active site to initiate the reaction. The absolute stereochemistry of the product is known for an MIO-dependent tyrosine aminomutase from Chondromyces crocatus (CcTAM) that isomerizes (S)-α-tyrosine to (R)-β-tyrosine. To evaluate the cryptic stereochemistry of the CcTAM mechanism, (2S,3S)-[2,3-(2)H2]- and (2S,3R)-[3-(2)H]-α-tyrosine were stereoselectively synthesized from unlabeled (or [(2)H]-labeled) (4'-hydroxyphenyl)acrylic acids by reduction with D2 (or H2) gas and a chiral Rh-Prophos catalyst. GC/EIMS analysis of the [(2)H]-β-tyrosine biosynthesized by CcTAM revealed that the α-amino group was transferred to Cβ of the phenylpropanoid skeleton with retention of configuration. These labeled substrates also showed that the pro-(3S) proton exchanges with protons from the bulk media during its migration to Cα during catalysis. (1)H- and (2)H NMR analyses of the [(2)H]-β-tyrosine derived from (2S)-[3,3-(2)H2]-α-tyrosine by CcTAM catalysis showed that the migratory proton attached to Cα of the product also with retention of configuration. CcTAM is stereoselective for (R)-β-tyrosine (85%) yet also forms the (S)-β-tyrosine enantiomer (15%) through inversion of configuration at both migration termini, as described herein. The proportion of the (S)-β-isomer made by CcTAM during steady state interestingly increased with solvent pH, and this effect on the proposed reaction mechanism is also discussed. PMID:23800193

  2. Asymmetric synthesis and absolute stereochemistry of a labdane-type diterpenoid isolated from the rhizomes of Isodan yuennanensis.

    PubMed

    Deng, Heping; Cao, Wei; Zhang, Zhijiang; Liu, Bo

    2016-07-14

    The first synthesis of a labdane-type diterpenoid isolated from Isodon yuennanensis was achieved in fourteen steps from commercially available starting material, (+)-sclareolide. The synthesis features the Barton nitrite ester reaction to introduce an oxime at the angular methyl group and the Jones oxidation to construct the lactone segment. By comparison of the optical rotation of our synthetic sample and the natural sample, the absolute stereochemistry of the natural diterpenoid has been determined. PMID:27251032

  3. Realism of procedural task trainers in a pediatric emergency medicine procedures course

    PubMed Central

    Shefrin, Allan; Khazei, Afshin; Cheng, Adam

    2015-01-01

    Background Pediatric emergency medicine (PEM) physicians have minimal experience in life saving procedures and have turned to task trainers to learn these skills. Realism of these models is an important consideration that has received little study. Method PEM physicians and trainees participated in a day long procedural training course that utilized commercially available and homemade task trainers to teach pericardiocentesis, chest tube insertion, cricothyroidotomy and central line insertion. Participants rated the realism of the task trainers as part of a post-course survey. Results The homemade task trainers received variable realism ratings, with 91% of participants rating the pork rib chest tube model as realistic, 82% rating the gelatin pericardiocentesis mold as realistic and 36% rating the ventilator tubing cricothyroidotomy model as realistic. Commercial trainers also received variable ratings, with 45% rating the chest drain and pericardiocentesis simulator as realistic, 74% rating the crichotracheotomy trainer as realistic and 80% rating the central line insertion trainer as realistic. Conclusions Task training models utilized in our course received variable realism ratings. When deciding what type of task trainer to use future courses should carefully consider the desired aspect of realism, and how it aligns with the procedural skill, balanced with cost considerations. PMID:26451232

  4. Separability and Non-Individuality: Is It Possible to Conciliate (At Least A Form Of) Einstein's Realism with Quantum Mechanics?

    NASA Astrophysics Data System (ADS)

    Krause, Décio; Arenhart, Jonas R. B.

    2014-12-01

    In this paper we argue that physical theories, including quantum mechanics, refer to some kind of `objects', even if only implicitly. We raise questions about the logico-mathematical apparatuses commonly employed in such theories, bringing to light some metaphysical presuppositions underlying such apparatuses. We point out to some incongruities in the discourse holding that quantum objects would be entities of some `new kind' while still adhering to the logico-mathematical framework we use to deal with classical objects. The use of such apparatus would hinder us from being in complete agreement with the ontological novelties the theories of quanta seem to advance. Thus, we join those who try to investigate a `logic of quantum mechanics', but from a different point of view: looking for a formal foundation for a supposed new ontology. As a consequence of this move, we can revisit Einstein's ideas on physical reality and propose that, by considering a new kind of object traditionally termed `non-individuals', it is possible to sustain that they still obey some of Einstein's conditions for `physical realities', so that it will be possible to talk of a `principle of separability' in a sense which is not in complete disagreement with quantum mechanics. So, Einstein's departure from quantum mechanics might be softened at least concerning a form of his realism, which sees separated physical objects as distinct `physical realities'.

  5. Isolation of brassicasterol, its synthetic prodrug-crystal structure, stereochemistry and theoretical studies

    NASA Astrophysics Data System (ADS)

    Sethi, Arun; Prakash, Rohit; Srivastava, Sangeeta; Amandeep; Bishnoi, Abha; Singh, Ranvijay Pratap

    2014-07-01

    In the present study brassicasterol (1), was isolated from the chloroform extract of the flowers of Allamanda violacea and identified with the help of different spectroscopic techniques like 1H, 13C, 2D NMR (1H-1H COSY), IR, UV and mass spectrometry. A novel prodrug was synthesized by carrying out esterification of brassicasterol (1) with the well known drug naproxen using Steglich esterification to give 3β-(2-(6-methoxynaphthalene-2yl) propionoxy) 24 methyl cholest-5, 22-dien (2). Compounds 2 was subjected to single crystal X-ray diffraction technique and crystallized out in monoclinic form having P21 space group and stabilized by CH-π interactions. Structure and stereochemistry of compound 2 was established with the help of modern spectroscopic techniques like 1H NMR, IR, UV, mass spectrometry as well as with single crystal X-ray diffraction. Molecular geometry and vibrational frequencies of compounds 1 and 2 were calculated by density functional method (DFT/B3LYP) using 6-31G (d, p) basis set, bond parameters and IR frequencies were correlated with the experimental data. 1H and 13C chemical shifts of compound 1 and 1H chemical shifts of compound 2 were calculated with GIAO method and correlated with experimental data. Hyperconjugative interactions were studied with the help of natural bond order analysis (NBO). Electronic properties of both the compounds such as HOMO-LUMO energies were measured with the help of time dependent DFT method.

  6. Regiochemistry and stereochemistry of the biosynthesis of vitamin B6 from triose units

    SciTech Connect

    Hill, R.E.; Iwanow, A.; Sayer, B.G.; Wysocka, W.; Spenser, I.D.

    1987-06-05

    /sup 13/C and /sup 2/H NMR spectroscopy has been employed to probe the biosynthesis of vitamin B6 in Escherichia coli. The /sup 13/C NMR spectrum of a sample of pyridoxol derived biosynthetically from D-(1,2,3,4,5,6-13C6)glucose shows that the bonds, C(2)-C(3) and C(4)-C(5), of the pyridine nucleus are the only two carbon-carbon bonds of pyridoxol which are generated de novo in the course of its biosynthesis from glucose. It follows that the pyridoxol skeleton is generated from two intact triose units and a triose-derived two-carbon unit, all of which are supplied by glucose. From the /sup 2/H NMR spectra of samples of pyridoxol derived from (R)-(1,1-/sup 2/H/sub 2/)glycerol and (S)-(1,1-/sup 2/H/sub 2/)glycerol, respectively, it can be deduced that the rehydroxymethyl group of glycerol enters C-2', C-4', and C-5' of the pyridoxol skeleton. It follows that each of the three fragments is derived from glycerol in stereo-specific fashion. These results answer questions concerning the regiochemistry and the stereochemistry of pyridoxol biosynthesis.

  7. Temperature-dependent annuloselectivity and stereochemistry in the reactions of methanesulfonyl sulfene with imines.

    PubMed

    Wu, Qiuyue; Yang, Zhanhui; Xu, Jiaxi

    2016-07-26

    The annuloselectivity in the reactions of methanesulfonyl sulfene and imines varies with temperature. At a relatively higher temperature of 20 °C, the [2(s) + 2(i)] annulation of different N-alkyl imines occurs exclusively, giving four-membered trans-β-sultams in up to 69% yields. At a lower temperature of -78 °C, the [2(s) + 2(i) + 2(i)] annulation of N-methyl imines takes place specifically, delivering six-membered 1,2,4-thiadiazine 1,1-dioxides, 4-aza-δ-sultams, in up to 80% yields, with diverse configurations at the C3, C5, and C6 stereocenters. The trans-stereochemistry involved in the [2(s) + 2(i)] annulations is attributed to the conrotatory ring closure of the thermodynamically stable 2,3-thiazabutadiene-type zwitterionic intermediates, while the diverse stereochemical outcomes in the [2(s) + 2(i) + 2(i)] annulations are caused by the iminium isomerization in the stepwise nucleophilic [4 + 2] annulation between the same zwitterionic intermediates and a second molecule of N-methyl imines. PMID:27384153

  8. Absolute stereochemistry of fungal beauveriolide III and ACAT inhibitory activity of four stereoisomers.

    PubMed

    Ohshiro, Taichi; Namatame, Ichiji; Nagai, Kenichiro; Sekiguchi, Takafumi; Doi, Takayuki; Takahashi, Takashi; Akasaka, Kazuaki; Rudel, Lawrence L; Tomoda, Hiroshi; Omura, Satoshi

    2006-09-29

    Fungal beauveriolide III (BeauIII, 1b), a cyclodepsipeptide inhibiting acyl-CoA:cholesterol acyltransferase (ACAT) and showing antiatherogenic activity in mouse models, consists of L-Phe, L-Ala, D-allo-Ile, and 3-hydroxy-4-methyloctanoic acid (HMA) moieties, but the stereochemistry of the HMA part has not until now been fully defined. To determine it, four HMA stereoisomers were synthesized and labeled with (S)-(+)-2-(anthracene-2,3-dicarboximido)-1-propyl trifluoromethane sulfonate (AP-OTf), a chiral fluorescent reagent. The derivatives were separated by HPLC and compared with the natural HMA derivative, which was thereby identified as (3S,4S)HMA in BeauIII. Furthermore, the four beauveriolide III isomers ((3S,4S)BeauIII (23a), (3R,4R)BeauIII (23b), (3R,4S)BeauIII (23c), and (3S,4R)BeauIII (23d)) were synthesized, and it was shown that all the spectral data for 23a were identical with those for natural 1b. Isomers 23a and 23d showed potent inhibitory activity of lipid droplet accumulation in macrophages, while the other two isomers caused weak inhibition. Thus, the 3S configuration of BeauIII is important for this activity. Furthermore, 23a and 23d showed rather specific inhibition against the ACAT1 isozyme. PMID:16995669

  9. Stereochemistry of 4-carboxymuconolactone decarboxylase and muconolactone isomerase in the. beta. -ketoadipate pathway

    SciTech Connect

    Whitman, C.P.; Chari, R.V.J.; Ngai, K.L.; Kozarich, J.W.

    1986-05-01

    The protocatechuate and catechol pathways, two separate and parallel branches of the ..beta..-ketoadipate pathway in Pseudomonas putida, converge at a common intermediate - ..beta..-ketoadipate enol-lactone. The enol-lactone is generated by 4-carboxymuconolactone decarboxylase in the protocatechuate pathway while muconolactone isomerase produces it in the catechol pathway. The presence of these enzymes as well as ..beta..-carboxymuconate cycloisomerase and its substrate, ..beta..-carboxy-cis,cis-muconate, in a NMR tube, leads to the following sequence of events. Lactonization of ..beta..-carboxy-cis,cis-muconate produces 4-carboxymuconolactone which decarboxylates enzymatically with deuteration by D/sub 2/O to afford 2-(/sup 2/H)-4-ketoadipate enol-lactone - the substrate for muconolactone isomerase. Further conversion of the monodeuterated enol-lactone by muconolactone isomerase affords muconolactone which is nearly completely deuterated at the 4 position. The proton ricochets between the 2 and 4 positions with concurrent washout while in the 2 position. Based on the known absolute stereochemistry of 4-carboxymuconolactone and muconolactone, these results suggest that both the decarboxylase and isomerase proceed by syn mechanisms, but operate on opposite faces of the common enol-lactone substrate.

  10. Sequence variation determining stereochemistry of a Δ11 desaturase active in moth sex pheromone biosynthesis.

    PubMed

    Ding, Bao-Jian; Carraher, Colm; Löfstedt, Christer

    2016-07-01

    A Δ11 desaturase from the oblique banded leaf roller moth Choristoneura rosaceana takes the saturated myristic acid and produces a mixture of (E)-11-tetradecenoate and (Z)-11-tetradecenoate with an excess of the Z isomer (35:65). A desaturase from the spotted fireworm moth Choristoneura parallela also operates on myristic acid substrate but produces almost pure (E)-11-tetradecenoate. The two desaturases share 92% amino acid identity and 97% amino acid similarity. There are 24 amino acids differing between these two desaturases. We constructed mutations at all of these positions to pinpoint the sites that determine the product stereochemistry. We demonstrated with a yeast functional assay that one amino acid at the cytosolic carboxyl terminus of the protein (258E) is critical for the Z activity of the C. rosaceana desaturase. Mutating the glutamic acid (E) into aspartic acid (D) transforms the C. rosaceana enzyme into a desaturase with C. parallela-like activity, whereas the reciprocal mutation of the C. parallela desaturase transformed it into an enzyme producing an intermediate 64:36 E/Z product ratio. We discuss the causal link between this amino acid change and the stereochemical properties of the desaturase and the role of desaturase mutations in pheromone evolution. PMID:27163509

  11. Correlation between the Stereochemistry and Bioactivity in Octahedral Rhodium Prolinato Complexes.

    PubMed

    Rajaratnam, Rajathees; Martin, Elisabeth K; Dörr, Markus; Harms, Klaus; Casini, Angela; Meggers, Eric

    2015-08-17

    Controlling the relative and absolute configuration of octahedral metal complexes constitutes a key challenge that needs to be overcome in order to fully exploit the structural properties of octahedral metal complexes for applications in the fields of catalysis, materials sciences, and life sciences. Herein, we describe the application of a proline-based chiral tridentate ligand to decisively control the coordination mode of an octahedral rhodium(III) complex. We demonstrate the mirror-like relationship of synthesized enantiomers and differences between diastereomers. Further, we demonstrate, using the established pyridocarbazole pharmacophore ligand as part of the organometallic complexes, the importance of the relative and absolute stereochemistry at the metal toward chiral environments like protein kinases. Protein kinase profiling and inhibition data confirm that the proline-based enantiopure rhodium(III) complexes, despite having all of the same constitution, differ strongly in their selectivity properties despite their unmistakably mutual origin. Moreover, two exemplary compounds have been shown to induce different toxic effects in an ex vivo rat liver model. PMID:26251218

  12. Did Ptolemy make novel predictions? Launching Ptolemaic astronomy into the scientific realism debate.

    PubMed

    Carman, Christián; Díez, José

    2015-08-01

    The goal of this paper, both historical and philosophical, is to launch a new case into the scientific realism debate: geocentric astronomy. Scientific realism about unobservables claims that the non-observational content of our successful/justified empirical theories is true, or approximately true. The argument that is currently considered the best in favor of scientific realism is the No Miracles Argument: the predictive success of a theory that makes (novel) observational predictions while making use of non-observational content would be inexplicable unless such non-observational content approximately corresponds to the world "out there". Laudan's pessimistic meta-induction challenged this argument, and realists reacted by moving to a "selective" version of realism: the approximately true part of the theory is not its full non-observational content but only the part of it that is responsible for the novel, successful observational predictions. Selective scientific realism has been tested against some of the theories in Laudan's list, but the first member of this list, geocentric astronomy, has been traditionally ignored. Our goal here is to defend that Ptolemy's Geocentrism deserves attention and poses a prima facie strong case against selective realism, since it made several successful, novel predictions based on theoretical hypotheses that do not seem to be retained, not even approximately, by posterior theories. Here, though, we confine our work just to the detailed reconstruction of what we take to be the main novel, successful Ptolemaic predictions, leaving the full analysis and assessment of their significance for the realist thesis to future works. PMID:26193785

  13. Computational plasma physics and supercomputers

    SciTech Connect

    Killeen, J.; McNamara, B.

    1984-09-01

    The Supercomputers of the 80's are introduced. They are 10 to 100 times more powerful than today's machines. The range of physics modeling in the fusion program is outlined. New machine architecture will influence particular codes, but parallel processing poses new coding difficulties. Increasing realism in simulations will require better numerics and more elaborate mathematics.

  14. Increasing combat realism: the effectiveness of stun belt use on soldiers for the enhancement of live training and testing exercises

    NASA Astrophysics Data System (ADS)

    Schricker, Bradley C.; Antalek, Christopher

    2006-05-01

    The ability to make correct decisions while operating in a combat zone enables American and Coalition warfighters to better respond to any threats they may encounter due to the minimization of negative training the warfighter encountered during their live, virtual, and constructive (LVC) training exercises. By increasing the physical effects encountered by one's senses during combat scenarios, combat realism is able to be increased, which is a key component in the reduction in negative training. The use of LVC simulations for training and testing augmentation purposes depends on a number of factors, not the least of which is the accurate representation of the training environment. This is particularly true in the realm of tactical engagement training through the use of Tactical Engagement Simulation Systems (TESS). The training environment is perceived through human senses, most notably sight and hearing. As with other haptic devices, the sense of touch is gaining traction as a viable medium through which to express the effects of combat battle damage from the synthetic training environment to participants within a simulated training exercise. New developments in this field are promoting the safe use of an electronic stun device to indicate to a trainee that they have been hit by a projectile, from either direct or indirect fire, through the course of simulated combat. A growing number of examples suggest that this added output medium can greatly enhance the realism of a training exercise and, thus, improve the training value. This paper serves as a literature survey of this concept, beginning with an explanation of TESS. It will then focus on how the electronic stun effect may be employed within a TESS and then detail some of the noted pros and cons of such an approach. The paper will conclude with a description of potential directions and work.

  15. Coronavirus receptor switch explained from the stereochemistry of protein-carbohydrate interactions and a single mutation.

    PubMed

    Bakkers, Mark J G; Zeng, Qinghong; Feitsma, Louris J; Hulswit, Ruben J G; Li, Zeshi; Westerbeke, Aniek; van Kuppeveld, Frank J M; Boons, Geert-Jan; Langereis, Martijn A; Huizinga, Eric G; de Groot, Raoul J

    2016-05-31

    Hemagglutinin-esterases (HEs) are bimodular envelope proteins of orthomyxoviruses, toroviruses, and coronaviruses with a carbohydrate-binding "lectin" domain appended to a receptor-destroying sialate-O-acetylesterase ("esterase"). In concert, these domains facilitate dynamic virion attachment to cell-surface sialoglycans. Most HEs (type I) target 9-O-acetylated sialic acids (9-O-Ac-Sias), but one group of coronaviruses switched to using 4-O-Ac-Sias instead (type II). This specificity shift required quasisynchronous adaptations in the Sia-binding sites of both lectin and esterase domains. Previously, a partially disordered crystal structure of a type II HE revealed how the shift in lectin ligand specificity was achieved. How the switch in esterase substrate specificity was realized remained unresolved, however. Here, we present a complete structure of a type II HE with a receptor analog in the catalytic site and identify the mutations underlying the 9-O- to 4-O-Ac-Sia substrate switch. We show that (i) common principles pertaining to the stereochemistry of protein-carbohydrate interactions were at the core of the transition in lectin ligand and esterase substrate specificity; (ii) in consequence, the switch in O-Ac-Sia specificity could be readily accomplished via convergent intramolecular coevolution with only modest architectural changes in lectin and esterase domains; and (iii) a single, inconspicuous Ala-to-Ser substitution in the catalytic site was key to the emergence of the type II HEs. Our findings provide fundamental insights into how proteins "see" sugars and how this affects protein and virus evolution. PMID:27185912

  16. Realism, Authenticity, and Learning in Healthcare Simulations: Rules of Relevance and Irrelevance as Interactive Achievements

    ERIC Educational Resources Information Center

    Rystedt, Hans; Sjoblom, Bjorn

    2012-01-01

    Because simulators offer the possibility of functioning as authentic representations of real-world tasks, these tools are regarded as efficient for developing expertise. The users' experience of realism is recognised as crucial, and is often regarded as an effect of the similarity between reality and the simulator itself. In this study, it is…

  17. Televised Entertainment-Education to Prevent Adolescent Alcohol Use: Perceived Realism, Enjoyment, and Impact

    ERIC Educational Resources Information Center

    van Leeuwen, Lonneke; Renes, Reint Jan; Leeuwis, Cees

    2013-01-01

    Alcohol use among adolescents is a concern in the Netherlands because of its high prevalence and risks. To discourage adolescents from drinking alcohol, a televised entertainment-education (E-E) intervention was developed. This study investigated responses of adolescents on perceived realism and enjoyment of the E-E intervention, as well as its…

  18. Fighting with Reality: Considering Mark Johnson's Pragmatic Realism through Bruce Lee's Jeet Kune Do Method

    ERIC Educational Resources Information Center

    Miller, Alexander David

    2015-01-01

    This dissertation considers the supportive and complementary relation between Mark Johnson's embodied realism and Bruce Lee's Jeet Kune Do as a philosophical practice. In exploring this relationship, the emphasis on one's embodiment condition and its relationship with metaphor and self-expression are the primary focus. First, this work involves…

  19. The Cultural Work of Magical Realism in Three Young Adult Novels

    ERIC Educational Resources Information Center

    Latham, Don

    2007-01-01

    Magical realism as a literary mode is often subversive and transgressive, questioning the values and assumptions of the dominant society that it depicts. Young adult literature, by contrast, is typically thought to serve a socializing function, helping to integrate young readers into adult society. What then is the cultural work of magical realism…

  20. Standpoint Theory, Realism and the Search for Objectivity in the Sociology of Education

    ERIC Educational Resources Information Center

    Edwards, Gail

    2014-01-01

    This paper evaluates the contribution of "social realism" in resolving questions of knowledge and curriculum in the sociology of education. Social realists argue that, in the interests of educational equality, all pupils should have access to "powerful" knowledge produced by specialist intellectual communities. Social realism…

  1. Intellectual Realism: The Role of Children's Interpretations of Pictures and Perceptual Verbs.

    ERIC Educational Resources Information Center

    Pillow, Bradford H.; Flavell, John H.

    1985-01-01

    Tested and confirmed, in three experiments, the hypothesis that children's interpretation of pictorial conventions and of the expression "look like" may increase their tendency toward intellectual realism. That is, a tendency to respond to requests for perceptual reports by indicating what is known about an object or array, rather than what is…

  2. Representational Drawing and the Transition from Intellectual to Visual Realism in Children with Autism

    ERIC Educational Resources Information Center

    Ford, Ruth M.; Rees, Elen Lord

    2008-01-01

    The present study compared the representational drawings of children with autism, children with Down syndrome and typically developing children. Participants were asked to draw a series of objects and their depictions were scored for the incidence of intellectual realism. The tasks sought evidence of conceptual as opposed to episodic influences on…

  3. The Influences of Stage of Leaving School on Vocational Maturity and Realism of Vocational Choice

    ERIC Educational Resources Information Center

    Kelso, Geoffrey I.

    1975-01-01

    Cross-sectional data were provided by 1484 male high school pupils. All subjects completed either the Otis Intermediate Test or the Otis Higher Test, Crites' Vocational Development Inventory (VDI), and the author's Student Survey. Results indicate that subjects' anticipated stage of leaving school was significantly related to realism of vocational…

  4. The Role of Realism in Memory for Computergraphics by Children and Adults.

    ERIC Educational Resources Information Center

    King, Alison

    1986-01-01

    The effects of realism on child and adult memory for computergraphics were examined. Recognition of images showed an unusual pattern of decline over time with the initial advantage for realistic and abstract computergraphics disappearing at a week's delay, while recognition for linear image was superior to that of realistic and abstract.…

  5. THE INTERSECTION OF INDEPENDENT LIES: INCREASING REALISM IN ECOLOGICAL RISK ASSESSMENT

    EPA Science Inventory

    In 1966, Levins presented a philosophical discussion on making inference about populations using clusters of models. In this article we provide an overview of model inference in ecological risk assessment, discuss the benefits and trade-offs of increasing model realism, show the...

  6. A Proposal for Testing Local Realism Without Using Assumptions Related to Hidden Variable States

    NASA Technical Reports Server (NTRS)

    Ryff, Luiz Carlos

    1996-01-01

    A feasible experiment is discussed which allows us to prove a Bell's theorem for two particles without using an inequality. The experiment could be used to test local realism against quantum mechanics without the introduction of additional assumptions related to hidden variables states. Only assumptions based on direct experimental observation are needed.

  7. Depressive Realism and Attributional Style: Implications for Individuals at Risk for Depression

    ERIC Educational Resources Information Center

    Moore, Michael T.; Fresco, David M.

    2007-01-01

    Prior research has found that depressed individuals are more realistic in their interpretations of certain events than nondepressed individuals. However, the implications of this finding for the etiology of depressive disorders have never been clarified. The current investigation sought to remedy this situation by exploring realism in the context…

  8. Explanation and Quantification in Educational Research: The Arguments of Critical and Scientific Realism

    ERIC Educational Resources Information Center

    Nash, Roy

    2005-01-01

    The influence of Bhaskar's critical realism has become increasingly evident in the debate on the nature of educational research. This philosophy, dedicated to the overthrow of positivist doctrines, in particular those of empiricism, nominalism, and causation as constant conjunction, is the foundation of contemporary proposals for new perspectives…

  9. Objectivity and Emancipation in Learning Disabilities: Holism from the Perspective of Critical Realism.

    ERIC Educational Resources Information Center

    Warner, Michael M.

    1993-01-01

    This article provides a critique of holism within the learning disabilities field, based on its incipient subjectivism. It examines the issue of objective, scientific study in relation to the works of Richard Iano, Mary Poplin, and Lous Heshusius and recommends consideration of the perspective of critical realism, based on the writing of Roy…

  10. Emotions Bias Perceptions of Realism in Audiovisual Media: Why We May Take Fiction for Real

    ERIC Educational Resources Information Center

    Konijn, Elly A.; Walma van der Molen, Juliette H.; van Nes, Sander

    2009-01-01

    This study investigated whether emotions induced in TV-viewers (either as an emotional state or co-occurring with emotional involvement) would increase viewers' perception of realism in a fake documentary and affect the information value that viewers would attribute to its content. To that end, two experiments were conducted that manipulated (a)…

  11. Absolute configuration of a chiral CHD group via neutron diffraction: confirmation of the absolute stereochemistry of the enzymatic formation of malic acid

    SciTech Connect

    Bau, R.; Brewer, I.; Chiang, M.Y.; Fujita, S.; Hoffman, J.; Watkins, M.I.; Koetzle, T.F.

    1983-09-30

    Neutron diffraction has been used to monitor the absolute stereochemistry of an enzymatic reaction. (-)(2S)malic-3-d acid was prepared by the action of fumarase on fumaric acid in D/sub 2/O. After a large number of cations were screened, it was found that (+)(R)..cap alpha..-phenylethylamine forms the large crystals necessary for a neutron diffraction analysis. The subsequent structure determination showed that (+)(R)..cap alpha..-phenylethylammonium (-)(2S)malate-3-d has an absolute configuration of R at the CHD site. This result confirms the absolute stereochemistry of fumarate-to-malate transformation as catalyzed by the enzyme fumarase.

  12. Alteration of Polyketide Stereochemistry from anti to syn by a Ketoreductase Domain Exchange in a Type I Modular Polyketide Synthase Subunit.

    PubMed

    Eng, Clara H; Yuzawa, Satoshi; Wang, George; Baidoo, Edward E K; Katz, Leonard; Keasling, Jay D

    2016-03-29

    Polyketide natural products have broad applications in medicine. Exploiting the modular nature of polyketide synthases to alter stereospecificity is an attractive strategy for obtaining natural product analogues with altered pharmaceutical properties. We demonstrate that by retaining a dimerization element present in LipPks1+TE, we are able to use a ketoreductase domain exchange to alter α-methyl group stereochemistry with unprecedented retention of activity and simultaneously achieve a novel alteration of polyketide product stereochemistry from anti to syn. The substrate promiscuity of LipPks1+TE further provided a unique opportunity to investigate the substrate dependence of ketoreductase activity in a polyketide synthase module context. PMID:26976746

  13. Positioning positivism, critical realism and social constructionism in the health sciences: a philosophical orientation.

    PubMed

    Cruickshank, Justin

    2012-03-01

    Positioning positivism, critical realism and social constructionism in the health sciences: a philosophical orientation This article starts by considering the differences within the positivist tradition and then it moves on to compare two of the most prominent schools of postpositivism, namely critical realism and social constructionism. Critical realists hold, with positivism, that knowledge should be positively applied, but reject the positivist method for doing this, arguing that causal explanations have to be based not on empirical regularities but on references to unobservable structures. Social constructionists take a different approach to postpositivism and endorse a relativist rejection of truth and hold that the task of research is to foster a scepticism that undermines any positive truth claim made. It is argued that social constructionism is a contradictory position. PMID:22212371

  14. Mapping new theoretical and methodological terrain for knowledge translation: contributions from critical realism and the arts

    PubMed Central

    Kontos, Pia C; Poland, Blake D

    2009-01-01

    Background Clinical practice guidelines have been a popular tool for the improvement of health care through the implementation of evidence from systematic research. Yet, it is increasingly clear that knowledge alone is insufficient to change practice. The social, cultural, and material contexts within which practice occurs may invite or reject innovation, complement or inhibit the activities required for success, and sustain or alter adherence to entrenched practices. However, knowledge translation (KT) models are limited in providing insight about how and why contextual contingencies interact, the causal mechanisms linking structural aspects of context and individual agency, and how these mechanisms influence KT. Another limitation of KT models is the neglect of methods to engage potential adopters of the innovation in critical reflection about aspects of context that influence practice, the relevance and meaning of innovation in the context of practice, and the identification of strategies for bringing about meaningful change. Discussion This paper presents a KT model, the Critical Realism and the Arts Research Utilization Model (CRARUM), that combines critical realism and arts-based methodologies. Critical realism facilitates understanding of clinical settings by providing insight into the interrelationship between its structures and potentials, and individual action. The arts nurture empathy, and can foster reflection on the ways in which contextual factors influence and shape clinical practice, and how they may facilitate or impede change. The combination of critical realism and the arts within the CRARUM model promotes the successful embedding of interventions, and greater impact and sustainability. Conclusion CRARUM has the potential to strengthen the science of implementation research by addressing the complexities of practice settings, and engaging potential adopters to critically reflect on existing and proposed practices and strategies for sustaining

  15. Exploring the relationship between object realism and object-based attention effects.

    PubMed

    Roque, Nelson; Boot, Walter R

    2015-09-01

    Visual attention prioritizes processing of locations in space, and evidence also suggests that the benefits of attention can be shaped by the presence of objects (object-based attention). However, the prevalence of object-based attention effects has been called into question recently by evidence from a large-sampled study employing classic attention paradigms (Pilz et al., 2012). We conducted two experiments to explore factors that might determine when and if object-based attention effects are observed, focusing on the degree to which the concreteness and realism of objects might contribute to these effects. We adapted the classic attention paradigm first reported by Egly, Driver, and Rafal (1994) by replacing abstract bar stimuli in some conditions with objects that were more concrete and familiar to participants: items of silverware. Furthermore, we varied the realism of these items of silverware, presenting either cartoon versions or photo-realistic versions. Contrary to predictions, increased realism did not increase the size of object-based effects. In fact, no clear object-based effects were observed in either experiment, consistent with previous failures to replicate these effects in similar paradigms. While object-based attention may exist, and may have important influences on how we parse the visual world, these and other findings suggest that the two-object paradigm typically relied upon to study object-based effects may not be the best paradigm to investigate these issues. PMID:26256694

  16. Design and Implementation of a Self-Directed Stereochemistry Lesson Using Embedded Virtual Three-Dimensional Images in a Portable Document Format

    ERIC Educational Resources Information Center

    Cody, Jeremy A.; Craig, Paul A.; Loudermilk, Adam D.; Yacci, Paul M.; Frisco, Sarah L.; Milillo, Jennifer R.

    2012-01-01

    A novel stereochemistry lesson was prepared that incorporated both handheld molecular models and embedded virtual three-dimensional (3D) images. The images are fully interactive and eye-catching for the students; methods for preparing 3D molecular images in Adobe Acrobat are included. The lesson was designed and implemented to showcase the 3D…

  17. Geological realism in hydrogeological and geophysical inverse modeling: A review

    NASA Astrophysics Data System (ADS)

    Linde, Niklas; Renard, Philippe; Mukerji, Tapan; Caers, Jef

    2015-12-01

    Scientific curiosity, exploration of georesources and environmental concerns are pushing the geoscientific research community toward subsurface investigations of ever-increasing complexity. This review explores various approaches to formulate and solve inverse problems in ways that effectively integrate geological concepts with geophysical and hydrogeological data. Modern geostatistical simulation algorithms can produce multiple subsurface realizations that are in agreement with conceptual geological models and statistical rock physics can be used to map these realizations into physical properties that are sensed by the geophysical or hydrogeological data. The inverse problem consists of finding one or an ensemble of such subsurface realizations that are in agreement with the data. The most general inversion frameworks are presently often computationally intractable when applied to large-scale problems and it is necessary to better understand the implications of simplifying (1) the conceptual geological model (e.g., using model compression); (2) the physical forward problem (e.g., using proxy models); and (3) the algorithm used to solve the inverse problem (e.g., Markov chain Monte Carlo or local optimization methods) to reach practical and robust solutions given today's computer resources and knowledge. We also highlight the need to not only use geophysical and hydrogeological data for parameter estimation purposes, but also to use them to falsify or corroborate alternative geological scenarios.

  18. Computational plasma physics and supercomputers. Revision 1

    SciTech Connect

    Killeen, J.; McNamara, B.

    1985-01-01

    The Supercomputers of the 80's are introduced. They are 10 to 100 times more powerful than today's machines. The range of physics modeling in the fusion program is outlined. New machine architecture will influence particular models, but parallel processing poses new programming difficulties. Increasing realism in simulations will require better numerics and more elaborate mathematical models.

  19. Three factors that influence the overall quality of the stereoscopic 3D content: image quality, comfort, and realism

    NASA Astrophysics Data System (ADS)

    Vlad, Raluca; Ladret, Patricia; Guérin, Anne

    2013-01-01

    In today's context, where 3D content is more abundant than ever and its acceptance by the public is probably de_nitive, there are many discussions on controlling and improving the 3D quality. But what does this notion represent precisely? How can it be formalized and standardized? How can it be correctly evaluated? A great number of studies have investigated these matters and many interesting approaches have been proposed. Despite this, no universal 3D quality model has been accepted so far that would allow a uniform across studies assessment of the overall quality of 3D content, as it is perceived by the human observers. In this paper, we are making a step forward in the development of a 3D quality model, by presenting the results of an exploratory study in which we started from the premise that the overall 3D perceived quality is a multidimensional concept that can be explained by the physical characteristics of the 3D content. We investigated the spontaneous impressions of the participants while watching varied 3D content, we analyzed the key notions that appeared in their discourse and identi_ed correlations between their judgments and the characteristics of our database. The test proved to be rich in results. Among its conclusions, we consider of highest importance the fact that we could thus determine three di_erent perceptual attributes ( image quality, comfort and realism ( that could constitute a _rst simplistic model for assessing the perceived 3D quality.

  20. Influence of the stereochemistry on the sensory properties of 4-mercapto-2-heptanol and its acetyl-derivatives.

    PubMed

    Nörenberg, Svenja; Reichardt, Bastian; Andelfinger, Verena; Eisenreich, Wolfgang; Engel, Karl-Heinz

    2013-03-01

    4-Mercapto-2-heptanol, previously described in cooked bell pepper, was used to determine the impact of the stereochemistry on the sensory properties of a thiol with a 1,3-oxygen-sulfur functionality. In addition, the acetyl-derivatives 4-acetylthio-2-heptanol, 4-mercapto-2-heptyl acetate and 4-acetylthio-2-heptyl acetate were investigated. The synthesized stereoisomers were separated via capillary gas chromatography (GC) using chiral stationary phases. The GC orders of elution were determined by assigning the absolute configurations via NMR analysis in combination with lipase-catalyzed kinetic resolutions. Odor thresholds and odor properties were determined by means of GC/Olfactometry. The data revealed that the sensory properties of the investigated compounds are not only significantly influenced by the acetylation but also by the configurations of the two asymmetric centers. PMID:23394583

  1. Classroom Enters the Courtroom: Stereochemistry of SN1 and SN2 Reactions in Enantiomer Patent Litigations of the Antidepressant Escitalopram.

    PubMed

    Michman, Elisheva; Agranat, Israel

    2016-01-01

    The role of elementary stereochemistry is illustrated in the patent litigations of the blockbuster antidepressant drug escitalopram oxalate. An undergraduate student of organic chemistry would recognize the stereochemical courses of the intramolecular SN 2 and SN 1 reactions of the single-enantiomer (S)-diol intermediate in the synthesis of the blockbuster antidepressant drug escitalopram oxalate: retention of configuration of the chiral carbon atom under basic conditions and racemization under acidic conditions, respectively. He/she, in searching for a stereoselective ring-closure reaction of the enantiomeric diol, will think of an SN 2 reaction in a basic medium. From these points of view, the process claim in the enantiomer patents of escitalopram is obvious/lacks an inventive step. An organic chemistry examination problem based on this scenario is offered. PMID:26477341

  2. Stereochemistry of 16a-hydroxyfriedelin and 3-Oxo-16-methylfriedel-16-ene established by 2D NMR spectroscopy.

    PubMed

    Duarte, Lucienir Pains; Silva de Miranda, Roqueline Rodrigues; Rodrigues, Salomão Bento Vasconcelos; de Fátima Silva, Grácia Divina; Vieira Filho, Sidney Augusto; Knupp, Vagner Fernandes

    2009-01-01

    Friedelin (1), 3beta-friedelinol (2), 28-hydroxyfriedelin (3), 16alpha-hydroxyfriedelin (4), 30-hydroxyfriedelin (5) and 16alpha,28-dihydroxyfriedelin (6) were isolated through fractionation of the hexane extract obtained from branches of Salacia elliptica. After a week in CDCl(3) solution, 16alpha-hydroxyfriedelin (4) reacted turning into 3-oxo-16-methylfriedel-16-ene (7). This is the first report of a dehydration followed by a Nametkin rearrangement of a pentacyclic triterpene in CDCl(3) solution occurring in the NMR tube. These seven pentacyclic triterpenes was identified through NMR spectroscopy and the stereochemistry of compound 4 and 7 was established by 2D NMR (NOESY) spectroscopy and mass spectrometry (GC-MS). It is also the first time that all the (13)C-NMR and 2D NMR spectral data are reported for compounds 4 and 7. PMID:19214150

  3. It's all about Me: methyl-induced control of coordination stereochemistry by a flexible tridentate N,C,N' ligand.

    PubMed

    Kariuki, Benson M; Platts, James A; Newman, Paul D

    2014-02-21

    A chiral, tridentate, pyridyl-functionalised NHC pro-ligand, S-L(Me)-H[PF₆], has been prepared diastereoselectively via a five step synthesis starting from 1R,3S-diamino-1,2,2-trimethylcyclopentane. The S prefix refers to the stereochemistry of a methyl substituted stereogenic carbon in one of the pyridyl arms which is generated by a stereoselective BH4(-) reduction of an imine precursor. The ligand has been coordinated to Rh(I) and Ir(I) to give trigonal bipyramidal complexes of the type [M(κ(3)-N,C,N'-S-L(Me))(1,5-COD)]PF6 (M = Rh, Ir) as single diastereomers. A combination of spectroscopic and X-ray techniques confirm the stereoselective formation of the thermodynamically preferred endo,endo isomer. Similar reactions with R,S-L(Me)-H[PF₆] gave a mixture of endo,endo-[M(κ(3)-N,C,N'-S-L(Me))(1,5-COD)](+) and exo,exo-[M(κ(3)-N,C,N'-R-L(Me))(1,5-COD)](+). The absolute configuration at the metal is, therefore, solely dictated by the stereochemistry of the single methylpyridyl carbon. The observation of stereoselection extends to the square planar Ni(II) complex [Ni(δ-κ(3)-N,C,N'-S-L(Me))Cl](+) which is isolated as one (δ) of the two possible conformational isomers. DFT studies have been employed to explain the observed stereoselectivity with the configurations observed in the solid state being confirmed as those of lowest energy. PMID:24346145

  4. Does the stereochemistry of methylated cuticular hydrocarbons contribute to mate recognition in the egg parasitoid wasp Ooencyrtus kuvanae?

    PubMed

    Ablard, Kelly; Gries, Regine; Khaskin, Grigori; Schaefer, Paul W; Gries, Gerhard

    2012-10-01

    Close-range sexual communication of the egg parasitoid wasp Ooencyrtus kuvanae (Hymenoptera: Encyrtidae) takes place on host gypsy moth, Lymantria dispar (Lepidoptera: Lymantriidae), egg masses. We tested the hypothesis that mate recognition in O. kuvanae is mediated, in part, by low-volatility cuticular hydrocarbon (CHC) pheromone components. Gas chromatographic and GC-mass spectrometric analyses of body surface extracts of male and female wasps revealed no sex-specific components, but 5-methylheptacosane (5-me-27Hy) and 5,17-dimethylheptacosane (5,17-dime-27Hy) were consistently more abundant in extracts of males. The ratio of 5-me-27Hy and 5,17-dime-27Hy was similar in extracts of males and females, and quantitative differences alone seemed insufficient to impart sex-specific CHC profiles. Therefore, we further hypothesized that the absolute configuration of 5-me-27Hy and 5,17-dime-27Hy contributes to mate recognition or attraction. As the stereoisomers of 5-me-27Hy and 5,17-dime-27Hy cannot currently be separated chromatographically, we could not determine the stereochemistry of the insect-produced components. Instead, we synthesized all stereoisomers and bioassayed synthetic blends in laboratory experiments. Of eight 2-component blends, each blend containing one of the two enantiomers of 5-me-27Hy and one of the four stereoisomers of 5,17-dime-27Hy, the blend of (5S)-methylheptacosane and (5R,17S)-dimethylheptacosane attracted males, whereas the blend of (5R)-methylheptacosane and (5R,17R)-dimethylheptacosane repelled males. Apparent recognition of both pheromone components and pheromone antagonists by males supports the hypothesis that the stereochemistry of 5-me-27Hy and 5,17-dime-27Hy, and possibly other methylated CHCs, may differ between male and female O. kuvanae, and that these differences may serve in mate attraction and recognition. PMID:23007309

  5. Stereochemistry and Mechanistic Insight in the [2(k)+2(i)+2(i)] Annulations of Ketenes and Imines.

    PubMed

    Yang, Zhanhui; He, Wei; Cheng, Baoxiang; Xu, Jiaxi

    2016-06-01

    The stereochemistry and mechanistic insight in the annulations of one ketene molecule with two imine molecules ([2(k)+2(i)+2(i)] annulation) are studied by using six-membered 3,4-dihydroisoquinoline as an imine probe. A concerted hetero-Diels-Alder cycloaddition mechanism is proposed to explain the stereochemical outcomes. In most cases, the zwitterionic 2-aza-1,3-butadiene-type intermediates, generated from ketenes and imines, undergo endo hetero-Diels-Alder cycloaddition with the second imine molecule. For ketenes with electron-donating substituents, (2,4)-cis-(4,5)-cis-[2(k)+2(i)+2(i)] annuladducts formed stereospecifically, while, for ketenes with electron-accepting substituents, (2,4)-cis-(4,5)-trans-[2(k)+2(i)+2(i)] annuladducts are generated stereospecifically. The [2(k)+2(i)+2(i)] annulations of aryloxyketenes and 3,4-dihydroisoquinoline give stereodivergent products due to the occurrence of the stepwise nucleophilic annulation. However, in the [2(k)+2(i)+2(i)] annulations of seven-membered cyclic imine dibenzo[b,f][1,4]oxazepine, the zwitterionic aza-butadiene-type intermediates exclusively undergo exo hetero-Diels-Alder cycloadditions with another molecule of imine to yield (2,4)-trans-(4,5)-trans-[2(k)+2(i)+2(i)] annuladducts stereospecifically, regardless of the ketene substituents. The mechanistic model not only discloses the nature of the [2(k)+2(i)+2(i)] annulations, but also can be used to explain and predict the stereochemistry of the [2(k)+2(i)+2(i)] annuladducts from different ketenes and imines. PMID:27166848

  6. Physics.

    ERIC Educational Resources Information Center

    Bromley, D. Allan

    1980-01-01

    The author presents the argument that the past few years, in terms of new discoveries, insights, and questions raised, have been among the most productive in the history of physics. Selected for discussion are some of the most important new developments in physics research. (Author/SA)

  7. The Acquisition of Stereochemical Knowledge by Algerian Students Intending to Teach Physical Sciences

    ERIC Educational Resources Information Center

    Boukhechem, Mohamed-Salah; Dumon, Alain; Zouikri, Mohamed

    2011-01-01

    In this work we evaluated the level of difficulty found in learning stereochemistry concepts, by students intending to teach physical sciences at the Ecole Normale Superieure (ENS) Kouba (Algeria). A paper and pencil questionnaire was administered to 170 students to evaluate: their familiarity with Newman representations; their ability of linking…

  8. Optimistic bias and pessimistic realism in judgments of contingency with aversive or rewarding outcomes.

    PubMed

    Sonoda, Akihito

    2002-10-01

    A depressive personality influences judgments of contingency. This is called "depressive realism." The present experiment examined whether optimistic traits, as measured by various scales, are correlated with judgments of contingency. The valences of the target stimuli were aversive or rewarding (noise avoidance or gaining points). Analysis indicated that the optimistic subjects (as measured by explanatory style for negative events) tend to overestimate noncontingent events; however, optimism measured by other scales did not show such an effect. The findings are discussed in terms of a self-defensive attributional bias. PMID:12416837

  9. Back- and fore-grounding ontology: exploring the linkages between critical realism, pragmatism, and methodologies in health & rehabilitation sciences.

    PubMed

    DeForge, Ryan; Shaw, Jay

    2012-03-01

    Back- and fore-grounding ontology: exploring the linkages between critical realism, pragmatism, and methodologies in health & rehabilitation sciences As two doctoral candidates in a health and rehabilitation sciences program, we describe in this paper our respective paradigmatic locations along a quite nonlinear ontological-epistemological-axiological-methodological chain. In a turn-taking fashion, we unpack the tenets of critical realism and pragmatism, and then trace the linkages from these paradigmatic locations through to the methodological choices that address a community-based research problem. Beyond serving as an answer to calls for academics in training to demonstrate philosophical-theoretical-methodological integrity and coherence in their scholarship, this paper represents critical realism and its fore-grounding of a deeply stratified ontology in reflexive relation to pragmatism and its back-grounding of ontology. We conclude by considering the merits and challenges of conducting research from within singular versus proliferate paradigmatic perspectives. PMID:22212372

  10. A high-performance liquid chromatography with circular dichroism detector for determination of stereochemistry of 6, 9-oxygen bridge dibenzocyclooctadiene lignans from kadsura coccinea.

    PubMed

    Zhu, Hui; Xu, Liang; Yang, Shi-Lin; Li, He-Ran

    2015-10-01

    The stereochemistry of two 6, 9-oxygen bridge dibenzocyclooctadiene lignans from Kadsura coccinea, are difficult to separate and very unstable. The present study was designed to develop a high-performance liquid chromatography using circular dichroism detection for the analysis of the stereochemistry. A new 6, 9-oxygen bridge dibenzocyclooctadiene lignans named Kadsulignan Q was firstly found with an S-biphenyl configuration. The other compound was identified as Kadsulignan L with an R- biphenyl configuration. In order to obtain kinetic data on their reversible interconversion, the stability was measured at different deuterated solvents such as deuterated methanol, deuterated chloroform and deuterated dimethylsulfoxide. The lignans were more unstable and converted more easily in deuterated methanol than in deuterated chloroform and deuterated dimethylsulfoxide. PMID:26481381

  11. The NMR investigation of alkaloids. IX. /sup 13/C NMR spectra and stereochemistry of convolvine, convolamine, convoline, convolidine, subhirsine and 6-hydroxyhyoscyamine

    SciTech Connect

    Yagudaev, M.R.; Aripova, S.F.

    1986-07-01

    A correlation has been made on the basis of the results of a study of the C 13 NMR spectra, of the CSs of the C 13 carbon nuclei with the structure and stereochemistry of the tropane alkaloids convolvine, convolamine, convoline, convolidine, subhirsine, and 6-hydroxyhyoscyamine. It has been established that the N-CH/sub 3/ group in convolamine and the -OH group in convoline are oriented equatorially, and the N-CH/sub 3/ in hydroxyhyoscyamine axially.

  12. Structure and stereochemistry of the base excision repair glycosylase MutY reveal a mechanism similar to retaining glycosidases.

    PubMed

    Woods, Ryan D; O'Shea, Valerie L; Chu, Aurea; Cao, Sheng; Richards, Jody L; Horvath, Martin P; David, Sheila S

    2016-01-29

    MutY adenine glycosylases prevent DNA mutations by excising adenine from promutagenic 8-oxo-7,8-dihydroguanine (OG):A mismatches. Here, we describe structural features of the MutY active site bound to an azaribose transition state analog which indicate a catalytic role for Tyr126 and approach of the water nucleophile on the same side as the departing adenine base. The idea that Tyr126 participates in catalysis, recently predicted by modeling calculations, is strongly supported by mutagenesis and by seeing close contact between the hydroxyl group of this residue and the azaribose moiety of the transition state analog. NMR analysis of MutY methanolysis products corroborates a mechanism for adenine removal with retention of stereochemistry. Based on these results, we propose a revised mechanism for MutY that involves two nucleophilic displacement steps akin to the mechanisms accepted for 'retaining' O-glycosidases. This new-for-MutY yet familiar mechanism may also be operative in related base excision repair glycosylases and provides a critical framework for analysis of human MutY (MUTYH) variants associated with inherited colorectal cancer. PMID:26673696

  13. Octa(thymidine methanephosphonates) of partially defined stereochemistry: synthesis and effect of chirality at phosphorus on binding to pentadecadeoxyriboadenylic acid.

    PubMed Central

    Lesnikowski, Z J; Jaworska, M; Stec, W J

    1990-01-01

    Block condensation of MePOCI2 or MeP(NEt2)2 with appropriately protected tetra(thymidine methanephosphonates) of predetermined sense of chirality at asymmetric phosphonate centres gave two pairs of diastereomeric mixtures, namely (SpSpSpSpSpSpSp + SpSpSpRpSpSpSp) 5a and (RpRpRpRpRpRpRp + RpRpRpSpRpRpRp) 5b. A comparison of the CD spectra of 5a and 5b with those of octathymidylic acid (7) and a random mixture of diastereomers of octa(thymidine methanephosphonate) (6), and also a comparison of the Tm of complexes formed between 5a, 5b, 6 or 7, and pentadecadeoxyriboadenylic acid (8), indicates that octamer 5b and its complex with its complementary oligonucleotide has a well-ordered structure due to the 'outward' or 'pseudoequatorial' orientation of the methyl group of each internucleotide methanephosphonate function of Rp configuration. Results presented in this report clearly indicate that the stability of hybrids formed between octa(thymidine methanephosphonate) and pentadecadeoxyriboadenylic acid depends on the stereochemistry of each internucleotide methanephosphonate function and strongly suggests that stereoselective synthesis of P-chiral oligonucleotide analogues is an important goal. PMID:2336391

  14. Chiral triazole fungicide difenoconazole: absolute stereochemistry, stereoselective bioactivity, aquatic toxicity, and environmental behavior in vegetables and soil.

    PubMed

    Dong, Fengshou; Li, Jing; Chankvetadze, Bezhan; Cheng, Yongpu; Xu, Jun; Liu, Xingang; Li, Yuanbo; Chen, Xiu; Bertucci, Carlo; Tedesco, Daniele; Zanasi, Riccardo; Zheng, Yongquan

    2013-04-01

    In this study, the systemic assessments of the stereoisomers of triazole fungicide difenoconazole are reported for the first time, including absolute stereochemistry, stereoselective bioactivity toward pathogens (Alternaria sonali, Fulvia fulva, Botrytis cinerea, and Rhizoctonia solani), and toxicity toward aquatic organisms (Scenedesmus obliquus, Daphnia magna, and Danio rerio). Moreover, the stereoselective degradation of difenoconazole in vegetables (cucumber, Cucumis sativus and tomato, Lycopersicon esculentum) under field conditions and in soil under laboratory-controlled conditions (aerobic and anaerobic) was investigated. There were 1.33-24.2-fold and 1.04-6.78-fold differences in bioactivity and toxicity, respectively. Investigations on the stereoselective degradation of difenoconazole in vegetables showed that the highest-toxic and lowest-bioactive (2S,4S)-stereoisomer displays a different enrichment behavior in different plant species. Under aerobic or anaerobic conditions, (2R,4R)- and (2R,4S)-difenoconazole were preferentially degraded in the soil. Moreover, difenoconazole was configurationally stable in the test soil matrices. On the basis of biological activity, ecotoxicity, and environmental behavior, it is likely that the use of pure (2R,4S)-difenoconazole instead of the commercial stereoisomer mix may help to increase the bioactivity and reduce environmental pollution. PMID:23451708

  15. Structure and stereochemistry of the base excision repair glycosylase MutY reveal a mechanism similar to retaining glycosidases

    PubMed Central

    Woods, Ryan D.; O'Shea, Valerie L.; Chu, Aurea; Cao, Sheng; Richards, Jody L.; Horvath, Martin P.; David, Sheila S.

    2016-01-01

    MutY adenine glycosylases prevent DNA mutations by excising adenine from promutagenic 8-oxo-7,8-dihydroguanine (OG):A mismatches. Here, we describe structural features of the MutY active site bound to an azaribose transition state analog which indicate a catalytic role for Tyr126 and approach of the water nucleophile on the same side as the departing adenine base. The idea that Tyr126 participates in catalysis, recently predicted by modeling calculations, is strongly supported by mutagenesis and by seeing close contact between the hydroxyl group of this residue and the azaribose moiety of the transition state analog. NMR analysis of MutY methanolysis products corroborates a mechanism for adenine removal with retention of stereochemistry. Based on these results, we propose a revised mechanism for MutY that involves two nucleophilic displacement steps akin to the mechanisms accepted for ‘retaining’ O-glycosidases. This new-for-MutY yet familiar mechanism may also be operative in related base excision repair glycosylases and provides a critical framework for analysis of human MutY (MUTYH) variants associated with inherited colorectal cancer. PMID:26673696

  16. Stereochemistry of spiro-acetalized [60]fullerenes: how the exo and endo stereoisomers influence organic solar cell performance.

    PubMed

    Mikie, Tsubasa; Saeki, Akinori; Yamazaki, Yu; Ikuma, Naohiko; Kokubo, Ken; Seki, Shu

    2015-04-29

    Exploiting bis-addition products of fullerenes is a rational way to improve the efficiency of bulk heterojunction-type organic photovoltaic cells (OPV); however, this design inherently produces regio- and stereoisomers that may impair the ultimate performance and fabrication reproducibility. Here, we report unprecedented exo and endo stereoisomers of the spiro-acetalized [60]fullerene monoadduct with methyl- or phenyl-substituted 1,3-dioxane (SAF6). Although there is no chiral carbon in either the reagent or the fullerene, equatorial (eq) rather than axial (ax) isomers are selectively produced at an exo-eq:endo-eq ratio of approximately 1:1 and can be easily separated using silica gel column chromatography. Nuclear Overhauser effect measurements identified the conformations of the straight exo isomer and bent endo isomer. We discuss the origin of stereoselectivity, the anomeric effect, intermolecular ordering in the film state, and the performance of poly(3-hexylthiophene):substituted SAF6 OPV devices. Despite their identical optical and electrochemical properties, their solubilities and space-charge limited current mobilities are largely influenced by the stereoisomers, which leads to variation in the OPV efficiency. This study emphasizes the importance of fullerene stereochemistry for understanding the relationship between stereochemical structures and device output. PMID:25856417

  17. Versatile transformations of hydrocarbons in anaerobic bacteria: substrate ranges and regio- and stereo-chemistry of activation reactions†

    PubMed Central

    Jarling, René; Kühner, Simon; Basílio Janke, Eline; Gruner, Andrea; Drozdowska, Marta; Golding, Bernard T.; Rabus, Ralf; Wilkes, Heinz

    2015-01-01

    Anaerobic metabolism of hydrocarbons proceeds either via addition to fumarate or by hydroxylation in various microorganisms, e.g., sulfate-reducing or denitrifying bacteria, which are specialized in utilizing n-alkanes or alkylbenzenes as growth substrates. General pathways for carbon assimilation and energy gain have been elucidated for a limited number of possible substrates. In this work the metabolic activity of 11 bacterial strains during anaerobic growth with crude oil was investigated and compared with the metabolite patterns appearing during anaerobic growth with more than 40 different hydrocarbons supplied as binary mixtures. We show that the range of co-metabolically formed alkyl- and arylalkyl-succinates is much broader in n-alkane than in alkylbenzene utilizers. The structures and stereochemistry of these products are resolved. Furthermore, we demonstrate that anaerobic hydroxylation of alkylbenzenes does not only occur in denitrifiers but also in sulfate reducers. We propose that these processes play a role in detoxification under conditions of solvent stress. The thermophilic sulfate-reducing strain TD3 is shown to produce n-alkylsuccinates, which are suggested not to derive from terminal activation of n-alkanes, but rather to represent intermediates of a metabolic pathway short-cutting fumarate regeneration by reverse action of succinate synthase. The outcomes of this study provide a basis for geochemically tracing such processes in natural habitats and contribute to an improved understanding of microbial activity in hydrocarbon-rich anoxic environments. PMID:26441848

  18. Working with Cultural-Historical Activity Theory and Critical Realism to Investigate and Expand Farmer Learning in Southern Africa

    ERIC Educational Resources Information Center

    Mukute, Mutizwa; Lotz-Sisitka, Heila

    2012-01-01

    This article uses the theoretical and methodological tools of cultural historical activity theory and critical realism to examine three case studies of the introduction and expansion of sustainable agricultural practices in southern Africa. The article addresses relevant issues in the field of agricultural extension, which lacks a theoretical…

  19. Questioning the Value of Realism: Young Adults' Processing of Messages in Alcohol-Related Public Service Announcements and Advertising.

    ERIC Educational Resources Information Center

    Andsager, Julie L.; Austin, Erica Weintraub; Pinkleton, Bruce E.

    2001-01-01

    Finds that: (1) perceived realism and themes that students could identify with are important factors in increasing the salience and persuasiveness of alcohol-related public service announcements (PSAs) among undergraduate students; (2) realistic but logic-based PSAs were not as effective as unrealistic but enjoyable ads; and (3) low production…

  20. Impact of Dysphoria and Self-Consciousness on Perceptions of Social Competence: Test of the Depressive Realism Hypothesis

    ERIC Educational Resources Information Center

    Chau, Phuong M.; Milling, Leonard S.

    2006-01-01

    Depressive realism refers to a cognitive style wherein depressed people sometimes have more accurate perceptions of reality than nondepressed people. The notion of depressives being "sadder yet wiser" was controversial when first presented, and continues to be heavily debated. Self-perception studies provide maximum external validity, but have…

  1. Depressive Realism and Outcome Density Bias in Contingency Judgments: The Effect of the Context and Intertrial Interval

    ERIC Educational Resources Information Center

    Msetfi, Rachel M.; Murphy, Robin A.; Simpson, Jane; Kornbrot, Diana E.

    2005-01-01

    The perception of the effectiveness of instrumental actions is influenced by depressed mood. Depressive realism (DR) is the claim that depressed people are particularly accurate in evaluating instrumentality. In two experiments, the authors tested the DR hypothesis using an action-outcome contingency judgment task. DR effects were a function of…

  2. Realism, Instrumentalism, and Scientific Symbiosis: Psychological Theory as a Search for Truth and the Discovery of Solutions

    ERIC Educational Resources Information Center

    Cacioppo, John T.; Semin, Gun R.; Berntson, Gary G.

    2004-01-01

    Scientific realism holds that scientific theories are approximations of universal truths about reality, whereas scientific instrumentalism posits that scientific theories are intellectual structures that provide adequate predictions of what is observed and useful frameworks for answering questions and solving problems in a given domain. These…

  3. Child and Adult Witnesses: The Effect of Repetition and Invitation-Probes on Free Recall and Metamemory Realism

    ERIC Educational Resources Information Center

    Knutsson, Jens; Allwood, Carl Martin; Johansson, Marcus

    2011-01-01

    Witnesses' event recall and the realism in their evaluation of the correctness of their recall are of great importance in forensic processes. These issues were investigated in the present study by use of calibration methodology. More specifically, we analyzed the effects of two recalls of the same event ("repetition") and of "probes"…

  4. The (old) New Realism: what Holt has to offer for ecological psychology.

    PubMed

    Charles, Eric P

    2009-03-01

    As Ecological Psychology pushes into new areas, success will be made easier by a rediscovery its theoretical history, in particular the "New Realism", lead in part by E. B. Holt. Three New Realists tenants seem particularly relevant: (1) we experience reality, (2) relations are real, and (3) things are what you see when you see those things. Though the two groups differ in terms of their conception of perception, and what can be perceived, their conceptions are related in very insightful ways. Further, the comparison reemphasizes the extent of unique empirical claims ecological psychologists make, and grounds those claims within a larger framework for psychology as a whole. This makes obvious the need for further work on the mathematics of invariants, the physiological mechanisms of information extraction, and the behaviors of perception. PMID:18758875

  5. John Anderson's development of (situational) realism and its bearing on psychology today.

    PubMed

    Hibberd, Fiona J

    2009-10-01

    In 1927, the Scottish philosopher John Anderson arrived in Australia to take up the chair of Philosophy at the University of Sydney. By the late 1930s, the "macrostructure" of his realist system was in place. It includes a theory of process and a substantial metaphysics, one that opposes positivism, linguistic philosophy and all forms of idealism. However, beyond Australia it remains largely unknown, despite its bearing on a number of current issues in psychology and the social sciences generally. This article outlines Anderson's transition from Hegelian idealism to realism, describes aspects of his ontology and epistemology, compares some of Anderson's ideas with Dewey's pragmatism and explains their relevance to present-day psychology. PMID:20027696

  6. Critical realism: distinguishing the psychological subjectivity of the analyst from epistemological subjectivism.

    PubMed

    Hanly, C; Hanly, M A

    2001-01-01

    To clarify the concepts of critical realism, subjectivity, and subjectivism, distinctions are drawn among ontological subjectivism, moral subjectivity, psychological subjectivity, and epistemological subjectivism. Psychological subjectivity, including the ongoing affective life of the analyst, is an essential aspect of the analyst's response to the patient, and may either facilitate or distort an adequate observation of transference and countertransference dynamics and of the psychic reality of the patient. Subjectivism in current psychoanalytic literature involves an argument that there is an "irreducible" subjectivity in the analyst, who is bound to see things from an incorrigibly personal point of view, such that there is no substantial subject-object differentiation between analyst and patient. Issues of authoritarianism in the analyst, or of pathological certainty, should not be confused with the issues of epistemological objectivism. The concept of critical realism or scientific objectivism includes the essential idea that there is no pure knowledge, no complete knowledge, that often evidence is insufficient for knowledge of some aspect of nature, and that care must be to taken understand what is sufficient knowledge in a given area, in this case clinical psychoanalysis. The question is raised whether "projective identification" makes the sorting out of "what comes from whom" impossible. It is argued that when free association is sufficiently facilitated, when there are enough corrections of the distortions wrought by transference and countertransference, when defenses are analyzed, and when sufficient subject-object differentiation is recovered, the analyst can get to know enough of the patient's psychic reality for the therapeutic and scientific purposes of psychoanalysis. PMID:11508375

  7. Predictive model for epoxide hydrolase-generated stereochemistry in the biosynthesis of nine-membered enediyne antitumor antibiotics.

    PubMed

    Horsman, Geoffrey P; Lechner, Anna; Ohnishi, Yasuo; Moore, Bradley S; Shen, Ben

    2013-08-01

    Nine-membered enediyne antitumor antibiotics C-1027, neocarzinostatin (NCS), and kedarcidin (KED) possess enediyne cores to which activity-modulating peripheral moieties are attached via (R)- or (S)-vicinal diols. We have previously shown that this stereochemical difference arises from hydrolysis of epoxide precursors by epoxide hydrolases (EHs) with different regioselectivities. The inverting EHs, such as SgcF, hydrolyze an (S)-epoxide substrate to yield an (R)-diol in C-1027 biosynthesis, whereas the retaining EHs, such as NcsF2 and KedF, hydrolyze an (S)-epoxide substrate to yield an (S)-diol in NCS and KED biosynthesis. We now report the characterization of a series of EH mutants and provide a predictive model for EH regioselectivity in the biosynthesis of the nine-membered enediyne antitumor antibiotics. A W236Y mutation in SgcF increased the retaining activity toward (S)-styrene oxide by 3-fold, and a W236Y/Q237M double mutation in SgcF, mimicking NcsF2 and KedF, resulted in a 20-fold increase in the retaining activity. To test the predictive utility of these mutations, two putative enediyne biosynthesis-associated EHs were identified by genome mining and confirmed as inverting enzymes, SpoF from Salinospora tropica CNB-440 and SgrF (SGR_625) from Streptomyces griseus IFO 13350. Finally, phylogenetic analysis of EHs revealed a familial classification according to inverting versus retaining activity. Taken together, these results provide a predictive model for vicinal diol stereochemistry in enediyne biosynthesis and set the stage for further elucidating the origins of EH regioselectivity. PMID:23844627

  8. A predictive model for epoxide hydrolase-generated stereochemistry in the biosynthesis of 9-membered enediyne antitumor antibiotics

    PubMed Central

    Horsman, Geoffrey P.; Lechner, Anna; Ohnishi, Yasuo; Moore, Bradley S.; Shen, Ben

    2013-01-01

    Nine-membered enediyne antitumor antibiotics C-1027, neocarzinostatin (NCS), and kedarcidin (KED) possess enediyne cores to which activity-modulating peripheral moieties are attached via (R)- or (S)-vicinal diols. We have previously shown that this stereochemical difference arises from hydrolysis of epoxide precursors by epoxide hydrolases (EHs) with different regioselectivities – the “inverting” EH, such as SgcF, hydrolyzes an (S)-epoxide substrate to yield an (R)-diol in C-1027 biosynthesis, while the “retaining” EHs, such as NcsF2 and KedF, hydrolyze an (S)-epoxide substrate to yield an (S)-diol in NCS and KED biosynthesis. We now report the characterization of a series of EH mutants and provide a predictive model for EH regioselectivity in the biosynthesis of the 9-membered enediyne antitumor antibiotics. A W236Y mutation in SgcF increased the retaining activity towards (S)-styrene oxide 3-fold, and a W236Y/Q237M double mutation in SgcF, mimicking NcsF2 and KedF, resulted in a 20-fold increase in the retaining activity. To test the predictive utility of these mutations, two putative enediyne biosynthesis-associated EHs were identified by genome mining and confirmed as inverting enzymes – SpoF from Salinospora tropica CNB-440 and SgrF (SGR_625) from Streptomyces griseus IFO 13350. Finally, phylogenetic analysis of EHs revealed a familial classification according to inverting versus retaining activity. Taken together, these results provide a predictive model for the vicinal diol stereochemistry in enediyne biosynthesis and set the stage for further elucidating the origins of EH regioselectivity. PMID:23844627

  9. Assignment of the Stereochemistry and Anomeric Configuration of Sugars within Oligosaccharides Via Overlapping Disaccharide Ladders Using MSn

    NASA Astrophysics Data System (ADS)

    Konda, Chiharu; Londry, Frank A.; Bendiak, Brad; Xia, Yu

    2014-08-01

    A systematic approach is described that can pinpoint the stereo-structures (sugar identity, anomeric configuration, and location) of individual sugar units within linear oligosaccharides. Using a highly modified mass spectrometer, dissociation of linear oligosaccharides in the gas phase was optimized along multiple-stage tandem dissociation pathways (MSn, n = 4 or 5). The instrument was a hybrid triple quadrupole/linear ion trap mass spectrometer capable of high-efficiency bidirectional ion transfer between quadrupole arrays. Different types of collision-induced dissociation (CID), either on-resonance ion trap or beam-type CID could be utilized at any given stage of dissociation, enabling either glycosidic bond cleavages or cross-ring cleavages to be maximized when wanted. The approach first involves optimizing the isolation of disaccharide units as an ordered set of overlapping substructures via glycosidic bond cleavages during early stages of MSn, with explicit intent to minimize cross-ring cleavages. Subsequently, cross-ring cleavages were optimized for individual disaccharides to yield key diagnostic product ions ( m/ z 221). Finally, fingerprint patterns that establish stereochemistry and anomeric configuration were obtained from the diagnostic ions via CID. Model linear oligosaccharides were derivatized at the reducing end, allowing overlapping ladders of disaccharides to be isolated from MSn. High confidence stereo-structural determination was achieved by matching MSn CID of the diagnostic ions to synthetic standards via a spectral matching algorithm. Using this MSn ( n = 4 or 5) approach, the stereo-structures, anomeric configurations, and locations of three individual sugar units within two pentasaccharides were successfully determined.

  10. Carboxylation mechanism and stereochemistry of crotonyl-CoA carboxylase/reductase, a carboxylating enoyl-thioester reductase

    PubMed Central

    Erb, Tobias J.; Brecht, Volker; Fuchs, Georg; Müller, Michael; Alber, Birgit E.

    2009-01-01

    Chemo- and stereoselective reductions are important reactions in chemistry and biology, and reductases from biological sources are increasingly applied in organic synthesis. In contrast, carboxylases are used only sporadically. We recently described crotonyl-CoA carboxylase/reductase, which catalyzes the reduction of (E)-crotonyl-CoA to butyryl-CoA but also the reductive carboxylation of (E)-crotonyl-CoA to ethylmalonyl-CoA. In this study, the complete stereochemical course of both reactions was investigated in detail. The pro-(4R) hydrogen of NADPH is transferred in both reactions to the re face of the C3 position of crotonyl-CoA. In the course of the carboxylation reaction, carbon dioxide is incorporated in anti fashion at the C2 atom of crotonyl-CoA. For the reduction reaction that yields butyryl-CoA, a solvent proton is added in anti fashion instead of the CO2. Amino acid sequence analysis showed that crotonyl-CoA carboxylase/reductase is a member of the medium-chain dehydrogenase/reductase superfamily and shares the same phylogenetic origin. The stereospecificity of the hydride transfer from NAD(P)H within this superfamily is highly conserved, although the substrates and reduction reactions catalyzed by its individual representatives differ quite considerably. Our findings led to a reassessment of the stereospecificity of enoyl(-thioester) reductases and related enzymes with respect to their amino acid sequence, revealing a general pattern of stereospecificity that allows the prediction of the stereochemistry of the hydride transfer for enoyl reductases of unknown specificity. Further considerations on the reaction mechanism indicated that crotonyl-CoA carboxylase/reductase may have evolved from enoyl-CoA reductases. This may be useful for protein engineering of enoyl reductases and their application in biocatalysis. PMID:19458256

  11. Biosynthesis of monoterpenes. Stereochemistry of the enzymatic cyclizations of geranyl pyrophosphate to (+)-alpha-pinene and (-)-beta-pinene

    SciTech Connect

    Croteau, R.; Satterwhite, D.M.; Wheeler, C.J.; Felton, N.M.

    1989-02-05

    The conversion of geranyl pyrophosphate to (+)-alpha-pinene and to (-)-beta-pinene is considered to proceed by the initial isomerization of the substrate to (-)-(3R)- and to (+)-(3S)-linalyl pyrophosphate, respectively, and the subsequent cyclization of the anti, endo-conformer of these bound intermediates by mirror-image sequences which should result in the net retention of configuration at C1 of the geranyl precursor. Incubation of (1R)-(2-14C,1-3H)- and (1S)-(2-14C,1-3H)geranyl pyrophosphate with (+)-pinene cyclase and with (-)-pinene cyclase from common sage (Salvia officinalis) gave labeled (+)-alpha- and (-)-beta-pinene of unchanged 3H/14C ratio in all cases, and the (+)- and (-)-olefins were stereoselectively converted to (+)- and (-)-borneol, respectively, which were oxidized to the corresponding (+)- and (-)-isomers of camphor, again without change in isotope ratio. The location of the tritium was determined in each case by stereoselective, base-catalyzed exchange of the exo-alpha-hydrogens of these derived ketones. The results indicated that the configuration at C1 of the substrate was retained in the enzymatic transformations to the (+)- and (-)-pinenes, which is entirely consistent with the syn-isomerization of geranyl pyrophosphate to linalyl pyrophosphate, transoid to cisoid rotation, and anti, endo-cyclization of the latter. The absolute stereochemical elements of the antipodal reaction sequences were confirmed by the selective enzymatic conversions of (3R)- and (3S)-1Z-(1-3H)linalyl pyrophosphate to (+)-alpha-pinene and (-)-beta-pinene, respectively, and by the location of the tritium in the derived camphors as before. The summation of the results fully defines the overall stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to the antipodal pinenes.

  12. Hydrophobic Tail Length, Degree of Fluorination and Headgroup Stereochemistry are Determinants of the Biocompatibility of (Fluorinated) Carbohydrate Surfactants

    PubMed Central

    Li, Xueshu; Turánek, Jaroslav; Knötigová, Pavlína; Kudláčková, Hana; Mašek, Josef; Parkin, Sean; Rankin, Stephen E; Knutson, Barbara L; Lehmler, Hans-Joachim

    2009-01-01

    A series of hydrocarbon and fluorocarbon carbohydrate surfactants with different headgroups (i.e., gluco-, galacto- and maltopyranoside) and (fluorinated) alkyl tails (i.e., C7 and C14 to C19) was synthesized to investigate trends in their cytotoxicity and haemolytic activity, and how surfactant-lipid interactions of selected surfactants contribute to these two measures of biocompatibility. All surfactants displayed low cytotoxicity (EC50 = 25 to > 250 μM) and low haemolytic activity (EC50 = 0.2 to > 3.3 mM), with headgroup structure, tail length and degree of fluorination being important structural determinants for both endpoints. The EC50 values of hydrocarbon and fluorocarbon glucopyranoside surfactants displayed a “cut-off” effect (i.e., a maximum with respect to the chain length). According to steady-state fluorescence anisotropy studies, short chain (C7) surfactants partitioned less readily into model membranes, which explains their low cytotoxicity and haemolytic activity. Interestingly, galactopyranosides were less toxic compared to glucopyranosides with the same hydrophobic tail. Although both surfactant types only differ in the stereochemistry of the 4-OH group, hexadecyl gluco- and galactopyranoside surfactants had similar apparent membrane partition coefficients, but differed in their overall effect on the phase behaviour of DPPC model membranes, as assessed using steady-state fluorescence anisotropy studies. These observations suggest that highly selective surfactant-lipid interactions may be responsible for the differential cytotoxicity and, possible, haemolytic activity of hydrocarbon and fluorocarbon carbohydrate surfactants intended for a variety of pharmaceutical and biomedical applications. PMID:19481909

  13. Balancing practicality and hydrologic realism: Insights from applications of a parsimonious model of unsaturated-zone preferential flow

    NASA Astrophysics Data System (ADS)

    Mirus, B. B.; Perkins, K. S.; Nimmo, J. R.

    2011-12-01

    Simple assessments are often needed to inform local land-management decisions. Preferential flow, a crucial process in many land-management decisions, presents a considerable challenge to the parameterization and evaluation of commonly used hydrologic models. Traditional unsaturated flow theory (i.e., Richards equation) does not accurately represent the physics of preferential flow and often underestimates the arrival time and magnitude of fluxes when applied in situations where preferential flow is important. Another shortcoming of traditional modeling approaches is the considerable data required to characterize the distribution of subsurface hydraulic properties. A source-responsive model has been developed based on film-flow theory to provide more realistic approximations of unsaturated-zone preferential flow when limited data and site characterization are available. The term source-responsive is used to describe the sensitivity of preferential flow to changing conditions at the source of water input, which are typically better quantified than hydraulic properties. We present applications of this parsimonious model for sites in Idaho and Nevada with heterogeneous vadose zones (40 m and 1000 m in thickness, respectively) where radionuclide contamination poses a threat to groundwater quality. Despite differences in input data for each application, results from both applications provide reasonable flux estimates, which are useful for characterizing worst-case scenarios for advective transport of conservative contaminants. We contrast the results for the two applications in terms of the data employed for each and discuss the advantages of the model parameterization, which relies heavily on the quantity and timing of net infiltration. There are several opportunities for improvements in model performance, but these involve greater model complexity with a corresponding increase in free parameters and data requirements. The tradeoff between hydrologic realism and

  14. Correlations among experimental and theoretical NMR data to determine the absolute stereochemistry of darcyribeirine, a pentacyclic indole alkaloid isolated from Rauvolfia grandiflora

    NASA Astrophysics Data System (ADS)

    Cancelieri, Náuvia Maria; Ferreira, Thiago Resende; Vieira, Ivo José Curcino; Braz-Filho, Raimundo; Piló-Veloso, Dorila; Alcântara, Antônio Flávio de Carvalho

    2015-10-01

    Darcyribeirine (1) is a pentacyclic indole alkaloid isolated from Rauvolfia grandiflora. Stereochemistry of 1 was previously proposed based on 1D (coupling constant data) and 2D (NOESY correlations) NMR techniques, having been established a configuration 3R, 15S, and 20R (isomer 1a). Stereoisomers of 1 (i.e., 1a-1h) can be grouped into four sets of enantiomers. Carbon chemical shifts and hydrogen coupling constants were calculated using BLYP/6-31G* theory level for the eight isomers of 1. Calculated NMR data of 1a-1h were correlated with the corresponding experimental data of 1. The best correlations between theoretical and experimental carbon chemical shift data were obtained for the set of enantiomers 1e/1f to structures in the gaseous phase and considering solvent effects (using PCM and explicit models). Similar results were obtained when the same procedure was performed to correlations between theoretical and experimental coupling constant data. Finally, optical rotation calculations indicate 1e as its absolute stereochemistry. Orbital population analysis indicates that the hydrogen bonding between N-H of 1e and DMSO is due to contributions of its frontier unoccupied molecular orbitals, mainly LUMO+1, LUMO+2, and LUMO+3.

  15. Toward a limited realism for psychiatric nosology based on the coherence theory of truth.

    PubMed

    Kendler, K S

    2015-04-01

    A fundamental debate in the philosophy of science is whether our central concepts are true or only useful instruments to help predict and manipulate the world. The first position is termed 'realism' and the second 'instrumentalism'. Strong support for the instrumentalist position comes from the 'pessimistic induction' (PI) argument. Given that many key scientific concepts once considered true (e.g., humors, ether, epicycles, phlogiston) are now considered false, how, the argument goes, can we assert that our current concepts are true? The PI argument applies strongly to psychiatric diagnoses. Given our long history of abandoned diagnoses, arguments that we have finally 'gotten it right' and developed definitive psychiatric categories that correspond to observer-independent reality are difficult to defend. For our current diagnostic categories, we should settle for a less ambitious vision of truth. For this, the coherence theory, which postulates that something is true when it fits well with the other things we confidently know about the world, can serve us well. Using the coherence theory, a diagnosis is real to the extent that it is well integrated into our accumulating scientific data base. Furthermore, the coherence theory establishes a framework for us to evaluate our diagnostic categories and can provide a set of criteria, closely related to our concept of validators, for deciding when they are getting better. Finally, we need be much less skeptical about the truth status of the aggregate concept of psychiatric illness than we are regarding the specific categories in our current nosology. PMID:25181016

  16. Reality Without Realism: On the Ontological and Epistemological Architecture of Quantum Mechanics

    NASA Astrophysics Data System (ADS)

    Plotnitsky, Arkady; Khrennikov, Andrei

    2015-10-01

    First, this article considers the nature of quantum reality (the reality responsible for quantum phenomena) and the concept of realism (our ability to represent this reality) in quantum theory, in conjunction with the roles of locality, causality, and probability and statistics there. Second, it offers two interpretations of quantum mechanics, developed by the authors of this article, the second of which is also a different (from quantum mechanics) theory of quantum phenomena. Both of these interpretations are statistical. The first interpretation, by A. Plotnitsky, "the statistical Copenhagen interpretation," is nonrealist, insofar as the description or even conception of the nature of quantum objects and processes is precluded. The second, by A. Khrennikov, is ultimately realist, because it assumes that the quantum-mechanical level of reality is underlain by a deeper level of reality, described, in a realist fashion, by a model, based in the pre-quantum classical statistical field theory, the predictions of which reproduce those of quantum mechanics. Moreover, because the continuous fields considered in this model are transformed into discrete clicks of detectors, experimental outcomes in this model depend on the context of measurement in accordance with N. Bohr's interpretation and the statistical Copenhagen interpretation, which coincides with N. Bohr's interpretation in this regard.

  17. Feeling and Time: The Phenomenology of Mood Disorders, Depressive Realism, and Existential Psychotherapy

    PubMed Central

    Ghaemi, S. Nassir

    2007-01-01

    Phenomenological research suggests that pure manic and depressive states are less common than mixtures of the two and that the two poles of mood are characterized by opposite ways of experiencing time. In mania, the subjective experience of time is sped up and in depression it is slowed down, perhaps reflecting differences in circadian pathophysiology. The two classic mood states are also quite different in their effect on subjective awareness: manic patients lack insight into their excitation, while depressed patients are quite insightful into their unhappiness. Consequently, insight plays a major role in overdiagnosis of unipolar depression and misdiagnosis of bipolar disorder. The phenomenology of depression also is relevant to types of psychotherapies used to treat it. The depressive realism (DR) model, in contrast to the cognitive distortion model, appears to better apply to many persons with mild to moderate depressive syndromes. I suggest that existential psychotherapy is the necessary corollary of the DR model in those cases. Further, some depressive morbidities may in fact prove, after phenomenological study, to involve other mental states instead of depression. The chronic subsyndromal depression that is often the long-term consequence of treated bipolar disorder may in fact represent existential despair, rather than depression proper, again suggesting intervention with existential psychotherapeutic methods. PMID:17122410

  18. Pattern cladistics and the 'realism-antirealism debate' in the philosophy of biology.

    PubMed

    Vergara-Silva, Francisco

    2009-06-01

    Despite the amount of work that has been produced on the subject over the years, the 'transformation of cladistics' is still a misunderstood episode in the history of comparative biology. Here, I analyze two outstanding, highly contrasting historiographic accounts on the matter, under the perspective of an influential dichotomy in the philosophy of science: the opposition between Scientific Realism and Empiricism. Placing special emphasis on the notion of 'causal grounding' of morphological characters (sensu Olivier Rieppel) in modern developmental biology's (mechanistic) theories, I arrive at the conclusion that a 'new transformation of cladistics' is philosophically plausible. This 'reformed' understanding of 'pattern cladistics' entails retaining the interpretation of cladograms as 'schemes of synapomorphies', but in association to construing cladogram nodes as 'developmental-genetic taxic homologies', instead of 'standard Darwinian ancestors'. The reinterpretation of pattern cladistics presented here additionally proposes to take Bas Van Fraassen's 'constructive empiricism' as a philosophical stance that could properly support such analysis of developmental-genetic data for systematic purposes. The latter suggestion is justified through a reappraisal of previous ideas developed by prominent pattern cladists (mainly, Colin Patterson), which concerned a scientifically efficient 'observable/non-observable distinction' linked to the conceptual pair 'ontogeny and phylogeny'. Finally, I argue that a robust articulation of Antirealist alternatives in systematics may provide a rational basis for its disciplinary separation from evolutionary biology, as well as for a critical reconsideration of the proper role of certain Scientific Realist positions, currently popular in comparative biology. PMID:19507040

  19. New realism in north Korean propaganda: The death of Pak Chong-ch`ol. Final report

    SciTech Connect

    Shaw, W.

    1987-04-01

    North Korea`s Voice of National Salvation (VNS) broadcasts to South Korea in January and February gave considerable attention to the 13 January 1987 death under police torture of Seoul National University student Pak Chong-ch`ol. VNS commentary emphasized the routine nature of police torture in South Korea and sharply criticized the South Korean Government for blocking attendance at memorial services on 7 February and 3 March. Many VNS comments on the Pak case closely paralleled reactions of the South Korean press and parliamentary opposition, demonstrating close North Korean attention to opinion trends in the South. In a new mood of realism, P`yongyang also used the Pak case to urge South Korean radical students to drop their `avant-gardism`, including excessively leftist slogans and violent tactics that alienate the general populace. P` yongyang clearly wants students to take advantage of issues that have wide public appeal and to broaden resistance to the Chon Tu-hwan Government to include social groups beyond the student population. In P`yongyang`s view, such issues include the Pak case and the signature campaign for constitutional revision in early 1986. If South Korea`s radical students take P`yonyyang`s advice, and if the Republic of Korea Government fails to curb and punish abuses like the Pak killing, this shift in tactics could have significant influence during the coming spring demonstration season.

  20. [Painting realism and medicine: the two surgical clinics of Thomas Eakins].

    PubMed

    Cabello, Felipe

    2015-06-01

    Realism is a painting style that began with Millet and Courbet in politically convulsed France in the middle of the nineteenth century. In the second half of that century, the pragmatic and democratic tradition of the United States fostered the careers of many realist painters, including that of Thomas Eakins. Eakins, trained in France, developed his career completely associated with Philadelphia at a time when this city was in the vanguard of American emerging industry, culture and medicine. Eakins "The clinic of Dr. Gross" and the "The clinic of Dr. Agnew" are icons of these developments and symbolize a perfect union of art and medicine. Both paintings permit the viewer to appreciate the artist's mastery, originality and Americanism while simultaneously tracking the progress of surgery as evidenced by the introduction of asepsis, anesthesia and nursing. Eakins mastery is revealed by its use of some European Old Masters approaches to portray medical professionals undertaking their daily duties in their work environments with critical and unadorned vision. This combination of vision and skills led Eakins to create a highly original yet analytical art. Unfortunately, his representations were far ahead of his time and resulted in under appreciation of his paintings and a censorious reaction to their content. His contemporaries rejection of Eakins work negatively affected his career as a painter, as a teacher and even his private life. This judgment was overturned in subsequent years and by the twentieth century Eakins was recognized as an American master without parallel. PMID:26230562

  1. Beyond idealism and realism: Canadian NGO/government relations during the negotiation of the FCTC.

    PubMed

    Lencucha, Raphael; Labonté, Ronald; Rouse, Michael J

    2010-04-01

    The Framework Convention on Tobacco Control (FCTC) marks a unique point in the history of global health governance. This convention produced the first legally binding treaty under the auspices of the World Health Organization. Another first was the extent to which non-governmental organizations (NGOs) participated in the negotiation process. This article explores the relationship between one group of NGOs and their respective government during the negotiation of the FCTC. Documentary analyses and 18 individual in-depth interviews were conducted with both government and NGO representatives. In contrast to the polar perspectives of idealism (NGOs as unique and autonomous) and realism (NGOs as funded arms of the government), our findings suggest that neither opposition nor conformity on the part of the NGOs characterize the relationship between the NGOs and government. While specific to the case under study (the FCTC), our findings nonetheless indicate the need for a nuanced view of the relationship between governments and NGOs, at least during the process of multilateral health policy negotiations. PMID:20200527

  2. Contextualism adds realism: nursing students' perceptions of and performance in numeracy skills tests.

    PubMed

    Ramjan, Lucie M

    2011-11-01

    This project investigated nursing students' perceptions of and performance in a de-contextualised diagnostic maths paper (i.e. questions only) and a contextualised diagnostic maths paper (i.e. visual pictures along with questions). Sampling was purposive, the criteria being that participants would be from the population of student nurses (n=700) in their second year, of a three-year Bachelor of Nursing course, undertaking a Unit 'Medical-Surgical Nursing 1' (MSN1) at one of four campuses across the University of Western Sydney (UWS), NSW, Australia. The numerical test scores for both papers were analysed with the assistance of SPSS software and a Professional Development Officer. The survey data were analysed manually and thematically by the researcher. There was a substantive improvement in scores from Test 1 (de-contextualised) to Test 2 (contextualised). It is uncertain whether the change occurred because Test 2 is a genuinely better presentation than Test 1 or just a practice effect. Nevertheless, the contextualised paper was preferred by the majority of students (80%). Students preferred the visual images and revealed that it led to a "deeper learning" of numeracy skills, reduced stress and anxiety levels and simulated 'the real life' clinical setting, thus adding "an element of realism" to the situation. PMID:21126812

  3. REALISM WITHOUT TRUTH: A REVIEW OF GIERE'S SCIENCE WITHOUT LAWS AND SCIENTIFIC PERSPECTIVISM

    PubMed Central

    Hackenberg, Timothy D

    2009-01-01

    An increasingly popular view among philosophers of science is that of science as action—as the collective activity of scientists working in socially-coordinated communities. Scientists are seen not as dispassionate pursuers of Truth, but as active participants in a social enterprise, and science is viewed on a continuum with other human activities. When taken to an extreme, the science-as-social-process view can be taken to imply that science is no different from any other human activity, and therefore can make no privileged claims about its knowledge of the world. Such extreme views are normally contrasted with equally extreme views of classical science, as uncovering Universal Truth. In Science Without Laws and Scientific Perspectivism, Giere outlines an approach to understanding science that finds a middle ground between these extremes. He acknowledges that science occurs in a social and historical context, and that scientific models are constructions designed and created to serve human ends. At the same time, however, scientific models correspond to parts of the world in ways that can legitimately be termed objective. Giere's position, perspectival realism, shares important common ground with Skinner's writings on science, some of which are explored in this review. Perhaps most fundamentally, Giere shares with Skinner the view that science itself is amenable to scientific inquiry: scientific principles can and should be brought to bear on the process of science. The two approaches offer different but complementary perspectives on the nature of science, both of which are needed in a comprehensive understanding of science. PMID:19949495

  4. A framework to assess the realism of model structures using hydrological signatures

    NASA Astrophysics Data System (ADS)

    Euser, T.; Winsemius, H. C.; Hrachowitz, M.; Fenicia, F.; Uhlenbrook, S.; Savenije, H. H. G.

    2013-05-01

    The use of flexible hydrological model structures for hypothesis testing requires an objective and diagnostic method to identify whether a rainfall-runoff model structure is suitable for a certain catchment. To determine if a model structure is realistic, i.e. if it captures the relevant runoff processes, both performance and consistency are important. We define performance as the ability of a model structure to mimic a specific part of the hydrological behaviour in a specific catchment. This can be assessed based on evaluation criteria, such as the goodness of fit of specific hydrological signatures obtained from hydrological data. Consistency is defined as the ability of a model structure to adequately reproduce several hydrological signatures simultaneously while using the same set of parameter values. In this paper we describe and demonstrate a new evaluation Framework for Assessing the Realism of Model structures (FARM). The evaluation framework tests for both performance and consistency using a principal component analysis on a range of evaluation criteria, all emphasizing different hydrological behaviour. The utility of this evaluation framework is demonstrated in a case study of two small headwater catchments (Maimai, New Zealand, and Wollefsbach, Luxembourg). Eight different hydrological signatures and eleven model structures have been used for this study. The results suggest that some model structures may reveal the same degree of performance for selected evaluation criteria while showing differences in consistency. The results also show that some model structures have a higher performance and consistency than others. The principal component analysis in combination with several hydrological signatures is shown to be useful to visualise the performance and consistency of a model structure for the study catchments. With this framework performance and consistency are evaluated to identify which model structure suits a catchment better compared to other model

  5. A framework to assess the realism of model structures using hydrological signatures

    NASA Astrophysics Data System (ADS)

    Euser, T.; Winsemius, H. C.; Hrachowitz, M.; Fenicia, F.; Uhlenbrook, S.; Savenije, H. H. G.

    2012-11-01

    The use of flexible hydrological model structures for hypothesis testing requires an objective and diagnostic method to identify whether a rainfall-runoff model structure is suitable for a certain catchment. To determine if a model structure is realistic, i.e. if it captures the relevant runoff processes, both performance and consistency are important. Performance describes the ability of a model structure to mimic a specific part of the hydrological behaviour in a specific catchment. This can be assessed based on evaluation criteria, such as the goodness of fit of specific hydrological signatures obtained from hydrological data. Consistency describes the ability of a model structure to adequately reproduce several hydrological signatures simultaneously, while using the same set of parameter values. In this paper we describe and demonstrate a new evaluation Framework for Assessing the Realism of Model structures (FARM). The evaluation framework tests for both performance and consistency using a principal component analysis on a range of evaluation criteria, all emphasizing different hydrological behaviour. The utility of this evaluation framework is demonstrated in a case study of two small headwater catchments (Maimai, New Zealand and Wollefsbach, Luxembourg). Eight different hydrological signatures and eleven model structures have been used for this study. The results suggest that some model structures may reveal the same degree of performance for selected evaluation criteria, while showing differences in consistency. The results also show that some model structures have a higher performance and consistency than others. The principal component analysis in combination with several hydrological signatures is shown to be useful to visualize the performance and consistency of a model structure for the study catchments. With this framework performance and consistency can be tested to identify which model structures suit a catchment better than other model structures.

  6. Role of the side chain stereochemistry in the α-glucosidase inhibitory activity of kotalanol, a potent natural α-glucosidase inhibitor. Part 2.

    PubMed

    Tanabe, Genzoh; Matsuoka, Kanjyun; Yoshinaga, Masahiro; Xie, Weijia; Tsutsui, Nozomi; A Amer, Mumen F; Nakamura, Shinya; Nakanishi, Isao; Wu, Xiaoming; Yoshikawa, Masayuki; Muraoka, Osamu

    2012-11-01

    To examine the role of the side chain of kotalanol (2), a potent natural α-glucosidase inhibitor isolated from Salacia reticulata, on inhibitory activity, four diastereomers (11a-11d) with reversed configuration (S) at the C-4' position in the side chain were synthesized and evaluated. Two of the four (11b and 11d) significantly lost their inhibitory activity against both maltase and sucrase, while the other two (11a and 11c) sustained the inhibitory activity to a considerable extent, showing distinct activity in response to the change of stereochemistry of the hydroxyls at the 5'and 6' positions. Different activities were rationalized with reference to in silico docking studies on these inhibitors with hNtMGAM. Against isomaltase, all four analogs showed potent inhibitory activity as well as 2, and 11b and 11d exhibited enzyme selectivity. PMID:23031648

  7. Differentiation of the Stereochemistry and Anomeric Configuration for 1-3 Linked Disaccharides Via Tandem Mass Spectrometry and 18O-labeling

    NASA Astrophysics Data System (ADS)

    Konda, Chiharu; Bendiak, Brad; Xia, Yu

    2012-02-01

    Collision-induced dissociation (CID) of deprotonated hexose-containing disaccharides ( m/z 341) with 1-2, 1-4, and 1-6 linkages yields product ions at m/z 221, which have been identified as glycosyl-glycolaldehyde anions. From disaccharides with these linkages, CID of m/z 221 ions produces distinct fragmentation patterns that enable the stereochemistries and anomeric configurations of the non-reducing sugar units to be determined. However, only trace quantities of m/z 221 ions can be generated for 1-3 linkages in Paul or linear ion traps, preventing further CID analysis. Here we demonstrate that high intensities of m/z 221 ions can be built up in the linear ion trap (Q3) from beam-type CID of a series of 1-3 linked disaccharides conducted on a triple quadrupole/linear ion trap mass spectrometer. 18O-labeling at the carbonyl position of the reducing sugar allowed mass-discrimination of the "sidedness" of dissociation events to either side of the glycosidic linkage. Under relatively low energy beam-type CID and ion trap CID, an m/z 223 product ion containing 18O predominated. It was a structural isomer that fragmented quite differently than the glycosyl-glycolaldehydes and did not provide structural information about the non-reducing sugar. Under higher collision energy beam-type CID conditions, the formation of m/z 221 ions, which have the glycosyl-glycolaldehyde structures, were favored. Characteristic fragmentation patterns were observed for each m/z 221 ion from higher energy beam-type CID of 1-3 linked disaccharides and the stereochemistry of the non-reducing sugar, together with the anomeric configuration, were successfully identified both with and without 18O-labeling of the reducing sugar carbonyl group.

  8. Evaluating the realism of climate model hydrological cycle via comparisons with the observed moisture mixing ratio distribution (Invited)

    NASA Astrophysics Data System (ADS)

    Kursinski, E. R.; Kursinski, A. L.

    2010-12-01

    The water vapor feedback is the largest feedback in climate models and is tightly coupled to other fundamental and difficult to predict climate variables such as clouds, precipitation, lapse rates and dynamics. It is therefore critical that climate models accurately represent the hydrological cycle and the processes controlling the moisture distribution. There has long been concern that vertical coupling of water vapor in models may be too strong and causing the water vapor feedback to be overestimated in models. Evaluating models requires tight and unique observational constraints that leave the models little wiggle room, in order to ensure that if models get the right answer, they get it for the right reasons. Along these lines, an approach to evaluating models is to compare the observed and model-generated distributions of water vapor mixing ratios at radiatively important levels in the troposphere. The extremes of the moisture distribution are particularly important to evaluating model realism. Earth’s ability to cool itself is linked directly to and depends critically on the dryness of the free troposphere in the subtropics which have been referred to as the radiator fins of the climate system. At the other end of the distribution is air at or near saturation, rising from below, and providing source of moisture in the free troposphere. It is the source of much of the clouds and most of the precipitation and is tied closely to and is partially the driver of atmospheric circulation. One can infer that models that produce reasonable circulation and precipitation amounts and patterns while missing the upper end of the water vapor distribution must contain erroneous physics and parameterizations that somehow compensate for the systematic errors in the moisture distribution. We also note that observations must quantify the properties of supersaturated air, which is now recognized to occur commonly at altitudes above the freezing level, for comparison with models

  9. Is This Real Life? Is This Just Fantasy?: Realism and Representations in Learning with Technology

    NASA Astrophysics Data System (ADS)

    Sauter, Megan Patrice

    Students often engage in hands-on activities during science learning; however, financial and practical constraints often limit the availability of these activities. Recent advances in technology have led to increases in the use of simulations and remote labs, which attempt to recreate hands-on science learning via computer. Remote labs and simulations are interesting from a cognitive perspective because they allow for different relations between representations and their referents. Remote labs are unique in that they provide a yoked representation, meaning that the representation of the lab on the computer screen is actually linked to that which it represents: a real scientific device. Simulations merely represent the lab and are not connected to any real scientific devices. However, the type of visual representations used in the lab may modify the effects of the lab technology. The purpose of this dissertation is to examine the relation between representation and technology and its effects of students' psychological experiences using online science labs. Undergraduates participated in two studies that investigated the relation between technology and representation. In the first study, participants performed either a remote lab or a simulation incorporating one of two visual representations, either a static image or a video of the equipment. Although participants in both lab conditions learned, participants in the remote lab condition had more authentic experiences. However, effects were moderated by the realism of the visual representation. Participants who saw a video were more invested and felt the experience was more authentic. In a second study, participants performed a remote lab and either saw the same video as in the first study, an animation, or the video and an animation. Most participants had an authentic experience because both representations evoked strong feelings of presence. However, participants who saw the video were more likely to believe the

  10. Realism and Perspectivism: a Reevaluation of Rival Theories of Spatial Vision.

    NASA Astrophysics Data System (ADS)

    Thro, E. Broydrick

    1990-01-01

    My study reevaluates two theories of human space perception, a trigonometric surveying theory I call perspectivism and a "scene recognition" theory I call realism. Realists believe that retinal image geometry can supply no unambiguous information about an object's size and distance--and that, as a result, viewers can locate objects in space only by making discretionary interpretations based on familiar experience of object types. Perspectivists, in contrast, think viewers can disambiguate object sizes/distances on the basis of retinal image information alone. More specifically, they believe the eye responds to perspective image geometry with an automatic trigonometric calculation that not only fixes the directions and shapes, but also roughly fixes the sizes and distances of scene elements in space. Today this surveyor theory has been largely superceded by the realist approach, because most vision scientists believe retinal image geometry is ambiguous about the scale of space. However, I show that there is a considerable body of neglected evidence, both past and present, tending to call this scale ambiguity claim into question. I maintain that this evidence against scale ambiguity could hardly be more important, if one considers its subversive implications for the scene recognition theory that is not only today's reigning approach to spatial vision, but also the foundation for computer scientists' efforts to create space-perceiving robots. If viewers were deemed to be capable of automatic surveying calculations, the discretionary scene recognition theory would lose its main justification. Clearly, it would be difficult for realists to maintain that we viewers rely on scene recognition for space perception in spite of our ability to survey. And in reality, as I show, the surveyor theory does a much better job of describing the everyday space we viewers actually see--a space featuring stable, unambiguous relationships among scene elements, and a single horizon and

  11. Emergence of realism: Enhanced visual artistry and high accuracy of visual numerosity representation after left prefrontal damage.

    PubMed

    Takahata, Keisuke; Saito, Fumie; Muramatsu, Taro; Yamada, Makiko; Shirahase, Joichiro; Tabuchi, Hajime; Suhara, Tetsuya; Mimura, Masaru; Kato, Motoichiro

    2014-05-01

    Over the last two decades, evidence of enhancement of drawing and painting skills due to focal prefrontal damage has accumulated. It is of special interest that most artworks created by such patients were highly realistic ones, but the mechanism underlying this phenomenon remains to be understood. Our hypothesis is that enhanced tendency of realism was associated with accuracy of visual numerosity representation, which has been shown to be mediated predominantly by right parietal functions. Here, we report a case of left prefrontal stroke, where the patient showed enhancement of artistic skills of realistic painting after the onset of brain damage. We investigated cognitive, functional and esthetic characteristics of the patient׳s visual artistry and visual numerosity representation. Neuropsychological tests revealed impaired executive function after the stroke. Despite that, the patient׳s visual artistry related to realism was rather promoted across the onset of brain damage as demonstrated by blind evaluation of the paintings by professional art reviewers. On visual numerical cognition tasks, the patient showed higher performance in comparison with age-matched healthy controls. These results paralleled increased perfusion in the right parietal cortex including the precuneus and intraparietal sulcus. Our data provide new insight into mechanisms underlying change in artistic style due to focal prefrontal lesion. PMID:24631259

  12. Beyond Gisin's Theorem and its Applications: Violation of Local Realism by Two-Party Einstein-Podolsky-Rosen Steering.

    PubMed

    Chen, Jing-Ling; Su, Hong-Yi; Xu, Zhen-Peng; Wu, Yu-Chun; Wu, Chunfeng; Ye, Xiang-Jun; Żukowski, Marek; Kwek, L C

    2015-01-01

    We demonstrate here that for a given mixed multi-qubit state if there are at least two observers for whom mutual Einstein-Podolsky-Rosen steering is possible, i.e. each observer is able to steer the other qubits into two different pure states by spontaneous collapses due to von Neumann type measurements on his/her qubit, then nonexistence of local realistic models is fully equivalent to quantum entanglement (this is not so without this condition). This result leads to an enhanced version of Gisin's theorem (originally: all pure entangled states violate local realism). Local realism is violated by all mixed states with the above steering property. The new class of states allows one e.g. to perform three party secret sharing with just pairs of entangled qubits, instead of three qubit entanglements (which are currently available with low fidelity). This significantly increases the feasibility of having high performance versions of such protocols. Finally, we discuss some possible applications. PMID:26108704

  13. Critical realism: a practical ontology to explain the complexities of smoking and tobacco control in different resource settings

    PubMed Central

    Oladele, Dunsi; Clark, Alexander M.; Richter, Solina; Laing, Lory

    2013-01-01

    Background This paper presents critical realism (CR) as an innovative system for research in tobacco prevention and control. CR argues that underlying mechanisms are considered and explored to ensure effective implementation of any program/policy or intervention. Any intervention or program/policy that is transposed from one country to another or one setting to another is complex. Methods The research was undertaken and analyzed through a critical ethnography lens using CR as a philosophical underpinning. The study relied upon the following components: original fieldwork in Nigeria including participant observation of smokers, in-depth interviews and focus groups with smokers, and in-depth interviews with health professionals working in the area of tobacco control in Nigeria. Results Findings from this small ethnographic study in Nigeria, suggest that Critical Realism holds promise for addressing underlying mechanism that links complex influences on smoking. Conclusion This paper argues that understanding the underlying mechanisms associated with smoking in different societies will enable a platform for effective implementation of tobacco control policies that work in various settings. PMID:23561029

  14. Can Virtual Reality Increase the Realism of Role Plays Used to Teach College Women Sexual Coercion and Rape-Resistance Skills?

    ERIC Educational Resources Information Center

    Jouriles, Ernest N.; McDonald, Renee; Kullowatz, Antje; Rosenfield, David; Gomez, Gabriella S.; Cuevas, Anthony

    2009-01-01

    The present study evaluated whether virtual reality (VR) can enhance the realism of role plays designed to help college women resist sexual attacks. Sixty-two female undergraduate students were randomly assigned to either the Role Play (RP) or Virtual Role Play (VRP) conditions, which were differentiated only by the use of VR technology in the VRP…

  15. A Study for Visual Realism of Designed Pictures on Computer Screens by Investigation and Brain-Wave Analyses.

    PubMed

    Wang, Lan-Ting; Lee, Kun-Chou

    2016-08-01

    In this article, the visual realism of designed pictures on computer screens is studied by investigation and brain-wave analyses. The practical electroencephalogram (EEG) measurement is always time-varying and fluctuating so that conventional statistical techniques are not adequate for analyses. This study proposes a new scheme based on "fingerprinting" to analyze the EEG. Fingerprinting is a technique of probabilistic pattern recognition used in electrical engineering, very like the identification of human fingerprinting in a criminal investigation. The goal of this study was to assess whether subjective preference for pictures could be manifested physiologically by EEG fingerprinting analyses. The most important advantage of the fingerprinting technique is that it does not require accurate measurement. Instead, it uses probabilistic classification. Participants' preference for pictures can be assessed using fingerprinting analyses of physiological EEG measurements. PMID:27324166

  16. Effects of realism on extended violent and nonviolent video game play on aggressive thoughts, feelings, and physiological arousal.

    PubMed

    Barlett, Christopher P; Rodeheffer, Christopher

    2009-01-01

    Previous research has shown that playing violent video game exposure can increase aggressive thoughts, aggressive feelings, and physiological arousal. This study compared the effects that playing a realistic violent, unrealistic violent, or nonviolent video game for 45 min has on such variables. For the purpose of this study, realism was defined as the probability of seeing an event in real life. Participants (N=74; 39 male, 35 female) played either a realistic violent, unrealistic violent, or nonviolent video game for 45 min. Aggressive thoughts and aggressive feelings were measured four times (every 15 min), whereas arousal was measured continuously. The results showed that, though playing any violent game stimulated aggressive thoughts, playing a more realistic violent game stimulated significantly more aggressive feelings and arousal over the course of play. PMID:19280624

  17. Effects of stereochemistry, saturation, and hydrocarbon chain length on the ability of synthetic constrained azacyclic sphingolipids to trigger nutrient transporter down-regulation, vacuolation, and cell death.

    PubMed

    Perryman, Michael S; Tessier, Jérémie; Wiher, Timothy; O'Donoghue, Heather; McCracken, Alison N; Kim, Seong M; Nguyen, Dean G; Simitian, Grigor S; Viana, Matheus; Rafelski, Susanne; Edinger, Aimee L; Hanessian, Stephen

    2016-09-15

    Constrained analogs containing a 2-hydroxymethylpyrrolidine core of the natural sphingolipids sphingosine, sphinganine, N,N-dimethylsphingosine and N-acetyl variants of sphingosine and sphinganine (C2-ceramide and dihydro-C2-ceramide) were synthesized and evaluated for their ability to down-regulate nutrient transporter proteins and trigger cytoplasmic vacuolation in mammalian cells. In cancer cells, the disruptions in intracellular trafficking produced by these sphingolipids lead to cancer cell death by starvation. Structure activity studies were conducted by varying the length of the hydrocarbon chain, the degree of unsaturation and the presence or absence of an aryl moiety on the appended chains, and stereochemistry at two stereogenic centers. In general, cytotoxicity was positively correlated with nutrient transporter down-regulation and vacuolation. This study was intended to identify structural and functional features in lead compounds that best contribute to potency, and to develop chemical biology tools that could be used to isolate the different protein targets responsible for nutrient transporter loss and cytoplasmic vacuolation. A molecule that produces maximal vacuolation and transporter loss is expected to have the maximal anti-cancer activity and would be a lead compound. PMID:27475534

  18. Analysis of HSD3B7 knockout mice reveals that a 3α-hydroxyl stereochemistry is required for bile acid function

    PubMed Central

    Shea, Heidi C.; Head, Daphne D.; Setchell, Kenneth D. R.; Russell, David W.

    2007-01-01

    Primary bile acids are synthesized from cholesterol in the liver and thereafter are secreted into the bile and small intestine. Gut flora modify primary bile acids to produce secondary bile acids leading to a chemically diverse bile acid pool that is circulated between the small intestine and liver. A majority of primary and secondary bile acids in higher vertebrates have a 3α-hydroxyl group. Here, we characterize a line of knockout mice that cannot epimerize the 3β-hydroxyl group of cholesterol and as a consequence synthesize a bile acid pool in which 3β-hydroxylated bile acids predominate. This alteration causes death in 90% of newborn mice and decreases the absorption of dietary cholesterol in surviving adults. Negative feedback regulation of bile acid synthesis mediated by the farnesoid X receptor (FXR) is disrupted in the mutant mice. We conclude that the correct stereochemistry of a single hydroxyl group at carbon 3 in bile acids is required to maintain their physiologic and regulatory functions in mammals. PMID:17601774

  19. Conformational flexibility and absolute stereochemistry of (3R)-3-hydroxy-4-aryl-β-lactams investigated by chiroptical properties and TD-DFT calculations.

    PubMed

    Tedesco, Daniele; Zanasi, Riccardo; Guerrini, Andrea; Bertucci, Carlo

    2012-09-01

    The effect of conformational flexibility on the chiroptical properties of a series of synthetic (3R)-3-hydroxy-4-aryl-β-lactams of known stereochemistry (1-6) was investigated by means of electronic circular dichroism (ECD) measurements and time-dependent density functional theory (TD-DFT) calculations. The application of the β-lactam sector rules allowed a correct stereochemical characterization of these compounds, with the exception of a thienyl-substituted derivative (cis-). TD-DFT calculations yielded accurate predictions of experimental ECD spectra and [α](D) values, allowing us to assign the correct absolute configuration to all the investigated compounds. A detailed analysis of the β-lactam ring equilibrium geometry on optimized conformers identified regular patterns for the arrangement of atoms around the amide chromophore, confirming the validity of the β-lactam sector rules. However, relevant variations in theoretical chiroptical properties were found for compounds bearing a heterocyclic substituent at C4 or a phenyl substituent at C3, whose conformers deviate from these regular geometric patterns. This behavior explains the failure of the β-lactam sector rules in cis-. This study showed the importance of conformational flexibility for the determination of chiroptical properties and highlighted the strengths and weaknesses of the different methods for the stereochemical characterization of chiral molecules in solution. PMID:22544665

  20. Dynamic NMR and Quantum-Chemical Study of the Stereochemistry and Stability of the Chiral MoO2(acac)2 Complex in Solution.

    PubMed

    Conte, Marco; Hippler, Michael

    2016-09-01

    The stereochemistry and dynamics of MoO2(acac)2 in benzene, chloroform, and toluene were investigated by variable temperature (1)H NMR, density functional theory (SOGGA11-X, B3LYP), and ab initio (MP2) methods. In solution, an equilibrium between two chiral enantiomers with C2 symmetry was identified, Λ-cis-MoO2(acac)2 and Δ-cis-MoO2(acac)2. The two enantiomers are connected via achiral cis transition states that switch the enantiomeric conformations via a Ray-Dutt, Bailar, and a newly described racemization twisting mechanism. All three mechanisms have similar calculated activation energies. Activation parameters Ea, ΔH(‡), and ΔS(‡) were experimentally determined for the exchange process, with a small, negative ΔS(‡), and a positive ΔH(‡) of 68.1 kJ mol(-1) in benzene, 54.9 kJ mol(-1) in chloroform, and 60.6 kJ mol(-1) in toluene, in reasonable general agreement with the calculations. Trans configurations of MoO2(acac)2 are very much higher in energy than cis and are not relevant in the temperature range experimentally studied, 243-340 K. The enantiomers interconvert within seconds near room temperature and much faster at elevated temperatures. Racemization will thus prevent the use of enantiomerically pure MoO2(acac)2 for chiral catalysis under practical conditions. PMID:27510306

  1. Methyl iodide oxidative addition to [Rh(acac)(CO)(PPh3)]: an experimental and theoretical study of the stereochemistry of the products and the reaction mechanism.

    PubMed

    Conradie, Marrigje M; Conradie, Jeanet

    2011-08-28

    Density functional theory was used to investigate the oxidative addition and subsequent carbonyl insertion and deinsertion steps of the reaction of methyl iodide to a rhodium(I) acetylacetonato complex of the formula [Rh(acac)(CO)(PPh(3))] (Hacac = acetylacetone). This process has been studied experimentally for many rhodium β-diketonato complexes, but, to the best of our knowledge, this is the first systematic computational study of the complete reaction sequence. Experimental (1)H techniques complement the theoretical results on the stereochemistry of the reaction intermediates and products. (1)H NMR also revealed the existence of a second rhodium(III)-acyl product, which has not been previously observed in this reaction. The calculated Gibbs free energy of activation of the oxidative addition reaction is 71 kJ mol(-1), which is in agreement with the experimental value of 82(1) kJ mol(-1). The DFT-calculated oxidative addition corresponds to an associative S(N)2 nucleophilic attack by the rhodium metal centre on the methyl iodide, which is in agreement with calculated and experimental (in brackets) activation parameters of the reaction, 27 (38.8) kJ mol(-1) for ΔH((≠)) and -147 (-146) J K(-1) mol(-1) for ΔS((≠)). PMID:21761056

  2. Chiral Cyclobutane β-Amino Acid-Based Amphiphiles: Influence of Cis/Trans Stereochemistry on Condensed Phase and Monolayer Structure.

    PubMed

    Sorrenti, Alessandro; Illa, Ona; Ortuño, Rosa M; Pons, Ramon

    2016-07-12

    New diastereomeric nonionic amphiphiles, cis- and trans-1, based on an optically pure cyclobutane β-amino ester moiety have been investigated to gain insight into the influence exerted by cis/trans stereochemistry and stereochemical constraints on the physicochemical behavior, molecular organization, and morphology of their Langmuir monolayers and dry solid states. All these features are relevant to the rational design of functional materials. trans-1 showed a higher thermal stability than cis-1. For the latter, a higher fluidity of its monolayers was observed when compared with the films formed by trans-1 whose BAM images revealed the formation of condensed phase domains with a dendritic shape, which are chiral, and all of them feature the same chiral sign. Although the formation of LC phase domains was not observed by BAM for cis-1, compact dendritic crystals floating on a fluid subphase were observed beyond the collapse, which are attributable to multilayered 3D structures. These differences can be explained by the formation of hydrogen bonds between the amide groups of consecutive molecules allowing the formation of extended chains for trans-1 giving ordered arrangements. However, for cis-1, this alignment coexists with another one that allows the simultaneous formation of two hydrogen bonds between the amide and the ester groups of adjacent molecules. In addition, the propensity to form intramolecular hydrogen bonds must be considered to justify the formation of different patterns of hydrogen bonding and, consequently, the formation of less ordered phases. Those characteristics are congruent also with the results obtained from SAXS-WAXS experiments which suggest a more bent configuration for cis-1 than for trans-1. PMID:27327214

  3. Trajectory studies of SN2 nucleophilic substitution. III. Dynamical stereochemistry and energy transfer pathways for the Cl - +CH3Cl association and direct substitution reactions

    NASA Astrophysics Data System (ADS)

    Hase, William L.; Cho, Young June

    1993-06-01

    Classical trajectory calculations are performed to determine differences in the microscopic dynamics for two fundamental processes for the Cla-+CH3Clb→ClaCH3+Clb- reactive system: Cla--CH3Clb complex formation and directly attaining the [Cla-CH3-Clb]- central barrier without first forming the complex. This latter process becomes important when the C-Clb stretch mode is excited in the CH3Clb reactant. The total cross section for complex formation and directly attaining the central barrier increases as nC-Clb is increased. The value for the Cla-—C-Clb angle θ as the reactants interact, the dynamical stereochemistry, is found to be a very important property for distinguishing between the mechanisms for the two fundamental processes. Directly attaining the central barrier requires oriented reactants with θ≊π, while orientation suppresses complex formation. Substantial reactant orientation only occurs for CH3Clb rotational temperatures less than 300 K. The complex is formed by a T→R energy transfer process which involves coupling between the reactant orbital angular momentum and CH3Clb rotational angular momentum. Complex formation does not involve energy transfer to the CH3Clb vibrational modes, which is consistent with an earlier finding that the CH3Clb intramolecular modes are inactive during decomposition of the Cla--CH3Clb complex. Orientation of CH3Clb enhances coupling between the Cla-+CH3Clb radial motion and the C-Clb stretch mode. This coupling leads to the above direct substitution process and extensive deactivation of the excited C-Clb stretch during direct unreactive collisions. Considerably less deactivation results from Cla--CH3Clb complex formation followed by dissociation to the reactants. Rotationally exciting CH3Clb eliminates orientation and, thus, suppresses deactivation of the C-Clb stretch.

  4. Stereochemistry of LinB-catalyzed biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-pentabromocyclododecanol.

    PubMed

    Heeb, Norbert V; Zindel, Daniel; Graf, Heidi; Azara, Valeria; Schweizer, W Bernd; Geueke, Birgit; Kohler, Hans-Peter E; Lienemann, Peter

    2013-02-01

    The haloalkane dehalogenase LinB from Sphingobium indicum B90A converts β-hexachlorocyclohexane (β-HCH), the most persistent HCH stereoisomer, to mono- and dihydroxylated metabolites. Recently, we reported that LinB also transforms α-, β- and γ-hexabromocyclododecanes (HBCDs), which are structurally related to HCHs. Here, we show that LinB catalyzes the hydroxylation of δ-HBCD to two pentabromocyclododecanols (PBCDOHs) and two tetrabromocyclododecadiols (TBCDDOHs). The stereochemistry of this enzymatic transformation was deduced from XRD crystal structure data of the substrate δ-HBCD and α(2)-PBCDOH, one of the biotransformation products. Five stereocenters of δ-HBCD are unchanged but the one at C6 is converted to an alcohol with inversion from S- to R-configuration in a nucleophilic, S(N)2-like substitution reaction. Only α(2)-PBCDOH with the 1R,2R,5S,6R,9R,10S-configuration is obtained but not its enantiomer. With only two of the 64 PBCDOHs formed, these transformations indeed are regio- and stereoselective. A conformational analysis revealed that the triple-turn motive, which is predominant in δ-HBCD and in several other HBCD stereoisomers, is also found in the product. This shows that LinB preferentially converted reactive bromine atoms but not those in the conserved triple-turn motive. The widespread contamination with HCHs triggered the bacterial evolution of dehalogenases which acquired the ability to convert these pollutants and their metabolites. We here demonstrate that LinB of S. indicum also transforms HBCDs regio- and stereoselectively following a similar mechanism. PMID:23177717

  5. MMORPG escapism predicts decreased well-being: examination of gaming time, game realism beliefs, and online social support for offline problems.

    PubMed

    Kaczmarek, Lukasz D; Drążkowski, Dariusz

    2014-05-01

    Massively multiplayer online role-playing game (MMORPG) escapists are individuals who indulge in the MMORPG environment to avoid real world problems. Though a relationship between escapism and deteriorated well-being has been established, little is known about particular pathways that mediate this relationship. In the current study, we examined this topic by testing an integrative model of MMORPG escapism, which includes game realism beliefs, gaming time, offline social support, and online social support for offline problems. MMORPG players (N=1,056) completed measures of escapist motivation, game realism beliefs, social support, well-being, and reported gaming time. The tested structural equation model had a good fit to the data. We found that individuals with escapist motivation endorsed stronger game realism beliefs and spent more time playing MMORPGs, which, in turn, increased online support but decreased offline social support. Well-being was favorably affected by both online and offline social support, although offline social support had a stronger effect. The higher availability of online social support for offline problems did not compensate for the lower availability of offline support among MMORPG escapists. Understanding the psychological factors related to depletion of social resources in MMORPG players can help optimize MMORPGs as leisure activities. PMID:24605951

  6. Total Synthesis of the GRP78-Downregulatory Macrolide (+)-Prunustatin A, the Immunosuppressant (+)-SW-163A, and a JBIR-04 Diastereoisomer That Confirms JBIR-04 Has Nonidentical Stereochemistry to (+)-Prunustatin A.

    PubMed

    Manaviazar, Soraya; Nockemann, Peter; Hale, Karl J

    2016-06-17

    A unified total synthesis of the GRP78-downregulator (+)-prunustatin A and the immunosuppressant (+)-SW-163A based upon [1 + 1 + 1 + 1]-fragment condensation and macrolactonization between O(4) and C(5) is herein described. Sharpless asymmetric dihydroxylation was used to set the C(2) stereocenter present in both targets. In like fashion, coupling of the (+)-prunustatin A macrolide amine with benzoic acid furnished a JBIR-04 diastereoisomer whose NMR spectra did not match those of JBIR-04, thus confirming that it has different stereochemistry than (+)-prunustatin A. PMID:27232270

  7. Shock treatment: using immersive digital realism to restage and re-examine milgram's 'obedience to authority' research.

    PubMed

    Haslam, S Alexander; Reicher, Stephen D; Millard, Kathryn

    2015-01-01

    Attempts to revisit Milgram's 'Obedience to Authority' (OtA) paradigm present serious ethical challenges. In recent years new paradigms have been developed to circumvent these challenges but none involve using Milgram's own procedures and asking naïve participants to deliver the maximum level of shock. This was achieved in the present research by using Immersive Digital Realism (IDR) to revisit the OtA paradigm. IDR is a dramatic method that involves a director collaborating with professional actors to develop characters, the strategic withholding of contextual information, and immersion in a real-world environment. 14 actors took part in an IDR study in which they were assigned to conditions that restaged Milgrams's New Baseline ('Coronary') condition and four other variants. Post-experimental interviews also assessed participants' identification with Experimenter and Learner. Participants' behaviour closely resembled that observed in Milgram's original research. In particular, this was evidenced by (a) all being willing to administer shocks greater than 150 volts, (b) near-universal refusal to continue after being told by the Experimenter that "you have no other choice, you must continue" (Milgram's fourth prod and the one most resembling an order), and (c) a strong correlation between the maximum level of shock that participants administered and the mean maximum shock delivered in the corresponding variant in Milgram's own research. Consistent with an engaged follower account, relative identification with the Experimenter (vs. the Learner) was also a good predictor of the maximum shock that participants administered. PMID:25730318

  8. Testing the realism of model structures to identify karst system processes using water quality and quantity signatures

    NASA Astrophysics Data System (ADS)

    Hartmann, A.; Wagener, T.; Rimmer, A.; Lange, J.; Brielmann, H.; Weiler, M.

    2013-06-01

    Many hydrological systems exhibit complex subsurface flow and storage behavior. Runoff observations often only provide insufficient information for unique process identification. Quantitative modeling of water and solute fluxes presents a potentially more powerful avenue to explore whether hypotheses about system functioning can be rejected or conditionally accepted. In this study we developed and tested four hydrological model structures, based on different hypotheses about subsurface flow and storage behavior, to identify the functioning of a large Mediterranean karst system. Using eight different system signatures, i.e., indicators of particular hydrodynamic and hydrochemical characteristics of the karst system, we applied a novel model evaluation strategy to identify the best conceptual model representation of the karst system within our set of possible system representations. Our approach to test model realism consists of three stages: (1) evaluation of model performance with respect to system signatures using automatic calibration, (2) evaluation of parameter identifiability using Sobol's sensitivity analysis, and (3) evaluation of model plausibility by combining the results of stages (1) and (2). These evaluation stages eliminated three out of four model structures and lead to a unique hypothesis about the functioning of the studied karst system. We used the estimated parameter values to further quantify subsurface processes. The chosen model is able to simultaneously provide high performances for eight system signatures with realistic parameter values. Our approach demonstrates the benefits of interpreting different tracers in a hydrologically meaningful way during model evaluation and identification.

  9. On Physical Properties of Tetraether Lipid Membranes: Effects of Cyclopentane Rings

    PubMed Central

    Chong, Parkson Lee-Gau; Ayesa, Umme; Prakash Daswani, Varsha; Hur, Ellah Chay

    2012-01-01

    This paper reviews the recent findings related to the physical properties of tetraether lipid membranes, with special attention to the effects of the number, position, and configuration of cyclopentane rings on membrane properties. We discuss the findings obtained from liposomes and monolayers, composed of naturally occurring archaeal tetraether lipids and synthetic tetraethers as well as the results from computer simulations. It appears that the number, position, and stereochemistry of cyclopentane rings in the dibiphytanyl chains of tetraether lipids have significant influence on packing tightness, lipid conformation, membrane thickness and organization, and headgroup hydration/orientation. PMID:23028246

  10. On the contributions of astroparticle physics to cosmology

    NASA Astrophysics Data System (ADS)

    Falkenburg, Brigitte

    2014-05-01

    Studying astroparticle physics sheds new light on scientific explanation and on the ways in which cosmology is empirically underdetermined or not. Astroparticle physics extends the empirical domain of cosmology from purely astronomical data to "multi-messenger astrophysics", i.e., measurements of all kinds of cosmic rays including very high energetic gamma rays, neutrinos, and charged particles. My paper investigates the ways in which these measurements contribute to cosmology and compares them with philosophical views about scientific explanation, the relation between theory and data, and scientific realism. The "standard models" of cosmology and particle physics lack of unified foundations. Both are "piecemeal physics" in Cartwright's sense, but contrary to her metaphysics of a "dappled world" the work in both fields of research aims at unification. Cosmology proceeds "top-down", from models to data and from large scale to small-scale structures of the universe. Astroparticle physics proceeds "bottom-up", from data taking to models and from subatomic particles to large-scale structures of the universe. In order to reconstruct the causal stories of cosmic rays and the nature of their sources, several pragmatic unifying strategies are employed. Standard views about scientific explanation and scientific realism do not cope with these "bottom-up" strategies and the way in which they contribute to cosmology. In addition it has to be noted that the shift to "multi-messenger astrophysics" transforms the relation between cosmological theory and astrophysical data in a mutually holistic way.

  11. Physics of the universe

    NASA Astrophysics Data System (ADS)

    Sachs, Mendel

    ch. 1. Physics of the universe. Introduction. Is Newton's theory an explanation of gravity? The expanding universe. The oscillating universe cosmology. The theory of general relativity. The role of space and time. Geometry and matter. Generalization of Einstein's field equations. A unified field theory -- ch. 2. A language of cosmology: the mathematical basis of general relativity. Introduction. Einstein's tensor formulation. The Riemann curvature tensor. The geodesic equation. The vacuum equation. The crucial tests of general relativity. The logic of the spacetime language -- ch. 3. A unified field theory in general relativity: extension from the tensor to the quaternion language. Introduction. Factorization of Einstein's tensor field equations. The Riemann curvature tensor in quaternion form. The quaternion metrical field equations. A symmetric tensor-antisymmetric tensor representation of general relativity - gravity and electromagnetism. The Einstein field equations from the symmetric tensor part. The Maxwell field equations from the antisymmetric tensor part. Conclusions -- ch. 4. An oscillating, spiral universe cosmology. introduction. Dynamics of the expansion and contraction of the universe. Dynamics of the oscillating universe cosmology. Derivation of the Hubble law as an approximation. The spiral structure of the universe. Concluding remarks -- ch. 5. Dark matter. Introduction. The field equations and the ground state solution for the bound particle-antiparticle pair. Olber's paradox -- ch. 6. Concluding remarks. Black holes. Pulsars. On the human race and cosmology -- ch. 7. Philosophical considerations. On truth. Positivism versus realism, subjectivity versus objectivity. On Mach's influence in physics and cosmology. References and notes -- Postscript. Physics in the 21st century. Holism. The universe. The Mach principle and the origin of inertia from general relativity.

  12. Beyond Gisin’s Theorem and its Applications: Violation of Local Realism by Two-Party Einstein-Podolsky-Rosen Steering

    PubMed Central

    Chen, Jing-Ling; Su, Hong-Yi; Xu, Zhen-Peng; Wu, Yu-Chun; Wu, Chunfeng; Ye, Xiang-Jun; Żukowski, Marek; Kwek, L. C.

    2015-01-01

    We demonstrate here that for a given mixed multi-qubit state if there are at least two observers for whom mutual Einstein-Podolsky-Rosen steering is possible, i.e. each observer is able to steer the other qubits into two different pure states by spontaneous collapses due to von Neumann type measurements on his/her qubit, then nonexistence of local realistic models is fully equivalent to quantum entanglement (this is not so without this condition). This result leads to an enhanced version of Gisin’s theorem (originally: all pure entangled states violate local realism). Local realism is violated by all mixed states with the above steering property. The new class of states allows one e.g. to perform three party secret sharing with just pairs of entangled qubits, instead of three qubit entanglements (which are currently available with low fidelity). This significantly increases the feasibility of having high performance versions of such protocols. Finally, we discuss some possible applications. PMID:26108704

  13. Critical Aesthetic Realism

    ERIC Educational Resources Information Center

    McMahon, Jennifer A.

    2011-01-01

    A clear-cut concept of the aesthetic is elusive. Kant's "Critique of Judgment" presents one of the more comprehensive aesthetic theories from which one can extract a set of features, some of which pertain to aesthetic experience and others to the logical structure of aesthetic judgment. When considered together, however, these features present a…

  14. The stereochemistry of chlorophyll-c₃ from the haptophyte Emiliania huxleyi: the (13²R)-enantiomers of chlorophylls-c are exclusively selected as the photosynthetically active pigments in chromophyte algae.

    PubMed

    Mizoguchi, Tadashi; Kimura, Yuki; Yoshitomi, Taichi; Tamiaki, Hitoshi

    2011-11-01

    Chlorophyll(Chl)-c pigments in algae, diatoms and some prokaryotes are characterized by the fully conjugated porphyrin π-system as well as the acrylate residue at the 17-position. The precise structural characterization of Chl-c(3) from the haptophyte Emiliania huxleyi was performed. The conformations of the π-conjugated peripheral substituents, the 3-/8-vinyl, 7-methoxycarbonyl and 17-acrylate moieties were evaluated, in a solution, using nuclear Overhauser enhancement correlations and molecular modeling calculations. The rotation of the 17-acrylate residue was considerably restricted, whereas the other three substituents readily rotated at ambient temperature. Moreover, the stereochemistry at the 13²-position was determined by combination of chiral high-performance liquid chromatography (HPLC) with circular dichroism (CD) spectroscopy. Compared with the CD spectra of the structurally related, synthetic (13²R)- and (13²S)-protochlorophyllide(PChlide)-a, naturally occurring Chl-c₃ had exclusively the (13²R)-configuration. To elucidate this natural selection of a single enantiomer, we analyzed the three major Chl-c pigments (Chl-c₁, c₂ and c₃) in four phylogenetically distinct classes of Chl-c containing algae, i.e., heterokontophyta, dinophyta, cryptophyta and haptophyta using chiral HPLC. All the photosynthetic organisms contained only the (13²R)-enantiomerically pure Chls-c, and lacked the corresponding enantiomeric (13²S)-forms. Additionally, Chl-c₂ was found in all the organisms as the common Chl-c. These results throw a light on the biosynthesis as well as photosynthetic function of Chl-c pigments: Chl-c₂ is derived from 8-vinyl-PChlide-a by dehydrogenation of the 17-propionate to acrylate residues as generally proposed, and the (13²R)-enantiomers of Chls-c function as photosynthetically active, light-harvesting pigments together with the principal Chl-a and carotenoids. PMID:21806961

  15. Using the PhysX engine for Physics-based Virtual Surgery with Force Feedback

    PubMed Central

    Maciel, Anderson; Halic, Tansel; Lu, Zhonghua; Nedel, Luciana P.; De, Suvranu

    2010-01-01

    Background The development of modern surgical simulators is highly challenging as they must support complex simulation environments. The demand for higher realism in such simulators has driven researchers to adopt physics-based models which are computationally very demanding. This poses a major problem since real time interactions must permit graphical updates of 30 Hz and a much higher rate of 1 kHz for force feedback (haptics). Recently several physics engines have been developed which offer multi-physics simulation capabilities including rigid and deformable bodies, cloth and fluids. While such physics engines provide unique opportunities for the development of surgical simulators, their higher latencies, compared to what is necessary for real time graphics and haptics, offer significant barriers to their use in interactive simulation environments. Methods In this work, we propose solutions to this problem and demonstrate how a multimodal surgical simulation environment may be developed based on NVIDIA’s PhysX physics library. Hence, models that are undergoing relatively low frequency updates in PhysX can exist in an environment that demands much higher frequency updates for haptics. We use a collision handling layer to interface between the physical response provided by PhysX and the haptic rendering device to provide both real time tissue response and force feedback. Results Our simulator integrates a bimanual haptic interface for force-feedback and per-pixel shaders for graphics realism in real time. To demonstrate the effectiveness of our approach, we present the simulation of the Laparoscopic Adjustable Gastric Banding (LAGB) procedure as a case study. Conclusions To develop complex and realistic surgical trainers with realistic organ geometries and tissue properties demands stable physics-based deformation methods which are not always compatible with the interaction level required for such trainers. We have shown that combining different modeling

  16. Shock Treatment: Using Immersive Digital Realism to Restage and Re-examine Milgram’s ‘Obedience to Authority’ Research

    PubMed Central

    Haslam, S. Alexander; Reicher, Stephen D.; Millard, Kathryn

    2015-01-01

    Attempts to revisit Milgram’s ‘Obedience to Authority’ (OtA) paradigm present serious ethical challenges. In recent years new paradigms have been developed to circumvent these challenges but none involve using Milgram’s own procedures and asking naïve participants to deliver the maximum level of shock. This was achieved in the present research by using Immersive Digital Realism (IDR) to revisit the OtA paradigm. IDR is a dramatic method that involves a director collaborating with professional actors to develop characters, the strategic withholding of contextual information, and immersion in a real-world environment. 14 actors took part in an IDR study in which they were assigned to conditions that restaged Milgrams’s New Baseline (‘Coronary’) condition and four other variants. Post-experimental interviews also assessed participants’ identification with Experimenter and Learner. Participants’ behaviour closely resembled that observed in Milgram’s original research. In particular, this was evidenced by (a) all being willing to administer shocks greater than 150 volts, (b) near-universal refusal to continue after being told by the Experimenter that “you have no other choice, you must continue” (Milgram’s fourth prod and the one most resembling an order), and (c) a strong correlation between the maximum level of shock that participants administered and the mean maximum shock delivered in the corresponding variant in Milgram’s own research. Consistent with an engaged follower account, relative identification with the Experimenter (vs. the Learner) was also a good predictor of the maximum shock that participants administered. PMID:25730318

  17. Testing the realism of a topography-driven model (FLEX-Topo) in the nested catchments of the Upper Heihe, China

    NASA Astrophysics Data System (ADS)

    Gao, H.; Hrachowitz, M.; Fenicia, F.; Gharari, S.; Savenije, H. H. G.

    2014-05-01

    Although elevation data are globally available and used in many existing hydrological models, their information content is still underexploited. Topography is closely related to geology, soil, climate and land cover. As a result, it may reflect the dominant hydrological processes in a catchment. In this study, we evaluated this hypothesis through four progressively more complex conceptual rainfall-runoff models. The first model (FLEXL) is lumped, and it does not make use of elevation data. The second model (FLEXD) is semi-distributed with different parameter sets for different units. This model uses elevation data indirectly, taking spatially variable drivers into account. The third model (FLEXT0), also semi-distributed, makes explicit use of topography information. The structure of FLEXT0 consists of four parallel components representing the distinct hydrological function of different landscape elements. These elements were determined based on a topography-based landscape classification approach. The fourth model (FLEXT) has the same model structure and parameterization as FLEXT0 but uses realism constraints on parameters and fluxes. All models have been calibrated and validated at the catchment outlet. Additionally, the models were evaluated at two sub-catchments. It was found that FLEXT0 and FLEXT perform better than the other models in nested sub-catchment validation and they are therefore better spatially transferable. Among these two models, FLEXT performs better than FLEXT0 in transferability. This supports the following hypotheses: (1) topography can be used as an integrated indicator to distinguish between landscape elements with different hydrological functions; (2) FLEXT0 and FLEXT are much better equipped to represent the heterogeneity of hydrological functions than a lumped or semi-distributed model, and hence they have a more realistic model structure and parameterization; (3) the soft data used to constrain the model parameters and fluxes in FLEXT

  18. Actuality of transcendental æsthetics for modern physics

    NASA Astrophysics Data System (ADS)

    Petitot, Jean

    1. The more mathematics and physics unify themselves in the physico-mathematical modern theories, the more an objective epistemology becomes necessary. Only such a transcendental epistemology is able to thematize correctly the status of the mathematical determination of physical reality. 2. There exists a transcendental history of the synthetic a priori and of the construction of physical categories. 3. The transcendental approach allows to supersed Wittgenstein's and Carnap's antiplatonist thesis according to which pure mathematics are physically applicable only if they lack any descriptive, cognitive or objective, content and reduce to mere prescriptive and normative devices. In fact, pure mathematics are prescriptive-normative in physics because: (i) the categories of physical objectivity are prescriptive-normative, and (ii) their categorial content is mathematically “constructed” through a Transcendental Aesthetics. Only a transcendental approach make compatible, in the one hand, a grammatical conventionalism of Wittgensteinian or Carnapian type and, on the other hand, a platonist realism of Gödelian type. Mathematics are not a grammar of the world but a mathematical hermeneutics of the intuitive forms and of the categorial grammar of the world.

  19. Sports physical

    MedlinePlus

    ... this page: //medlineplus.gov/ency/patientinstructions/000673.htm Sports physical To use the sharing features on this ... or routine checkups. Why do you Need a Sports Physical? The sports physical is done to: Find ...

  20. On the Stereochemistry of 2-Hydroxyethylphosphonate Dioxygenase

    PubMed Central

    2011-01-01

    Stereochemical investigations have shown that the conversion of 2-hydroxyethylphosphonate to hydroxymethylphosphonate by the enzyme HEPD involves removal of the pro-S hydrogen at C2 and, surprisingly, the loss of stereochemical information at C1. As a result, the mechanisms previously proposed for HEPD must be re-evaluated. PMID:21381767

  1. How Stereochemistry Considerations can Improve Pesticide Safety

    EPA Science Inventory

    About 30% of pesticides are chiral molecules and therefore exist as two or more stereoisomers, which can differ significantly in their toxicity, biodegradation, and persistence. Such differences can impact their relative safety to humans and environmental species. Enantiomers, mi...

  2. Aspects of the stereochemistry of torularhodin biosynthesis

    PubMed Central

    Tefft, R. E.; Goodwin, T. W.; Simpson, K. L.

    1970-01-01

    1. The incorporation of [2-14C]acetate, [2-14C]mevalonic acid and [2-14C,2-3H2]-mevalonic acid into torulene and torularhodin by Rhodotorula rubra and Rhodotorula glutinis was studied. 2. A recovery of 14.3% of the label was obtained on decarboxylation of the torularhodin biosynthesized from [2-14C]mevalonic acid. 3. An analysis of the 3H/14C ratio in torularhodin gave a value of 9.44:8. 4. These results, obtained by different experimental techniques, show that the reactions in the conversion of the dimethyl group of isopentenyl pyrophosphate into the 16′,17′-position of torularhodin must be free from randomization. A mechanism for the isomerization of isopentenyl pyrophosphate to dimethylallyl pyrophosphate is suggested. PMID:5465554

  3. Death: Realism in Children's Books.

    ERIC Educational Resources Information Center

    Danielson, Kathy Everts

    In the past, books for children treated death fearfully, morbidly, and didactically, but now children's literature treats death in a more realistic manner and is sensitive to its emotional aspects. Current theories suggest that children perceive death differently at various ages. G. P. Koocher (1973) used J. Piaget's cognitive stages as the basis…

  4. Dynamical Realism and Uncertainty Propagation

    NASA Astrophysics Data System (ADS)

    Park, Inkwan

    In recent years, Space Situational Awareness (SSA) has become increasingly important as the number of tracked Resident Space Objects (RSOs) continues their growth. One of the most significant technical discussions in SSA is how to propagate state uncertainty in a consistent way with the highly nonlinear dynamical environment. In order to keep pace with this situation, various methods have been proposed to propagate uncertainty accurately by capturing the nonlinearity of the dynamical system. We notice that all of the methods commonly focus on a way to describe the dynamical system as precisely as possible based on a mathematical perspective. This study proposes a new perspective based on understanding dynamics of the evolution of uncertainty itself. We expect that profound insights of the dynamical system could present the possibility to develop a new method for accurate uncertainty propagation. These approaches are naturally concluded in goals of the study. At first, we investigate the most dominant factors in the evolution of uncertainty to realize the dynamical system more rigorously. Second, we aim at developing the new method based on the first investigation enabling orbit uncertainty propagation efficiently while maintaining accuracy. We eliminate the short-period variations from the dynamical system, called a simplified dynamical system (SDS), to investigate the most dominant factors. In order to achieve this goal, the Lie transformation method is introduced since this transformation can define the solutions for each variation separately. From the first investigation, we conclude that the secular variations, including the long-period variations, are dominant for the propagation of uncertainty, i.e., short-period variations are negligible. Then, we develop the new method by combining the SDS and the higher-order nonlinear expansion method, called state transition tensors (STTs). The new method retains advantages of the SDS and the STTs and propagates uncertainty analytically and nonlinearly.

  5. Nuclear deterrence, morality, and realism

    SciTech Connect

    Finnis, J.; Boyle, J.M. Jr.; Grisez, G.

    1987-01-01

    Nuclear deterrence deserves rigorous, objective ethical analysis. In providing it, the authors of this book face realities - the Soviet threat, possible nuclear holocaust, strategic imperatives - but they also unmask moral evasions - deterrence cannot be bluff, pure counterforce, the lesser (or greater) evil, or a step towards disarmament. They conclude that the deterrent is unjustifiable and examine the new questions of conscience that this raises for everyone.

  6. Physical Allergy

    MedlinePlus

    ... physical stimulus. Physical stimuli include the following: Cold Sunlight Heat or other stimuli that cause sweating (such ... a foreign substance and attacks it. Sensitivity to sunlight (photosensitivity) is an example. Ultraviolet light changes proteins ...

  7. Physical activity

    MedlinePlus

    ... this page: //medlineplus.gov/ency/article/001941.htm Physical activity To use the sharing features on this page, please enable JavaScript. Physical activity -- which includes an active lifestyle and routine exercise -- ...

  8. Physics Notes

    ERIC Educational Resources Information Center

    School Science Review, 1976

    1976-01-01

    Described are 13 physics experiments/demonstrations applicable to introductory physics courses. Activities include: improved current balance, division circuits, liquid pressure, convection, siphons, oscillators and modulation, electrical resistance, soap films, Helmholtz coils, radioactive decay, and springs. (SL)

  9. Physics Notes

    ERIC Educational Resources Information Center

    School Science Review, 1972

    1972-01-01

    Seventeen experiments in physics are described to demonstrate various physical phenomena. These include the areas of velocity of sound, damped oscillations, plastic deformation of wires, materials, testing, air resistance, spectrum optical filtering, and some new improvised apparatus. (PS)

  10. Sports Physicals

    MedlinePlus

    ... stronger athlete. previous continue When & Where Should I Go for a Sports Physical? Some people go to their own doctor for a sports physical; ... one at school. During school physicals, you may go to half a dozen or so "stations" set ...