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Sample records for physical realism stereochemistry

  1. Structural realism beyond physics.

    PubMed

    Tulodziecki, Dana

    2016-10-01

    The main purpose of this paper is to test structural realism against (one example from) the historical record. I begin by laying out an existing challenge to structural realism - that of providing an example of a theory exhibiting successful structures that were abandoned - and show that this challenge can be met by the miasma theory of disease. However, rather than concluding that this is an outright counterexample to structural realism, I use this case to show why it is that structural realism, in its current form, has trouble dealing with theories outside physics. I end by making some concrete suggestions for structural realists to pursue if, indeed, they are serious about extending structural realism to other domains.

  2. 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.

  3. Perception of realism during mock resuscitations by pediatric housestaff: the impact of simulated physical features.

    PubMed

    Donoghue, Aaron J; Durbin, Dennis R; Nadel, Frances M; Stryjewski, Glenn R; Kost, Suzanne I; Nadkarni, Vinay M

    2010-02-01

    Physical signs that can be seen, heard, and felt are one of the cardinal features that convey realism in patient simulations. In critically ill children, physical signs are relied on for clinical management despite their subjective nature. Current technology is limited in its ability to effectively simulate some of these subjective signs; at the same time, data supporting the educational benefit of simulated physical features as a distinct entity are lacking. We surveyed pediatric housestaff as to the realism of scenarios with and without simulated physical signs. Residents at three children's hospitals underwent a before-and-after assessment of performance in mock resuscitations requiring Pediatric Advanced Life Support (PALS), with a didactic review of PALS as the intervention between the assessments. Each subject was randomized to a simulator with physical features either activated (simulator group) or deactivated (mannequin group). Subjects were surveyed as to the realism of the scenarios. Univariate analysis of responses was done between groups. Subjects in the high-fidelity group were surveyed as to the relative importance of specific physical features in enhancing realism. Fifty-one subjects completed all surveys. Subjects in the high-fidelity group rated all scenarios more highly than low-fidelity subjects; the difference achieved statistical significance in scenarios featuring a patient in asystole or pulseless ventricular tachycardia (P < 0.04 for both comparisons). Chest wall motion and palpable pulses were rated most highly among physical features in contributing to realism. PALS scenarios were rated as highly realistic by pediatric residents. Slight differences existed between subjects exposed to simulated physical features and those not exposed to them; these differences were most pronounced in scenarios involving pulselessness. Specific physical features were rated as more important than others by subjects. Data from these surveys may be informative

  4. Shifting to structures in physics and biology: a prophylactic for promiscuous realism.

    PubMed

    French, Steven

    2011-06-01

    Within the philosophy of science, the realism debate has been revitalised by the development of forms of structural realism. These urge a shift in focus from the object oriented ontologies that come and go through the history of science to the structures that remain through theory change. Such views have typically been elaborated in the context of theories of physics and are motivated by, first of all, the presence within such theories of mathematical equations that allow straightforward representation of the relevant structures; and secondly, the implications of such theories for the individuality and identity of putative objects. My aim in this paper is to explore the possibility of extending such views to biological theories. An obvious concern is that within the context of the latter it is typically insisted that we cannot find the kinds of highly mathematised structures that structural realism can point to in physics. I shall indicate how the model-theoretic approach to theories might help allay such concerns. Furthermore, issues of identity and individuality also arise within biology. Thus Dupré has recently noted that there exists a 'General Problem of Biological Individuality' which relates to the issue of how one divides 'massively integrated and interconnected' systems into discrete components. In response Dupré advocates a form of 'Promiscuous Realism' that holds, for example, that there is no unique way of dividing the phylogenetic tree into kinds. Instead I shall urge serious consideration of those aspects of the work of Dupré and others that lean towards a structuralist interpretation. By doing so I hope to suggest possible ways in which a structuralist stance might be extended to biology.

  5. 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.

  6. 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.

  7. Practical Stereochemistry.

    PubMed

    Kellogg, Richard M

    2017-03-01

    The relationship between fundamental and applied is often uneasy, particularly in modern political climates. A familiar political view, aimed negatively at the scientific community, is that the former is a waste of money whereas the latter gives value for investment. The answer that fundamental is required as the basis for practical suffers from the fact that the timelines between fundamental and practical are often long and the routes contorted and unexpected. This has been my experience. In this Account, examples are given from the research in which I have been involved wherein quite fundamental considerations have led to various applications. The longer the time, the clearer and broader the relationship. Fundamental can and does lead to application. They need and depend on each other. I have seen this both from the side of academia and from small companies. In the course of the past 40 plus years, I have been involved in various aspects of stereochemistry and, in particular, chirality. It has been rewarding to see that several of the developments, most originally grounded in fundamental research considerations, have been used in the chemical community and given new dimensions and often practical applications by others. In this Account, a path-not planned deliberately by me-from orbital symmetry and Woodward-Hoffmann rules through crown ethers to conformational analysis to diastereomeric resolutions to deracemizations powered by Ostwald ripening and the Gibbs-Thomson effect to nucleation to helicenes is described. In order of discussion, the orbital symmetry aspects have via an unusual and unpredicted path has resulted in, among other things, a synthesis of hindered alkenes useful for the production of molecular motors. The crown ether aspects led to discovery of the utility of cesium salts particularly for racemization sensitive nucleophilic substitutions. Work on diastereomeric resolutions has concentrated on the mechanistic as well as practical

  8. 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…

  9. 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…

  10. A Quiz on Stereochemistry.

    ERIC Educational Resources Information Center

    Ghosh, Abhik

    1987-01-01

    Presents five problems on organic stereochemistry in the form of an open-book quiz meant for senior undergraduates and graduate students in chemistry. Provides some acceptable solutions to the problems. (TW)

  11. Stereochemistry of kahalalide F.

    PubMed

    Bonnard, Isabelle; Manzanares, Ignacio; Rinehart, Kenneth L

    2003-11-01

    The stereochemistry of the amino acids in the marine-derived cyclic depsipeptide kahalalide F has been defined by a series of degradation reactions (hydrolysis, ozonolysis, Edman degradation, and Marfey derivatization), yielding smaller fragments of the marine natural product. The results from these reactions agree with the structure originally proposed by Hamann and Scheuer and with the same stereochemistry of most of the component amino acids more recently proposed by Goetz, Yoshida, and Scheuer. However, our assignments of d-Val(3) and l-Val(4) are the reverse of previous assignments made as l-Val(3) and d-Val(4). The present (reversed) stereochemistry is crucial for the antitumor activity of kahalalide F.

  12. Extensional scientific realism vs. intensional scientific realism.

    PubMed

    Park, Seungbae

    2016-10-01

    Extensional scientific realism is the view that each believable scientific theory is supported by the unique first-order evidence for it and that if we want to believe that it is true, we should rely on its unique first-order evidence. In contrast, intensional scientific realism is the view that all believable scientific theories have a common feature and that we should rely on it to determine whether a theory is believable or not. Fitzpatrick argues that extensional realism is immune, while intensional realism is not, to the pessimistic induction. I reply that if extensional realism overcomes the pessimistic induction at all, that is because it implicitly relies on the theoretical resource of intensional realism. I also argue that extensional realism, by nature, cannot embed a criterion for distinguishing between believable and unbelievable theories.

  13. 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.

  14. Quantum mechanics is compatible with realism

    SciTech Connect

    Burgos, M.E.

    1987-08-01

    A new paradox of quantum mechanics has recently been proposed by an author claiming that any attempt to inject realism in physical theory is bound to lead to inconsistencies. In this paper the author shows that the mentioned paradox is not such a one and that at present there are no reasons to reject realism.

  15. Stereochemistry in Drug Action

    PubMed Central

    McConathy, Jonathan; Owens, Michael J.

    2003-01-01

    The importance of stereochemistry in drug action is gaining greater attention in medical practice, and a basic knowledge of the subject will be necessary for clinicians to make informed decisions regarding the use of single-enantiomer drugs. Many of the drugs currently used in psychiatric practice are mixtures of enantiomers. For some therapeutics, single-enantiomer formulations can provide greater selectivities for their biological targets, improved therapeutic indices, and/or better pharmacokinetics than a mixture of enantiomers. This article reviews the nomenclature for describing stereochemistry and enantiomers, emphasizes the potential biological and pharmacologic differences between the 2 enantiomers of a drug, and highlights the clinical experience with single enantiomers of the selective serotonin reuptake inhibitors fluoxetine and citalopram. In some cases, both a mixture of enantiomers and a single-enantiomer formulation of a drug will be available simultaneously. In these cases, familiarity with stereochemistry and its pharmacologic implications will aid the practicing physician to provide optimal pharmacotherapy to his or her patients. PMID:15156233

  16. 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.

  17. Can a virtual supermarket bring realism into the lab? Comparing shopping behavior using virtual and pictorial store representations to behavior in a physical store.

    PubMed

    van Herpen, Erica; van den Broek, Eva; van Trijp, Hans C M; Yu, Tian

    2016-12-01

    Immersive virtual reality techniques present new opportunities for research into consumer behavior. The current study examines whether the increased realism of a virtual store compared to pictorial (2D) stimuli elicits consumer behavior that is more in line with behavior in a physical store. We examine the number, variety, and type of products selected, amount of money spent, and responses to price promotions and shelf display, in three product categories (fruit & vegetables, milk, and biscuits). We find that virtual reality elicits behavior that is more similar to behavior in the physical store compared to the picture condition for the number of products selected (Milk: Mstore = 1.19, Mvirtual = 1.53, Mpictures = 2.58) and amount of money spent (Milk: Mstore = 1.27, Mvirtual = 1.53, Mpictures = 2.60 Euro), and for the selection of products from different areas of the shelf, both vertically (purchases from top shelves, milk and biscuits: Pstore = 21.6%, Pvirtual = 33.4%, Ppictures = 50.0%) and horizontally (purchase from left shelf, biscuits: Pstore = 35.5%, Pvirtual = 53.3%, Ppictures = 66.7%). This indicates that virtual reality can improve realism in responses to shelf allocation. Virtual reality was not able to diminish other differences between lab and physical store: participants bought more products and spent more money (for biscuits and fruit & vegetables), bought more national brands, and responded more strongly to price promotions in both virtual reality and pictorial representations than in the physical store. Implications for the use of virtual reality in studies of consumer food choice behavior as well as for future improvement of virtual reality techniques are discussed.

  18. 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…

  19. 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…

  20. Realism and quantum flux tunneling

    NASA Astrophysics Data System (ADS)

    Ballentine, L. E.

    1987-10-01

    The suggestion of Leggett and Garg (1985) that the phenomenon of quantum flux tunneling oscillations contradicts the predictions of quantum mechanics (QM) in the assumptions of both macroscopic realism and noninvasive measurability is reexamined. It is shown that the contradiction of QM is produced solely by the assumption of noninvasive measurability, and that no contradiction between QM and realism can be demonstrated in this case. These findings are illustrated by the calculation of the distribution function for successive flux measurements. It is noted that the previously suggested analogy between the Bell-type inequalities and the inequalities of Leggett and Garg is misleading because the physical principles of the Bell-type inequalities are not applicable to the presently considered SQUID.

  1. Local realism is dead, long live local realism?

    NASA Astrophysics Data System (ADS)

    Holmes, Rebecca

    2017-06-01

    Rebecca Holmes describes groundbreaking experiments that finally closed the long-standing loopholes in Bell tests, suggesting the end of the road for local realism. But could local realism yet live on?

  2. Revisiting Folk Moral Realism.

    PubMed

    Pölzler, Thomas

    2017-01-01

    Moral realists believe that there are objective moral truths. According to one of the most prominent arguments in favour of this view, ordinary people experience morality as realist-seeming, and we have therefore prima facie reason to believe that realism is true. Some proponents of this argument have claimed that the hypothesis that ordinary people experience morality as realist-seeming is supported by psychological research on folk metaethics. While most recent research has been thought to contradict this claim, four prominent earlier studies (by Goodwin and Darley, Wainryb et al., Nichols, and Nichols and Folds-Bennett) indeed seem to suggest a tendency towards realism. My aim in this paper is to provide a detailed internal critique of these four studies. I argue that, once interpreted properly, all of them turn out in line with recent research. They suggest that most ordinary people experience morality as "pluralist-" rather than realist-seeming, i.e., that ordinary people have the intuition that realism is true with regard to some moral issues, but variants of anti-realism are true with regard to others. This result means that moral realism may be less well justified than commonly assumed.

  3. Moral realism in nursing.

    PubMed

    Edwards, Steven D

    2014-04-01

    For more than 15 years Professor Per Nortvedt has been arguing the case for moral realism in nursing and the health-care context more generally. His arguments focus on the clinical contexts of nursing and medicine and are supplemented by a series of persuasive examples. Following a description of moral realism, and the kinds of considerations that support it, criticisms of it are developed that seem persuasive. It is argued that our moral responses are explained by our beliefs as opposed to moral realities. In particular, two key arguments presented by Nortvedt are challenged: the so-called argument from convergence and the argument from clinical sensitivity. Both of these key planks in the case for moral realism are rejected, and an alternative 'social conditioning' account briefly sketched, which, it is claimed, has the same explanatory power as Nortvedt's thesis but does not rest on an appeal to independently existing moral properties.

  4. Stereochemistry of the Brivaracetam Diastereoisomers.

    PubMed

    Qiu, Shi; Tehrani, Kourosch Abbaspour; Sergeyev, Sergey; Bultinck, Patrick; Herrebout, Wouter; Mathieu, Benoit

    2016-03-01

    The stereochemistry of all four stereoisomers of brivaracetam was determined using vibrational circular dichroism (VCD) spectroscopy. By comparing experimentally obtained VCD spectra and computationally simulated ones, the absolute configurations can be confidently assigned without prior knowledge of their relative stereochemistry. Neither the corrected mean absolute errors analysis of the nuclear magnetic resonance (NMR) data, nor the matching of experimental and calculated infrared spectra allowed the diastereoisomers to be distinguished. VCD spectroscopy itself suffices to establish the absolute configurations of all diastereoisomers. The relative stereochemistry could also be statistically confirmed by matching experimental and computed NMR spectra using the CP3 algorithm. The combination of VCD and NMR is recommended for molecules bearing more than one chiral center, as the relative configurations obtained from NMR serve as an independent check for those established with VCD. Analysis of the calculated VCD spectra reveals that the localized NH2 scissoring mode at around 1600 cm(-1) is characteristic for intramolecular hydrogen bonding, while the orientation of the ethyl group is reflected by the delocalized modes between 1150 and 1050 cm(-1).

  5. The evolution of process-based hydrologic models: historical challenges and the collective quest for physical realism

    DOE PAGES

    Clark, Martyn P.; Bierkens, Marc F. P.; Samaniego, Luis; ...

    2017-07-11

    The diversity in hydrologic models has historically led to great controversy on the correct approach to process-based hydrologic modeling, with debates centered on the adequacy of process parameterizations, data limitations and uncertainty, and computational constraints on model analysis. Here, we revisit key modeling challenges on requirements to (1) define suitable model equations, (2) define adequate model parameters, and (3) cope with limitations in computing power. We outline the historical modeling challenges, provide examples of modeling advances that address these challenges, and define outstanding research needs. We also illustrate how modeling advances have been made by groups using models of different type and complexity,more » and we argue for the need to more effectively use our diversity of modeling approaches in order to advance our collective quest for physically realistic hydrologic models.« less

  6. The evolution of process-based hydrologic models: historical challenges and the collective quest for physical realism

    NASA Astrophysics Data System (ADS)

    Clark, Martyn P.; Bierkens, Marc F. P.; Samaniego, Luis; Woods, Ross A.; Uijlenhoet, Remko; Bennett, Katrina E.; Pauwels, Valentijn R. N.; Cai, Xitian; Wood, Andrew W.; Peters-Lidard, Christa D.

    2017-07-01

    The diversity in hydrologic models has historically led to great controversy on the correct approach to process-based hydrologic modeling, with debates centered on the adequacy of process parameterizations, data limitations and uncertainty, and computational constraints on model analysis. In this paper, we revisit key modeling challenges on requirements to (1) define suitable model equations, (2) define adequate model parameters, and (3) cope with limitations in computing power. We outline the historical modeling challenges, provide examples of modeling advances that address these challenges, and define outstanding research needs. We illustrate how modeling advances have been made by groups using models of different type and complexity, and we argue for the need to more effectively use our diversity of modeling approaches in order to advance our collective quest for physically realistic hydrologic models.

  7. Improving the Physical Realism and Structural Accuracy of Protein Models by a Two-Step Atomic-Level Energy Minimization

    PubMed Central

    Xu, Dong; Zhang, Yang

    2011-01-01

    Most protein structural prediction algorithms assemble structures as reduced models that represent amino acids by a reduced number of atoms to speed up the conformational search. Building accurate full-atom models from these reduced models is a necessary step toward a detailed function analysis. However, it is difficult to ensure that the atomic models retain the desired global topology while maintaining a sound local atomic geometry because the reduced models often have unphysical local distortions. To address this issue, we developed a new program, called ModRefiner, to construct and refine protein structures from Cα traces based on a two-step, atomic-level energy minimization. The main-chain structures are first constructed from initial Cα traces and the side-chain rotamers are then refined together with the backbone atoms with the use of a composite physics- and knowledge-based force field. We tested the method by performing an atomic structure refinement of 261 proteins with the initial models constructed from both ab initio and template-based structure assemblies. Compared with other state-of-art programs, ModRefiner shows improvements in both global and local structures, which have more accurate side-chain positions, better hydrogen-bonding networks, and fewer atomic overlaps. ModRefiner is freely available at http://zhanglab.ccmb.med.umich.edu/ModRefiner. PMID:22098752

  8. 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.

  9. "Old" and "New" Realism in Adolescents' Literature

    ERIC Educational Resources Information Center

    Oliver, Jo Ellen

    1978-01-01

    Discusses whether the "old" realism has matured and the "new" realism (drugs, abortion, and homosexuality) in current books for young people. Compares "Skinny" (in the traditional vein) and "Mom, the Wolf Man and Me" (in terms of new realism). (JM)

  10. Epistemological Realism in Cognitive Theory.

    ERIC Educational Resources Information Center

    Yates, Jack

    An inappropriate epistemological realism continues to dominate cognitive science. Realism, the idea that there is a single, univocal world which exists independently of us but which we can come to know, is tacitly accepted by almost the whole body of cognitive science. The fatal flaw in any realist approach to cognition and perception is that the…

  11. 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…

  12. Depressive Realism: Wiser or Quieter?

    ERIC Educational Resources Information Center

    Blanco, Fernando; Matute, Helena; Vadillo, Miguel A.

    2009-01-01

    Depressive realism consists of the lower personal control over uncontrollable events perceived by depressed as compared to nondepressed individuals. In this article, we propose that the realism of depressed individuals is caused not by an increased accuracy in perception, but by their more comprehensive exposure to the actual environmental…

  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. Depressive Realism: Wiser or Quieter?

    ERIC Educational Resources Information Center

    Blanco, Fernando; Matute, Helena; Vadillo, Miguel A.

    2009-01-01

    Depressive realism consists of the lower personal control over uncontrollable events perceived by depressed as compared to nondepressed individuals. In this article, we propose that the realism of depressed individuals is caused not by an increased accuracy in perception, but by their more comprehensive exposure to the actual environmental…

  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…

  16. What is ontic structural realism?

    NASA Astrophysics Data System (ADS)

    Ainsworth, Peter Mark

    In recent years a doctrine known as ontic structural realism (OSR) has achieved a degree of notoriety, but many people remain confused as to what exactly the doctrine amounts. In this paper three main variants of OSR are defined and discussed: (i) OSR1, which is the view that relations are ontologically primitive but objects and properties are not; (ii) OSR2, which is the view that objects and relations are ontologically primitive but properties are not; (iii) OSR3, which is the view that properties and relations are ontologically primitive but objects are not. Proponents of OSR claim that it is a "naturalistic" metaphysics, arguing that metaphysical views that take objects and/or properties as ontologically primitive are undermined by contemporary physics. In this paper it is argued that OSR1 and OSR2 are themselves undermined by contemporary physics. On the other hand, it is also argued that considerations about the objects of quantum mechanics and general relativity do seem to suggest that we should abandon some of our "common-sense" metaphysical intuitions, and that OSR3 is one of the metaphysical views that is compatible with what these theories seem to tell us about fundamental ontology.

  17. Structural realism versus deployment realism: A comparative evaluation.

    PubMed

    Lyons, Timothy D

    2016-10-01

    In this paper I challenge and adjudicate between the two positions that have come to prominence in the scientific realism debate: deployment realism and structural realism. I discuss a set of cases from the history of celestial mechanics, including some of the most important successes in the history of science. To the surprise of the deployment realist, these are novel predictive successes toward which theoretical constituents that are now seen to be patently false were genuinely deployed. Exploring the implications for structural realism, I show that the need to accommodate these cases forces our notion of "structure" toward a dramatic depletion of logical content, threatening to render it explanatorily vacuous: the better structuralism fares against these historical examples, in terms of retention, the worse it fares in content and explanatory strength. I conclude by considering recent restrictions that serve to make "structure" more specific. I show however that these refinements will not suffice: the better structuralism fares in specificity and explanatory strength, the worse it fares against history. In light of these case studies, both deployment realism and structural realism are significantly threatened by the very historical challenge they were introduced to answer.

  18. Local realism of macroscopic correlations.

    PubMed

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

    2011-08-05

    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.

  19. 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.

  20. 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

  1. 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.

  2. An assessment tool for auditory realism

    NASA Astrophysics Data System (ADS)

    Lakatos, Stephen; Cook, Perry R.; Harbke, Colin R.

    2003-04-01

    An item-based survey was developed to evaluate how effectively physically-based models can yield sounds that appear realistic to the ear. Based on past research and current insights, realism as a construct was hypothesized to comprise eight orthogonal factors: detail, physical plausibility (biological and nonbiological), temporal consistency, vividness, presence, and whether a sound evokes sensory images and associated memories. Sets of 8-9 declarative statements were selected by committee for each factor from large initial lists of such statements. Another committee selected weak, moderate and strong sound exemplars for each factor from digital libraries that were felt to vary uniquely along that factor. In an exploratory phase, 82 participants rated how representative each sound exemplar was of each statement. Based on factor analyses, the three highest loading statements for each factor were compared across sound exemplars; statistically significant differences were found between exemplars for all factors. A subsequent confirmatory phase used new sounds, coupled with synthetic versions from physically-based simulations, to validate the proposed realism factors. Data from an additional 200 participants ratings for these stimuli supported the surveys construct validity. The survey should benefit sound engineers wishing to evaluate the degree to which their synthesis algorithms generate realistic output.

  3. 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.

  4. [Depressive realism: happiness or objectivity].

    PubMed

    Birinci, Fatih; Dirik, Gülay

    2010-01-01

    Realism is described as objective evaluations and judgments about the world; however, some research indicates that judgments made by "normal" people include a self-favored, positive bias in the perception of reality. Additionally, some studies report that compared to normal people, such cognitive distortions are less likely among depressive people. These findings gave rise to the depressive realism hypothesis. While results of several studies verify the notion that depressive people evaluate reality more objectively, other studies fail to support this hypothesis. Several causes for these inconsistent findings have been proposed, which can be characterized under 3 headings. One proposed explanation suggests that what is accepted as "realistic" in these studies is not quite objective and is in fact ambiguous. According to another perspective, the term "depressive" used in these studies is inconsistent with the criteria of scientific diagnostic methods. Another suggests that the research results can only be obtained under the specific experimental conditions. General negativity and limited processing are popular approaches used for explaining the depressive realism hypothesis. Nowadays, the debate over this hypothesis continues. The present review focuses on frequently cited research related to depressive realism and discusses the findings.

  5. 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.

  6. Absolute stereochemistry of altersolanol A and alterporriols.

    PubMed

    Kanamaru, Saki; Honma, Miho; Murakami, Takanori; Tsushima, Taro; Kudo, Shinji; Tanaka, Kazuaki; Nihei, Ken-Ichi; Nehira, Tatsuo; Hashimoto, Masaru

    2012-02-01

    The absolute stereochemistry of altersolanol A (1) was established by observing a positive exciton couplet in the circular dichroism (CD) spectrum of the C3,C4-O-bis(2-naphthoyl) derivative 10 and by chemical correlations with known compound 8. Before the discussion, the relative stereochemistry of 1 was confirmed by X-ray crystallographic analysis. The shielding effect at C7'-OMe group by C1-O-benzoylation established the relative stereochemical relationship between the C8-C8' axial bonding and the C1-C4/C1'-C4' polyol moieties of alterporriols E (3), an atropisomer of the C8-C8' dimer of 1. As 3 could be obtained by dimerization of 1 in vitro, the absolute configuration of its central chirality elements (C1-C4) must be identical to those of 1. Spectral comparison between the experimental and theoretical CD spectra supported the above conclusion. Axial stereochemistry of novel C4-O-deoxy dimeric derivatives, alterporriols F (4) and G (5), were also revealed by comparison of their CD spectra to those of 2 and 3.

  7. An experimental test of non-local realism.

    PubMed

    Gröblacher, Simon; Paterek, Tomasz; Kaltenbaek, Rainer; Brukner, Caslav; Zukowski, Marek; Aspelmeyer, Markus; Zeilinger, Anton

    2007-04-19

    Most working scientists hold fast to the concept of 'realism'--a viewpoint according to which an external reality exists independent of observation. But quantum physics has shattered some of our cornerstone beliefs. According to Bell's theorem, any theory that is based on the joint assumption of realism and locality (meaning that local events cannot be affected by actions in space-like separated regions) is at variance with certain quantum predictions. Experiments with entangled pairs of particles have amply confirmed these quantum predictions, thus rendering local realistic theories untenable. Maintaining realism as a fundamental concept would therefore necessitate the introduction of 'spooky' actions that defy locality. Here we show by both theory and experiment that a broad and rather reasonable class of such non-local realistic theories is incompatible with experimentally observable quantum correlations. In the experiment, we measure previously untested correlations between two entangled photons, and show that these correlations violate an inequality proposed by Leggett for non-local realistic theories. Our result suggests that giving up the concept of locality is not sufficient to be consistent with quantum experiments, unless certain intuitive features of realism are abandoned.

  8. The evolution of offensive realism.

    PubMed

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

    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.

  9. 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…

  10. 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…

  11. 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

  12. 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.

  13. The Universities and the Challenge of Realism

    ERIC Educational Resources Information Center

    Evans, Mary

    2010-01-01

    Universities are often enjoined to "get" with the "real world". In this article, Mary Evans gives an account of interpretations of literary realism in order to consider the "coercive realism" of the contemporary university. The prevailing assumptions that universities must contribute to the "real" world are…

  14. 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…

  15. The Universities and the Challenge of Realism

    ERIC Educational Resources Information Center

    Evans, Mary

    2010-01-01

    Universities are often enjoined to "get" with the "real world". In this article, Mary Evans gives an account of interpretations of literary realism in order to consider the "coercive realism" of the contemporary university. The prevailing assumptions that universities must contribute to the "real" world are…

  16. Young Adult Realism: Conventions, Narrators, and Readers.

    ERIC Educational Resources Information Center

    Ross, Catherine Sheldrick

    1985-01-01

    Examination of a subset of books popular with young adults--problem novels or young adult realism--is based on deductions concerning nature of reading response that text invites. Young adult realism as formula of popular culture, changes in conventions, narrators and narratees, and identification and distance are discussed. (34 references) (EJS)

  17. Interrogating the "Real" in Young Adult Realism.

    ERIC Educational Resources Information Center

    Brown, Joanne

    1999-01-01

    Discusses the complexities of defining "realism," examining how the term fueled many discussions in the author's college adolescent literature course. Looks at how writers and critics define the term. Shares alternatives to circuitous arguments about the relative realism of a text that helps students explore texts in effective ways that can lead…

  18. 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.

  19. 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.

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

    PubMed Central

    Chattopadhyay, Debaleena; MacDorman, Karl F.

    2016-01-01

    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

  1. 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.

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

    PubMed

    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.

  3. Relative stereochemistry of the A ring of plant bile pigments

    SciTech Connect

    Schoenleber, R.W.; Kim, Y.; Rapoport, H.

    1984-05-02

    The synthesis and characterization, including the stereochemistry, of a series of 3,4-dihydropyrromethenones and 2,3-dihydrodioxobilins are described. High-resolution /sup 1/H NMR spectral analysis allows the determination of the A ring coupling constants for a series of cis and trans model compounds. From these data and correlations, the relative stereochemistry in the A ring of phycocyanin and similar bile pigment structures can be concluded.

  4. Realism and Impartiality: Making Sustainability Effective in Decision-Making.

    PubMed

    Bastons, Miquel; Armengou, Jaume

    2016-11-24

    There is both individual and collective widespread concern in society about the impact of human activity and the effects of our decisions on the physical and social environment. This concern is included within the idea of sustainability. The meaning of the concept is still ambiguous and its practical effectiveness disputed. Like many other authors, this article uses as a starting point the definition proposed by the World Commission on Environment and Development (Our common future, Oxford University Press, Oxford, 1987), considering it to be a proposal for changing the assessment of the effects of decisions, from at least two perspectives: (1) what effects we should consider and (2) how we should assess them. Based on this double perspective, sustainability is explored as a method for decision-making which both expands the assessment of the consequences, and also provides an objective criterion for such assessment. It will be argued that the idea of sustainability, seen from this perspective, brings to decision-making two qualities which had been partially lost: realism and impartiality. In turn, the criteria for realism and impartiality in decision-making can be used to identify the limitations of some partial approaches to sustainability, which suffer from insufficient realism (emotional altruism), insufficient impartiality (tactical altruism) or both phenomena at once (egoism). The article concludes by demonstrating how realism and impartiality provide the basis for a new form of sustainable decision-making (ethical sustainability), which is dependent on the development of two moral virtues, prudence and benevolence, and which brings practical effectiveness and ethical sense to the concept of sustainability.

  5. Depressive realism: a meta-analytic review.

    PubMed

    Moore, Michael T; Fresco, David M

    2012-08-01

    The current investigation represents the first meta-analysis of the depressive realism literature. A search of this literature revealed 75 relevant studies representing 7305 participants from across the US and Canada, as well as from England, Spain, and Israel. Results generally indicated a small overall depressive realism effect (Cohen's d=-.07). Overall, however, both dysphoric/depressed individuals (d=.14) and nondysphoric/nondepressed individuals evidenced a substantial positive bias (d=.29), with this bias being larger in nondysphoric/nondepressed individuals. Examination of potential moderator variables indicated that studies lacking an objective standard of reality (d=-.15 versus -.03, for studies possessing such a standard) and that utilize self-report measures to measure symptoms of depression (d=.16 versus -.04, for studies which utilize structured interviews) were more likely to find depressive realism effects. Methodological paradigm was also found to influence whether results consistent with depressive realism were found (d's ranged from -.09 to .14).

  6. Social acceptance of comparative optimism and realism.

    PubMed

    Milhabet, I; Verlhiac, J F

    2011-10-01

    Studies of optimism and realism (the accuracy of people's outlook on the future) seek to understand the respective effects of these elements on social approbation. Two experiments examined how comparative optimism (vs. pessimism) and realism (vs. unrealism) interacted to influence the targets' social acceptance based on their perceptions about the future. The results showed that realism, or accuracy of prediction, increased the positive social effects of a comparatively optimistic outlook on the future. In contrast, targets who exhibited comparative pessimism were more socially acceptable when their predictions were unrealistic rather than realistic. This phenomenon was examined by also considering the polarity of the events about which judgments were expressed. These results contribute to the body of research about the relationship between optimism and pessimism and the relationship between optimism and realism.

  7. Earth Observing System Covariance Realism Updates

    NASA Technical Reports Server (NTRS)

    Ojeda Romero, Juan A.; Miguel, Fred

    2017-01-01

    This presentation will be given at the International Earth Science Constellation Mission Operations Working Group meetings June 13-15, 2017 to discuss the Earth Observing System Covariance Realism updates.

  8. 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.

  9. 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…

  10. 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…

  11. 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).

  12. 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).

  13. Covariance and Uncertainty Realism in Space Surveillance and Tracking

    DTIC Science & Technology

    2016-06-27

    Covariance and Uncertainty Realism in Space Surveillance and Tracking Date: Monday 27th June, 2016 Working Group on Covariance Realism Edited By...always linear nor Gaussian, one may generalize covariance realism to uncertainty realism described by a potentially non-Gaussian probability density...problem due to the complex and numerous sources of uncertainty. To achieve a proper characterization of uncertainty, one must account for the uncertainty

  14. Realism, functions, and the a priori: Ernst Cassirer's philosophy of science.

    PubMed

    Heis, Jeremy

    2014-12-01

    This paper presents the main ideas of Cassirer's general philosophy of science, focusing on the two aspects of his thought that--in addition to being the most central ideas in his philosophy of science--have received the most attention from contemporary philosophers of science: his theory of the a priori aspects of physical theory, and his relation to scientific realism.

  15. New Tests of Macroscopic Local Realism

    NASA Astrophysics Data System (ADS)

    Reid, M. D.

    We show that quantum mechanics predicts an Einstein-Podolsky-Rosen paradox (EPR), and also a contradiction with local hidden variable theories, for photon number measurements which have limited resolving power, to the point of imposing an uncertainty in the photon number result which is macroscopic in absolute terms. We show how this can be interpreted as a failure of a new, very strong premise, called macroscopic local realism. We link this premise to the Schrodinger-cat paradox. Our proposed experiments ensure all fields incident on each measurement apparatus are macroscopic. We show that an alternative measurement scheme corresponds to balanced homodyne detection of quadrature phase amplitudes. The implication is that where either EPR correlations or failure of local realism is predicted for quadrature phase amplitude measurements, one can potentially perform a modified experiment which would lead to conclusions about the much stronger premise of macroscopic local realism.

  16. 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.

  17. The sad truth about depressive realism.

    PubMed

    Allan, Lorraine G; Siegel, Shepard; Hannah, Samuel

    2007-03-01

    In one form of a contingency judgement task individuals must judge the relationship between an action and an outcome. There are reports that depressed individuals are more accurate than are non-depressed individuals in this task. In particular, nondepressed individuals are influenced by manipulations that affect the salience of the outcome, especially outcome probability. They overestimate a contingency if the probability of an outcome is high--the "outcome-density effect". In contrast, depressed individuals display little or no outcome-density effect. This apparent knack for depressives not to be misled by outcome density in their contingency judgements has been termed "depressive realism", and the absence of an outcome-density effect has led to the characterization of depressives as "sadder but wiser". We present a critical summary of the depressive realism literature and provide a novel interpretation of the phenomenon. We suggest that depressive realism may be understood from a psychophysical analysis of contingency judgements.

  18. 48 CFR 1515.404-475 - Cost realism.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 48 Federal Acquisition Regulations System 6 2010-10-01 2010-10-01 true 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 competitive...

  19. 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…

  20. 48 CFR 1515.404-475 - Cost realism.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 48 Federal Acquisition Regulations System 6 2011-10-01 2011-10-01 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 competitive...

  1. 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…

  2. Metacognitive Realism: A Cognitive Style or a Learning Strategy?

    ERIC Educational Resources Information Center

    Jans, Veronique; Leclercq, Dieudonne

    1997-01-01

    Identifies metacognitive realism as the accurate assessment by a learner of their knowledge on a subject. Considers whether realism in metacognition is a stable trait, and possible influences. Briefly reviews the literature and experimental evidence and concludes that metacognitive realism is both style and strategy. (MJP)

  3. Queer Genes: Realism, Sexuality and Science

    PubMed Central

    Griffiths, David Andrew

    2016-01-01

    What are ‘gay genes’ and are they real? This article looks at key research into these hypothesized gay genes, made possible, in part, by the Human Genome Project. I argue that the complexity of both genetics and human sexuality demands a truly critical approach: one that takes into account feminist epistemologies of science and queer approaches to the body, while putting into conversation resources from agential realism and critical realism. This approach is able to maintain the agential complexity of genetic materiality, while also critically challenging the seemingly stable relationships between sex, gender and sexuality. PMID:28058037

  4. Queer Genes: Realism, Sexuality and Science.

    PubMed

    Griffiths, David Andrew

    2016-10-19

    What are 'gay genes' and are they real? This article looks at key research into these hypothesized gay genes, made possible, in part, by the Human Genome Project. I argue that the complexity of both genetics and human sexuality demands a truly critical approach: one that takes into account feminist epistemologies of science and queer approaches to the body, while putting into conversation resources from agential realism and critical realism. This approach is able to maintain the agential complexity of genetic materiality, while also critically challenging the seemingly stable relationships between sex, gender and sexuality.

  5. Moral Realism Revisited: On Achievable Morality.

    ERIC Educational Resources Information Center

    Ternasky, P. Lance

    1992-01-01

    The article discusses moral education in public schools. It proposes a realist model of moral realism derived from the work of Richard Boyd and Peter Railton, arguing that it offers relief from skepticism faced by moral educators and a foundation for teachable, achievable morality. (SM)

  6. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Realism and constructivism in social perception.

    PubMed

    Kihlstrom, John F

    2017-01-01

    Jussim's critique of social psychology's embrace of error and bias is needed and often persuasive. In opting for perceptual realism over social constructivism, however, he seems to ignore a third choice - a cognitive constructivism which has a long and distinguished history in the study of nonsocial perception, and which enables us to understand both accuracy and error.

  8. 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.

  9. Aesthetic Description and Realism in Art Education.

    ERIC Educational Resources Information Center

    Brown, Neil C. M.

    1989-01-01

    Looks at the usefulness of a stable realism for questions related to the description and understanding of art works. Explores two theories which may resolve the antagonism between representational meanings and their assertion as true properties of the work: (1) Wiggin's concept of authentic effect; and (2) Petit's theory of rectification and…

  10. Testing nonlocal realism with entangled coherent states

    SciTech Connect

    Paternostro, Mauro; Jeong, Hyunseok

    2010-03-15

    We investigate the violation of nonlocal realism using entangled coherent states (ECSs) under nonlinear operations and homodyne measurements. We address recently proposed Leggett-type inequalities, including a class of optimized incompatibility inequalities proposed by Branciard et al. [Nature Phys. 4, 681 (2008)], and thoroughly assess the effects of detection inefficiency.

  11. Locality and realism in contextual theories

    SciTech Connect

    Hoekzema, D.

    1987-08-01

    Two types of contextual theories are distinguished and shown to be related. For theories of each type a criterion of locality is formulated which is weaker than the classical requirement of separability at spacelike intervals. The relations between the concepts of locality, realism, and ontic chance are discussed.

  12. Violation of local realism versus detection efficiency

    SciTech Connect

    Massar, Serge; Pironio, Stefano

    2003-12-01

    We put bounds on the minimum detection efficiency necessary to violate local realism in Bell experiments. These bounds depend on simple parameters like the number of measurement settings or the dimensionality of the entangled quantum state. We derive them by constructing explicit local hidden variable models which reproduce the quantum correlations for sufficiently small detectors efficiency.

  13. Children's Perceived Realism of Family Television Series.

    ERIC Educational Resources Information Center

    Rabin, Beth E.; And Others

    This study examined the influence of grade level, program content, and ethnic match between viewer and television characters on children's perceptions of the realism of families portrayed in television series. In the 1986-87 school year, a sample of 1,692 children in 2nd, 5th, and 10th grades completed a 13-item questionnaire measuring their…

  14. 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

  15. An Adventure in Stereochemistry: Alice in Mirror Image Land

    ERIC Educational Resources Information Center

    Dinan, Frank J.; Yee, Gordon T.

    2004-01-01

    This case is based on an article that considered the problems that would arise if a person were to cross over into a mirror-image environment (Yee 2002). Some of the stereochemistry problems posed in that article are woven into this case study. (Contains 8 figures.)

  16. 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…

  17. Image Visual Realism: From Human Perception to Machine Computation.

    PubMed

    Fan, Shaojing; Ng, Tian-Tsong; Koenig, Bryan L; Herberg, Jonathan S; Jiang, Ming; Shen, Zhiqi; Zhao, Qi

    2017-08-30

    Visual realism is defined as the extent to which an image appears to people as a photo rather than computer generated. Assessing visual realism is important in applications like computer graphics rendering and photo retouching. However, current realism evaluation approaches use either labor-intensive human judgments or automated algorithms largely dependent on comparing renderings to reference images. We develop a reference-free computational framework for visual realism prediction to overcome these constraints. First, we construct a benchmark dataset of 2520 images with comprehensive human annotated attributes. From statistical modeling on this data, we identify image attributes most relevant for visual realism. We propose both empirically-based (guided by our statistical modeling of human data) and CNN-learned features to predict visual realism of images. Our framework has the following advantages: (1) it creates an interpretable and concise empirical model that characterizes human perception of visual realism; (2) it links computational features to latent factors of human image perception.

  18. 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

  19. 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.

  20. The ontology of quantum field theory: Structural realism vindicated?

    PubMed

    Glick, David

    2016-10-01

    In this paper I elicit a prediction from structural realism and compare it, not to a historical case, but to a contemporary scientific theory. If structural realism is correct, then we should expect physics to develop theories that fail to provide an ontology of the sort sought by traditional realists. If structure alone is responsible for instrumental success, we should expect surplus ontology to be eliminated. Quantum field theory (QFT) provides the framework for some of the best confirmed theories in science, but debates over its ontology are vexed. Rather than taking a stand on these matters, the structural realist can embrace QFT as an example of just the kind of theory SR should lead us to expect. Yet, it is not clear that QFT meets the structuralist's positive expectation by providing a structure for the world. In particular, the problem of unitarily inequivalent representations threatens to undermine the possibility of QFT providing a unique structure for the world. In response to this problem, I suggest that the structuralist should endorse pluralism about structure.

  1. Violation of local realism with freedom of choice

    PubMed Central

    Scheidl, Thomas; Ursin, Rupert; Kofler, Johannes; Ramelow, Sven; Ma, Xiao-Song; Herbst, Thomas; Ratschbacher, Lothar; Fedrizzi, Alessandro; Langford, Nathan K.; Jennewein, Thomas; Zeilinger, Anton

    2010-01-01

    Bell’s theorem shows that local realistic theories place strong restrictions on observable correlations between different systems, giving rise to Bell’s inequality which can be violated in experiments using entangled quantum states. Bell’s theorem is based on the assumptions of realism, locality, and the freedom to choose between measurement settings. In experimental tests, “loopholes” arise which allow observed violations to still be explained by local realistic theories. Violating Bell’s inequality while simultaneously closing all such loopholes is one of the most significant still open challenges in fundamental physics today. In this paper, we present an experiment that violates Bell’s inequality while simultaneously closing the locality loophole and addressing the freedom-of-choice loophole, also closing the latter within a reasonable set of assumptions. We also explain that the locality and freedom-of-choice loopholes can be closed only within nondeterminism, i.e., in the context of stochastic local realism. PMID:21041665

  2. 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…

  3. 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…

  4. Applying ontological realism to medically unexplained syndromes.

    PubMed

    Doing-Harris, Kristina; Meystre, Stephane M; Samore, Matthew; Ceusters, Werner

    2013-01-01

    The past decade has witnessed an increased interest in what are called "medically unexplained syndromes" (MUS). We address the question of whether structuring the domain knowledge for MUS can be achieved by applying the principles of Ontological Realism in light of criticisms about their usefulness in areas where science has not yet led to insights univocally endorsed by the relevant communities. We analyzed whether the different perspectives held by MUS researchers can be represented without taking any particular stance and whether existing ontologies based on Ontological Realism can be further built upon. We did not find refutation of the applicability of the principles. We found the Ontology of General Medical Science and Information Artifact Ontology to provide useful frameworks for analyzing certain MUS controversies, although leaving other questions open.

  5. Increasing the realism of a laparoscopic box trainer: a simple, inexpensive method.

    PubMed

    Hull, Louise; Kassab, Eva; Arora, Sonal; Kneebone, Roger

    2010-01-01

    Simulation-based training in medical education is increasing. Realism is an integral element of creating an engaging, effective training environment. Although physical trainers offer a low-cost alternative to expensive virtual reality (VR) simulators, many lack in realism. The aim of this research was to enhance the realism of a laparoscopic box trainer by using a simple, inexpensive method. Digital images of the abdominal cavity were captured from a VR simulator. The images were printed onto a laminated card that lined the bottom and sides of the box-trainer cavity. The standard black neoprene material that encloses the abdominal cavity was replaced with a skin-colored silicon model. The realism of the modified box trainer was assessed by surgeons, using quantitative and qualitative methodologies. Results suggest that the modified box trainer was more realistic than a standard box trainer alone. Incorporating this technique in the training of laparoscopic skills is an inexpensive means of emulating surgical reality that may enhance the engagement of the learner in simulation.

  6. Increasing Realism in Virtual Marksmanship Simulators

    DTIC Science & Technology

    2012-12-01

    2) improving or enhancing a factor, such as graphics quality , will have a positive effect on a participants objective score and/or their subjective...realism of virtual marksmanship simulators, and (2) improving or enhancing a factor, such as graphics quality , will have a positive effect on a...enhance the overall simulation? H02: Improving or enhancing a factor, such as graphics quality , will have no discernible effect on a participant’s

  7. The effect of an olfactory and visual cue on realism and engagement in a health care simulation experience.

    PubMed

    Nanji, Karen C; Baca, Kirsten; Raemer, Daniel B

    2013-06-01

    Fidelity has been identified as an important element in a subject's perception of realism and engagement in learning during a simulation experience. The purpose of this study was to determine whether an isolated visual and olfactory sensory change to the simulation environment affects the subjects' perceptions of realism during simulation cases. Using an electrosurgical unit applied to bovine muscle tissue, we created a model to simulate the characteristic operating room smoke and burning odor that occur during many procedures. Anesthesiologist subjects were randomly assigned to an intervention group that participated in a simulation involving the characteristic smoke and odor or a control group whose simulation involved no smoke or odor. Subjects completed a 7-question survey on the fidelity of the simulation, their perception of realism, and their learning engagement. We enrolled 103 subjects over 22 simulation courses in our study (intervention, n = 52; control, n = 51). The subjects' reactions to the physical (P = 0.73), conceptual (P = 0.34), and emotional (P = 0.12) fidelity and their perception of realism (P = 0.71) did not differ between the intervention and control groups. In a high-fidelity simulation environment, a visual and olfactory increment to physical fidelity did not affect subjects' overall ratings of fidelity, perceptions of realism, and engagement in the learning experience.

  8. Perceived game realism: a test of three alternative models.

    PubMed

    Ribbens, Wannes

    2013-01-01

    Perceived realism is considered a key concept in explaining the mental processing of media messages and the societal impact of media. Despite its importance, little is known about its conceptualization and dimensional structure, especially with regard to digital games. The aim of this study was to test a six-factor model of perceived game realism comprised of simulational realism, freedom of choice, perceptual pervasiveness, social realism, authenticity, and character involvement and to assess it against an alternative single- and five-factor model. Data were collected from 380 male digital game users who judged the realism of the first-person shooter Half-Life 2 based upon their previous experience with the game. Confirmatory factor analysis was applied to investigate which model fits the data best. The results support the six-factor model over the single- and five-factor solutions. The study contributes to our knowledge of perceived game realism by further developing its conceptualization and measurement.

  9. 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

  10. Dynamic Stereochemistry: A Simple Approach To Delineating Relative Configuration

    NASA Astrophysics Data System (ADS)

    Mandal, Dipak K.

    2007-02-01

    The stereochemistry of reactions at a tetrahedral center in organic molecules primarily involves inversion or retention of configuration at that center. In this context, a simple approach is presented for delineating relative stereochemistry of the product in reactions involving stereogenic center(s). The configuration at a tetrahedral center is defined by a pair of ligands related by a clockwise (or counterclockwise) arc and a front (or rear) ligand. The arc is drawn through the tetrahedral angle taking the tetrahedral center as the geometric center. The inversion or retention of configuration is assigned by examining whether the clockwise counterclockwise and front rear relationships of two ligand pairs in the starting material are maintained or changed in the product. One change of such relationship would lead to inversion while retention involves either no change or changes of both the relationships. The method is illustrated with suitable examples.

  11. 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.

  12. Stereochemistry of bistricyclic aromatic enes and related polycyclic systems.

    PubMed

    Biedermann, P Ulrich; Agranat, Israel

    2014-01-01

    Bistricyclic aromatic enes (BAEs) and related polycyclic systems are a class of molecular materials that display a rich variety of conformations, dynamic stereochemistry and switchable chirality, color, and spectroscopic properties. This is due to the a subtle interplay of the inherent preference for planarity of aromatic systems and the competing necessity of non-planarity due to intramolecular overcrowding in the fjord regions built into the general molecular structure of BAEs. The conformational, dynamic, and spectroscopic properties may be designed and fine-tuned, e.g., by variation of the bridging groups X and Y, the overcrowding in the fjord regions, extensions of the aromatic system, or other modifications of the general BAE structure, based on the fundamental understanding of the structure-property relationships (SPR). The present review provides an analysis of the conformational spaces and the dynamic stereochemistry of overcrowded bistricyclic aromatic enes applying fundamental symmetry considerations. The symmetry analysis presented here allows deeper insight into the conformations, chirality, and the mechanisms of the dynamic stereochemistry, and will be instrumental in future computational studies.

  13. Handling of tautomerism and stereochemistry in compound registration.

    PubMed

    Gobbi, Alberto; Lee, Man-Ling

    2012-02-27

    Automated registration of compounds from external sources is necessitated by the numerous compound acquisitions from vendors and by the increasing number of collaborations with external partners. A prerequisite for automating compound registration is a robust module for determining the structural novelty of the input structures. Any such tool needs to be able to take uncertainty about stereochemistry into account and to identify tautomeric forms of the same compound. It also needs to validate structures for potential mistakes in connectivity and stereochemistry. Genentech has implemented a Structure Normalization Module based on toolkits offered by OpenEye Scientific Software. The module is incorporated in a graphical application for single compound registration and in scripts for bulk registration. It is also used for checking compounds submitted by our collaborators via partner-specific Internet sites. The Genentech Structure Normalization Module employs the widely used V2000 molfile format to accommodate structures received from a wide variety of sources. To determine how much information is known about the stereochemistry of each compound, the module requires a separate stereochemical assignment. A structural uniqueness check is performed by comparing the canonical SMILES of a standard tautomer. This paper offers a discussion of the steps taken to validate the chemical structure and generate the canonical SMILES of the standard tautomer. It also describes the integration of the validation module in compound registration pathways.

  14. Violation of smooth observable macroscopic realism in a harmonic oscillator.

    PubMed

    Leshem, Amir; Gat, Omri

    2009-08-14

    We study the emergence of macrorealism in a harmonic oscillator subject to consecutive measurements of a squeezed action. We demonstrate a breakdown of dynamical realism in a wide parameter range that is maximized in a scaling limit of extreme squeezing, where it is based on measurements of smooth observables, implying that macroscopic realism is not valid in the harmonic oscillator. We propose an indirect experimental test of these predictions with entangled photons by demonstrating that local realism in a composite system implies dynamical realism in a subsystem.

  15. Revised stereochemistry of ceramide-trafficking inhibitor HPA-12 by X-ray crystallography analysis.

    PubMed

    Ueno, Masaharu; Huang, Yi-Yong; Yamano, Akihito; Kobayashi, Shū

    2013-06-07

    In response to Berkeš's report revising the stereochemistry of HPA-12, an important ceramide-trafficking inhibitor that was discovered and synthesized and its stereochemistry determined in 2001, the synthesis and the stereochemistry were reinvestigated. A large-scale synthetic method for HPA-12 based on a Zn-catalyzed asymmetric Mannich-type reaction in water was developed. Single crystals of HPA-12 for X-ray crystallographic analysis were obtained from ethyl propionate/n-hexane, and the stereochemistry was definitely determined to be 1R,3S, consistent with Berkeš's revised structure.

  16. Introduction of the (-)-berkelic acid side chain and assignment of the C-22 stereochemistry.

    PubMed

    Wu, Xiaoxing; Zhou, Jingye; Snider, Barry B

    2009-08-21

    A Kiyooka aldol condensation of an aldehyde with a trimethylsilyl ketene acetal and the oxazaborolidinone prepared from N-Ts-(S)-valine gives two of the four possible aldol adducts, which were oxidized and deprotected to complete the synthesis of (-)-berkelic acid and (-)-22-epi-berkelic acid. This synthesis establishes the absolute stereochemistry and assigns the stereochemistry at C-22. A biosynthetic pathway is proposed that is consistent with the known absolute stereochemistry at the quaternary carbon of spiciferone A, spicifernin, and berkelic acid and provides a simple explanation for the differing stereochemistry at C-18 and C-19 of spicifernin and berkelic acid.

  17. On reconciling quantum mechanics and local realism

    NASA Astrophysics Data System (ADS)

    Graft, Donald A.

    2013-10-01

    Accepting nonlocal quantum correlations requires us to reject special relativity and/or probability theory. We can retain both by revising our interpretation of quantum mechanics regarding the handling of separated systems, as quantum mechanics conflicts with local realism only in its treatment of separated systems. We cannot use the joint probability formula for cases of separated measurements. We use the marginals (partial traces) together with whatever priors we have from an understanding of the system. This program can reconcile quantum mechanics with local realism. An apparent obstacle to this program is the experimental evidence, but we argue that the experiments have been misinterpreted, and that when correctly interpreted they confirm local realism. We describe a local realistic account of one important Einstein-Poldosky-Rosen-Bohm (EPRB) experiment (Weihs et al6) that claims to demonstrate nonlocal entanglement. We present a local realistic system (experiment) that can be calibrated into both quantum and classical correlation domains via adjustment of parameters (`hidden variables') of the apparatus. Weihs incorrectly dismisses these parameters as uncritical. Nonlocal entanglement is seen to be an error. The rest of quantum mechanics remains intact, and remains highly valued as a powerful probability calculus for observables. Freed from the incoherent idea of nonlocal entanglement, we can leverage powerful classical ideas, such as semiclassical radiation theory, stochastic dynamics, classical noncommutativity/contextuality, measurement effects on state, etc., to augment or complement quantum mechanics. When properly interpreted and applied, quantum mechanics lives in peaceful harmony with the local realist conception, and both perspectives offer useful paradigms for describing systems.

  18. 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.

  19. 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…

  20. 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…

  1. 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…

  2. 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…

  3. 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…

  4. 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…

  5. Ideas of Western Man: Expressionism and Realism: English, Humanities.

    ERIC Educational Resources Information Center

    Hall, Peggy; Knappe, Shirley

    The course, "Ideas of Western Man: Expressionism and Realism," involves the analysis of some predominant schools and man's changing thought through the study of literature. In studying Expressionism and Realism as they have affected contemporary American Culture, philosophy is emphasized, and painting, sculpture, and music are used for…

  6. 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 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...

  7. 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...

  8. 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...

  9. Dramaturging Non-Realism: Creating a New Vocabulary.

    ERIC Educational Resources Information Center

    Haring-Smith, Tori

    2003-01-01

    Discusses the experiences of a professional and academic dramaturg as she learns how to respond to non-realist plays. Proposes that non-realism is not simply the absence of realism but is a form in itself. Presents a vocabulary for non-realist texts. Notes that to create this vocabulary the features of its style should be defined. Discusses the…

  10. 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.

  11. 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,…

  12. 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…

  13. Total synthesis and absolute stereochemistry of the proteasome inhibitors cystargolides A and B.

    PubMed

    Tello-Aburto, Rodolfo; Hallada, Liam P; Niroula, Doleshwar; Rogelj, Snezna

    2015-10-28

    The absolute stereochemistry of the cystargolides was determined by total synthesis. Evaluation of synthetic cystargolides and derivatives showed that the natural (2S,3R) stereochemistry is essential for activity. Moreover, benzyl esters (-)-10 and (-)-15 were found to be about 100 times more potent, and to selectively kill MCF-7 cancerous cells.

  14. 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…

  15. Total Synthesis and Absolute Stereochemistry of the Proteasome Inhibitors Cystargolides A and B

    PubMed Central

    Tello-Aburto, Rodolfo; Hallada, Liam P.; Niroula, Doleshwar; Rogelj, Snezna

    2015-01-01

    The absolute stereochemistry of the cystargolides was determined by total synthesis. Evaluation of synthetic cystargolides and derivatives showed that the natural (2S,3R) stereochemistry is essential for activity. Moreover, benzyl esters (−)-10 and (−)-15 were found to be about 100 times more potent, and to selectively kill MCF-7 cancerous cells. PMID:26400369

  16. Epoxidation with Possibilities: Discovering Stereochemistry in Organic Chemistry via Coupling Constants

    ERIC Educational Resources Information Center

    Treadwell, Edward M.; Yan, Zhiqing; Xiao, Xiao

    2017-01-01

    A one-day laboratory epoxidation experiment, requiring no purification, is described, wherein the students are given an "unknown" stereoisomer of 3-hexen-1-ol, and use [superscript 1]H NMR coupling constants to determine the stereochemistry of their product. From this they work backward to determine the stereochemistry of their starting…

  17. 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,…

  18. On the Stereochemistry of the Kulinkovich Cyclopropanation of Nitriles

    PubMed Central

    Astashko, Dmitry; Lee, Hyung Goo; Bobrov, Denis N.; Cha, Jin K.

    2009-01-01

    The stereochemistry of the Kulinkovich cyclopropanation of nitriles with alkenes has been examined by employing (E)-disubstituted alkenes and deuterium-labeled homoallylic alcohols as a stereochemical probe. An intramolecular cyclopropanation proceeds with preservation of the olefin configuration. On the other hand, intermolecular counterparts occur with both preservation and reversal of the olefin configuration, which corresponds to retention and inversion of configuration at the Ti–C bond, respectively, in the cyclopropane-forming step. These uncommon stereochemical outcomes contrast with that of the Kulinkovich cyclopropanation of tertiary amides. PMID:19527011

  19. 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.

  20. Retinal vascular tree reconstruction with anatomical realism.

    PubMed

    Lin, Kai-Shun; Tsai, Chia-Ling; Tsai, Chih-Hsiangng; Sofka, Michal; Chen, Shih-Jen; Lin, Wei-Yang

    2012-12-01

    Motivated by the goals of automatically extracting vessel segments and constructing retinal vascular trees with anatomical realism, this paper presents and analyses an algorithm that combines vessel segmentation and grouping of the extracted vessel segments. The proposed method aims to restore the topology of the vascular trees with anatomical realism for clinical studies and diagnosis of retinal vascular diseases, which manifest abnormalities in either venous and/or arterial vascular systems. Vessel segments are grouped using extended Kalman filter which takes into account continuities in curvature, width, and intensity changes at the bifurcation or crossover point. At a junction, the proposed method applies the minimum-cost matching algorithm to resolve the conflict in grouping due to error in tracing. The system was trained with 20 images from the DRIVE dataset, and tested using the remaining 20 images. The dataset contained a mixture of normal and pathological images. In addition, six pathological fluorescein angiogram sequences were also included in this study. The results were compared against the groundtruth images provided by a physician, achieving average success rates of 88.79% and 90.09%, respectively.

  1. Measurement contextuality is implied by macroscopic realism

    SciTech Connect

    Chen Zeqian; Montina, A.

    2011-04-15

    Ontological theories of quantum mechanics provide a realistic description of single systems by means of well-defined quantities conditioning the measurement outcomes. In order to be complete, they should also fulfill the minimal condition of macroscopic realism. Under the assumption of outcome determinism and for Hilbert space dimension greater than 2, they were all proved to be contextual for projective measurements. In recent years a generalized concept of noncontextuality was introduced that applies also to the case of outcome indeterminism and unsharp measurements. It was pointed out that the Beltrametti-Bugajski model is an example of measurement noncontextual indeterminist theory. Here we provide a simple proof that this model is the only one with such a feature for projective measurements and Hilbert space dimension greater than 2. In other words, there is no extension of quantum theory providing more accurate predictions of outcomes and simultaneously preserving the minimal labeling of events through projective operators. As a corollary, noncontextuality for projective measurements implies noncontextuality for unsharp measurements. By noting that the condition of macroscopic realism requires an extension of quantum theory, unless a breaking of unitarity is invoked, we arrive at the conclusion that the only way to solve the measurement problem in the framework of an ontological theory is by relaxing the hypothesis of measurement noncontextuality in its generalized sense.

  2. 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.

  3. Observing Local Realism Violations with a Combination of Sensitive and Insensitive Detectors

    SciTech Connect

    Yurke, B.; Stoler, D.

    1997-12-01

    Several systems are exhibited in which the establishment of local realism violation is achieved even when some of the detectors employed are insensitive. The insensitive detectors are homodyne detectors whose task is to determine if the amplitude of a coherent state is {alpha} or {minus}{alpha} . This determination can be achieved with low quantum efficiency detectors when {vert_bar}{alpha}{vert_bar} is large. The other detectors employed determine whether there is an even number or an odd number of photons in a state. These detectors are sensitive since they are required to resolve the difference of one photon. For the examples given, the local realism violation is not diminished as {vert_bar}{alpha}{vert_bar} is increased. {copyright} {ital 1997} {ital The American Physical Society}

  4. Stereochemistry-dependent cytotoxicity of some artemisinin derivatives.

    PubMed

    Beekman, A C; Barentsen, A R; Woerdenbag, H J; Van Uden, W; Pras, N; Konings, A W; el-Feraly, F S; Galal, A M; Wikström, H V

    1997-04-01

    We determined the cytotoxicity of some artemisinin derivatives against EN2 tumor cells using the MTT assay. Artemisinin (1) was clearly more cytotoxic than deoxyartemisinin (2), which lacks the endoperoxide bridge. Ether-linked dimers of dihydroartemisinin with defined stereochemistry were found to differ in the extent of cytotoxic effect on EN2 cells. The nonsymmetrical dimer (3) was more cytotoxic than the symmetrical dimer (4). The nonsymmetrical dimer of dihydrodeoxyartemisinin (5) lacking the endoperoxide bridges was also effective in the MTT assay, although less cytotoxic than 3 and 4. Similarly, the symmetrical dimer (6) was less effective than 5. Epoxides of artemisitene also showed that stereochemistry was an important factor for cytotoxicity. The results suggested that the endoperoxide bridge was not crucial for cytotoxicity to the tumor cells, but contributed to the cytotoxic effect apparently exerted by the ether linkage of the dimers. Flow cytometry data indicated that the dimers 3 and 4 caused an accumulation of the cells in the G1-phase of the cell cycle. In contrast, artemisinin (1) caused a slight increase of S-phase cells.

  5. Complex critical realism: tenets and application in nursing research.

    PubMed

    Clark, Alexander M; Lissel, Sue L; Davis, Caroline

    2008-01-01

    To outline the main tenets of critical realism (CR), its use, and future application in nursing. Little work has been done to discuss how CR can be applied to nursing research. The tenets of CR include recognition of reality independent of human perceptions, a generative view of causation in open systems, and a focus on explanations and methodological eclecticism using a postdisciplinary approach. Critical realism is useful for (1) understanding complex outcomes, (2) optimizing interventions, and (3) researching biopsychosocial pathways. Such questions are central to evidence-based practice, chronic disease management, and population health. Critical realism is philosophically strong and potentially useful for nursing research.

  6. 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.

  7. 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

    2016-04-06

    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.

  8. 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.

  9. Functional realism: a defense of narrative medicine.

    PubMed

    Vannatta, Seth; Vannatta, Jerry

    2013-02-01

    In this paper we (1) define and describe the practice of narrative medicine, (2) reveal the need for narrative medicine by exposing the presuppositions that give rise to its discounting, including a reductive empiricism and a strict dichotomy between scientific fact and narrative value, (3) show evidence of the effects of education in narrative competence in the medical clinic, and (4) present Peircean realism as the proper conceptual model for our argument that the medical school curriculum committees should give space to the employment of the scientific and literary knowledge in medical practice. On account of our argument, we contend that the medical community should tend to latitude and openness with regard to the tools we use to resolve medical problems. These tools include both biomedical and narrative knowledge.

  10. Improving the physiological realism of experimental models

    PubMed Central

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

    2016-01-01

    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

  11. 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

  12. "How much realism is needed?" - the wrong question in silico imagers have been asking.

    PubMed

    Badano, Aldo

    2017-05-01

    To discuss the use of realism as a first approximation for assessing computational imaging methods. Although in silico methods are increasingly becoming promising surrogates to physical experimentation for various stages of device development, their acceptance remains challenging. Realism is often considered as a first approximation for assessing computational imaging methods. However, realism is subjective and does not always ensure that key features of the methodologies reflect relevant aspects of devices of interest to imaging scientists, regulators, and medical practitioners. Moreover, in some cases (e.g., in computerized image analysis applications where human interpretation is not needed) how realistic in silico images are is irrelevant and perhaps misleading. I emphasize a divergence from this methodology by providing a rationale for evaluating in silico imaging methods and tools in an objective and measurable manner. Improved approaches for in silico imaging will lead to the rapid advancement and acceptance of computational techniques in medical imaging primarily but not limited to the regulatory evaluation of new imaging products. Published 2017. This article is a U.S. Government work and is in the public domain in the USA.

  13. Critical realism: an important theoretical perspective for midwifery research.

    PubMed

    Walsh, Denis; Evans, Kerry

    2014-01-01

    there is a dearth of papers in midwifery journals exploring the philosophical underpinnings of various research methods. However, explaining and justifying particular ontological and epistemological positions gives coherence and credibility to chosen research methods. to explore and explain the philosophical underpinning of critical realism and argue for it to be more widely adopted by midwifery researchers, using the exemplar of dystocia research. critical realism as originally espoused by Bhaskar sees reality as layered (realist ontology) and seeks to explore causative mechanisms for what is experienced and observed. In this way it illuminates the complexity of health care, though recognising that knowledge of this complexity is filtered through an interpretive lens (constructionist epistemology). Critical realism encourages a holistic exploration of phenomena, premised on multiple research questions that utilise multiple research methods. critical realism as a philosophical underpinning is therefore particularly apposite for researching midwifery issues and concerns. © 2013 Elsevier Ltd. All rights reserved.

  14. 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.

  15. Cost Realism Handbook for Assuring More Realistic Contractor Cost Proposals

    DTIC Science & Technology

    1985-05-01

    realism. Solicitation: Specify cost realism in addition ,:) Government estimated cost as cost evaluation sub- - ieria in the solicitation and specify the...Analogy techniques involve extrapolations from actual costs for similar systems. Other techniques may include the use of industry wide factors. Parametric...of sources (e.g., actual costs for similar systems and industry wide factors) may be used to supplement the estimates based on specific contractor

  16. Buried chloride stereochemistry in the Protein Data Bank

    PubMed Central

    2014-01-01

    Background Despite the chloride anion is involved in fundamental biological processes, its interactions with proteins are little known. In particular, we lack a systematic survey of its coordination spheres. Results The analysis of a non-redundant set (pairwise sequence identity?stereochemistry is closer to the expected geometry when the coordination number is 5, suggesting that this is the coordination number towards which the chlorides tend when they interact with proteins. Conclusions The results of these analyses are useful in interpreting, describing, and validating new protein crystal structures that contain chloride anions. PMID:25928393

  17. Relationships between the stereochemistry and biological activity of fungal phytotoxins.

    PubMed

    Evidente, Antonio; Andolfi, Anna; Cimmino, Alessio

    2011-10-01

    Toxins produced by phytopathogenic fungi assume great importance because of their involvement in several plant diseases. Although such pathogens are known to have seriously damaged crops, forest, and environmental resources, they represent a very important tool to develop new environmentally friendly herbicides and fungicides. This review deals with the relationships between the biological activity of some phytotoxins produced by pathogenic fungi for major forest plants and for damaging weeds and their stereochemistry. In particular, the methods used to determine their relative and/or absolute configuration will be illustrated. These include the application of Mosher's and Murata's methods, X-ray diffractometric analysis, circular dichroism, and the use of computational methods to determine the theoretical optical rotatory power as well as the CD spectrum. The importance of determining the absolute configuration to achieve the total synthesis of some phytotoxins, interesting for their potential practical application, is also discussed.

  18. The importance of realism in reservoir operation optimisation

    NASA Astrophysics Data System (ADS)

    Dobson, Barnaby

    2017-04-01

    In previous work, we find that one of the most important barriers to uptake of reservoir operation optimisation methods in practice is the focus on sophisticated optimisation techniques at the expense of realism in problem formulation. Water resource management problems may be simplified to improve optimisation or even just to aid method explanation, however this does not foster faith about the applicability of its solution in real-world. We aim to make the first step towards developing a methodology to identify the trade-off between estimated performance within the optimisation model and actual performance when the 'optimal' solutions are implemented in practice. We start by robustly optimising reservoir operation policies over a wide range of inflow scenarios and confirming whether this optimal performance estimate is robust under a wider range of input forcing and model structure uncertainties. Model structure uncertainties are addressed, for example, through increased temporal resolution and inclusion of more sophisticated physical representations such as water head, losses and maintenance. Demand uncertainty will be considered in a similar manner to inflow uncertainty through use of an ensemble of synthetic demand time series. A longer-term goal and extension of this study is to investigate how to incorporate such wider uncertainties directly into the optimisation process itself.

  19. Van't Hoff, Le Bel, and the Development of Stereochemistry: A Reassessment.

    ERIC Educational Resources Information Center

    Grossman, Robert B.

    1989-01-01

    Shows that two theories of stereochemistry were very different theories, grounded in different assumptions and were intended to explain different phenomena. Presents the original theories and later developments which caused a blending of the theories. (Author/MVL)

  20. Van't Hoff, Le Bel, and the Development of Stereochemistry: A Reassessment.

    ERIC Educational Resources Information Center

    Grossman, Robert B.

    1989-01-01

    Shows that two theories of stereochemistry were very different theories, grounded in different assumptions and were intended to explain different phenomena. Presents the original theories and later developments which caused a blending of the theories. (Author/MVL)

  1. 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)

  2. 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)

  3. 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.

  4. 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.

  5. 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

  6. Absolute Stereochemistry of 1,2-Diols from Lipids of Thermomicrobia.

    PubMed

    Lagutin, Kirill; Wong, Herbert; Vyssotski, Mikhail; MacKenzie, Andrew

    2016-03-01

    1,2-Diol based phospholipids are a well-known feature of bacteria from the class Thermomicrobia. Since these bacteria contain only lipids with an alkyldiol-1-phosphate backbone instead of sn-glycero-3-phosphate, it is important to elucidate the stereochemistry of the 1,2-diols. We have studied the absolute stereochemistry of long-chain 1,2-diols isolated from Thermorudis pharmacophila (formerly known as Thermomicrobia sp. WKT50.2) by nuclear magnetic resonance (NMR) using α-methoxyphenylacetic acid (MPA). Low-temperature (-60 °C) NMR of bis-(R)-MPA ester showed (R) stereochemistry of the 1,2-diols. This is the first report concerning the stereochemistry of natural 1,2-diols, which replace the glyceride moiety in phospholipids. The (R) stereochemistry of the diols is expected as it is the same configuration as for the common bacterial lipid backbone-sn-glycero-3-phosphate. This is the first application of low-temperature NMR of a single MPA derivative for assignment of stereochemistry of natural 1,2-diols. The results were confirmed by the comparison of NMR data with bis-(R)-MPA ester of (R) and rac-1,2-octanediol.

  7. Brain networks, structural realism, and local approaches to the scientific realism debate.

    PubMed

    Yan, Karen; Hricko, Jonathon

    2017-08-01

    We examine recent work in cognitive neuroscience that investigates brain networks. Brain networks are characterized by the ways in which brain regions are functionally and anatomically connected to one another. Cognitive neuroscientists use various noninvasive techniques (e.g., fMRI) to investigate these networks. They represent them formally as graphs. And they use various graph theoretic techniques to analyze them further. We distinguish between knowledge of the graph theoretic structure of such networks (structural knowledge) and knowledge of what instantiates that structure (nonstructural knowledge). And we argue that this work provides structural knowledge of brain networks. We explore the significance of this conclusion for the scientific realism debate. We argue that our conclusion should not be understood as an instance of a global structural realist claim regarding the structure of the unobservable part of the world, but instead, as a local structural realist attitude towards brain networks in particular. And we argue that various local approaches to the realism debate, i.e., approaches that restrict realist commitments to particular theories and/or entities, are problematic insofar as they don't allow for the possibility of such a local structural realist attitude. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. 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.

  9. Time perception and depressive realism: judgment type, psychophysical functions and bias.

    PubMed

    Kornbrot, Diana E; Msetfi, Rachel M; Grimwood, Melvyn J

    2013-01-01

    The effect of mild depression on time estimation and production was investigated. Participants made both magnitude estimation and magnitude production judgments for five time intervals (specified in seconds) from 3 sec to 65 sec. The parameters of the best fitting psychophysical function (power law exponent, intercept, and threshold) were determined individually for each participant in every condition. There were no significant effects of mood (high BDI, low BDI) or judgment (estimation, production) on the mean exponent, n = .98, 95% confidence interval (.96-1.04) or on the threshold. However, the intercept showed a 'depressive realism' effect, where high BDI participants had a smaller deviation from accuracy and a smaller difference between estimation and judgment than low BDI participants. Accuracy bias was assessed using three measures of accuracy: difference, defined as psychological time minus physical time, ratio, defined as psychological time divided by physical time, and a new logarithmic accuracy measure defined as ln (ratio). The ln (ratio) measure was shown to have approximately normal residuals when subjected to a mixed ANOVA with mood as a between groups explanatory factor and judgment and time category as repeated measures explanatory factors. The residuals of the other two accuracy measures flagrantly violated normality. The mixed ANOVAs of accuracy also showed a strong depressive realism effect, just like the intercepts of the psychophysical functions. There was also a strong negative correlation between estimation and production judgments. Taken together these findings support a clock model of time estimation, combined with additional cognitive mechanisms to account for the depressive realism effect. The findings also suggest strong methodological recommendations.

  10. Stereochemistry of ulapualides, a new family of tris-oxazole-containing macrolide ionophores from marine nudibranchs. A molecular mechanics study

    NASA Astrophysics Data System (ADS)

    Maddock, John; Pattenden, Gerald; Wight, Paul G.

    1993-10-01

    A molecular mechanics study of the marine metabolite ulapualide A, which is suggested to have ionophorie properties, has been carried out on various metal chelated complexes in order to predict the stereochemistry of the natural product. The results suggest a stereochemistry for ulapualide A which is closely similar to structurally related marine metabolites, whose stereochemistries have been established by X-ray crystallography and by partial synthesis.

  11. Comparison of Insect Kinin Analogs With cis-Peptide Bond Motif 4-Aminopyroglutamate Identifies Optimal Stereochemistry for Diuretic Activity

    DTIC Science & Technology

    2006-01-01

    Comparison of Insect Kinin Analogs With cis-Peptide Bond Motif 4-Aminopyroglutamate Identifies Optimal Stereochemistry for Diuretic Activity...the other three variants, which may explain its greater potency. The work identifies the optimal stereochemistry for the APy scaffold with which to...Comparison of Insect Kinin Analogs With cis-Peptide Bond Motif 4-Aminopyroglutamate Identifies Optimal Stereochemistry for Diuretic Activity Correspondence to

  12. 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.

  13. Two Potent OXE-R Antagonists: Assignment of Stereochemistry

    PubMed Central

    2014-01-01

    5-Oxo-6,8,11,14-eicosatetraenoic acid (5-oxo-ETE) is formed by the oxidation of 5-hydroxy-6E,8Z,11Z,14Z-eicosatetraenoic acid (5-HETE), which is a major metabolite of enzymatic oxidation of arachidonic acid (AA). 5-Oxo-ETE is the most potent lipid chemoattractant for human eosinophils. Its actions are mediated by the selective OXE receptor, which is therefore an attractive target in eosinophilic diseases such as allergic rhinitis and asthma. Recently, we have reported two excellent OXE receptor antagonists that have IC50 values at low nanomolar concentrations. Each of these antagonists has a chiral center, and the isolation of the individual enantiomers by chiral high-performance liquid chromatography (HPLC) revealed that in each case one enantiomer is over 300 times more potent than the other. To unambiguously assign the stereochemistry of these enantiomers and to provide access to larger amounts of the active compounds for biological testing, we report here their total synthesis. PMID:25050171

  14. Effects of stereochemistry and copolymerization on the LCST of PNIPAm

    NASA Astrophysics Data System (ADS)

    de Oliveira, Tiago E.; Mukherji, Debashish; Kremer, Kurt; Netz, Paulo A.

    2017-01-01

    Poly(N-isopropylacrylamide) (PNIPAm) is a smart polymer that presents a lower critical transition temperature (LCST) of 305 K. Interestingly, this transition point falls within the range of the human body temperature, making PNIPAm a highly suitable candidate for bio-medical applications. However, it is sometimes desirable to have a rather flexible tuning of the LCST of these polymers to further increase their range of applications. In this work, we use all-atom molecular dynamics simulations to study the LCST of PNIPAm-based (co-)polymers. We study different molecular architectures where the polymer sequences are tuned either by modifying its stereochemistry or by the co-polymerization of PNIPAm with acrylamide (Am) units. Our analysis connects global polymer conformations with the microscopic intermolecular interactions. These findings suggest that the collapse of a PNIPAm chain upon heating is dependent on the hydration structure around the monomers, which is strongly dependent on the tacticity and the presence of more hydrophilic acrylamide monomers. Our results are found to be in good agreement with the existing experimental data.

  15. Effects of stereochemistry and copolymerization on the LCST of PNIPAm.

    PubMed

    de Oliveira, Tiago E; Mukherji, Debashish; Kremer, Kurt; Netz, Paulo A

    2017-01-21

    Poly(N-isopropylacrylamide) (PNIPAm) is a smart polymer that presents a lower critical transition temperature (LCST) of 305 K. Interestingly, this transition point falls within the range of the human body temperature, making PNIPAm a highly suitable candidate for bio-medical applications. However, it is sometimes desirable to have a rather flexible tuning of the LCST of these polymers to further increase their range of applications. In this work, we use all-atom molecular dynamics simulations to study the LCST of PNIPAm-based (co-)polymers. We study different molecular architectures where the polymer sequences are tuned either by modifying its stereochemistry or by the co-polymerization of PNIPAm with acrylamide (Am) units. Our analysis connects global polymer conformations with the microscopic intermolecular interactions. These findings suggest that the collapse of a PNIPAm chain upon heating is dependent on the hydration structure around the monomers, which is strongly dependent on the tacticity and the presence of more hydrophilic acrylamide monomers. Our results are found to be in good agreement with the existing experimental data.

  16. Designed beta-hairpin peptides with defined tight turn stereochemistry.

    PubMed

    Das, C; Naganagowda, G A; Karle, I L; Balaram, P

    2001-03-01

    The conformational analysis of two synthetic octapeptides, Boc-Leu-Val-Val-D-Pro-L-Ala-Leu-Val-Val-OMe (1) and Boc-Leu-Val-Val-D-Pro-D-Ala-Leu-Val-Val-OMe (2) has been carried out in order to investigate the effect of beta-turn stereochemistry on designed beta-hairpin structures. Five hundred megahertz (1)H NMR studies establish that both peptides 1 and 2 adopt predominantly beta-hairpin conformations in methanol solution. Specific nuclear Overhauser effects provide evidence for a type II' beta-turn conformation for the D-Pro-L-Ala segment in 1, while the NMR data suggest that the type I' D-Pro-D-Ala beta-turn conformation predominates in peptide 2. Evidence for a minor conformation in peptide 2, in slow exchange on the NMR time scale, is also presented. Interstrand registry is demonstrated in both peptides 1 and 2. The crystal structure of 1 reveals two independent molecules in the crystallographic asymmetric unit, both of which adopt beta-hairpin conformations nucleated by D-Pro-L-Ala type II' beta-turns and are stabilized by three cross-strand hydrogen bonds. CD spectra for peptides 1 and 2 show marked differences, presumably as a consequence of the superposition of spectral bands arising from both beta-turn and beta-strand conformations. Copyright 2001 John Wiley & Sons, Inc.

  17. Stereochemistry of the acyl dihydroxyacetone phosphate acyl exchange reaction.

    PubMed

    Friedberg, S J; Satsangi, N; Weintraub, S T

    1991-02-01

    The fatty acid of acyl dihydroxyacetone phosphate can be exchanged enzymatically for another fatty acid. It has been shown that this reaction proceeds by cleavage of the oxygen bound to C-1 of the dihydroxyacetone phosphate (DHAP) moiety rather than by the more common cleavage at the acyl to oxygen bond. In the present study, the stereochemistry of this reaction was defined further; using deuterated substrates and fast atom bombardment-mass spectrometry, it was shown that the fatty acid exchange involves the stereospecific labilization of the pro-R hydrogen at C-1 of the DHAP moiety of acyl DHAP. The mechanism of ether bond formation, in which acyl DHAP is converted to O-alkyl DHAP, also proceeds via labilization of the pro-R hydrogen and cleavage of the fatty acid at the C-1 to oxygen bond. In addition, other workers have provided evidence that the enzyme responsible for the exchange reaction is O-alkyl DHAP synthetase. Therefore, the present results support the hypothesis that the acyl exchange is the reverse reaction of the first step in O-alkyl DHAP synthesis; in both of these reactions the pro-R hydrogen of C-1 of the DHAP moiety of acyl DHAP and the fatty acid moiety are labilized with cleavage of the fatty acid at the DHAP C-1 to oxygen bond.

  18. Stereochemistry in self-assembled encapsulation complexes: Constellational isomerism

    PubMed Central

    Yamanaka, Masamichi; Shivanyuk, Alexander; Rebek, Julius

    2004-01-01

    A previously uncharacterized form of stereochemistry, constellational isomerism, is described. The isomerism arises from different arrangements of small-molecule guests in the space of a self-assembled, cylindrical host. The cylindrical host detains three molecules each of CHCl3, 1,2-dichloroethane, or isopropyl chloride. The exchange of guests in and out of the host is slow on the NMR time scale. The dimensions of the capsular host and the sizes of the guests hinder the mobility of molecules inside, and separate NMR signals are seen for guests at the ends of the capsule and those near its center. When two different guests are encapsulated, the spectra show up to four additional species: two sets of constellational isomers. In every pairwise combination of the three guests, all isomers could be identified. The equilibrium distributions of isomers depended on the concentrations of the guests in the bulk solution. The relative stability of the constellational isomers was a function of the polarity of the guest molecule and its ability to interact with the components of the capsule. The different arrangements represent information, and some possibilities for their use in data storage are proposed. PMID:14981269

  19. Structure elucidation and absolute stereochemistry of isomeric monoterpene chromane esters.

    PubMed

    Batista, João M; Batista, Andrea N L; Mota, Jonas S; Cass, Quezia B; Kato, Massuo J; Bolzani, Vanderlan S; Freedman, Teresa B; López, Silvia N; Furlan, Maysa; Nafie, Laurence A

    2011-04-15

    Six novel monoterpene chromane esters were isolated from the aerial parts of Peperomia obtusifolia (Piperaceae) using chiral chromatography. This is the first time that chiral chromane esters of this kind, ones with a tethered chiral terpene, have been isolated in nature. Due to their structural features, it is not currently possible to assess directly their absolute stereochemistry using any of the standard classical approaches, such as X-ray crystallography, NMR, optical rotation, or electronic circular dichroism (ECD). Herein we report the absolute configuration of these molecules, involving four chiral centers, using vibrational circular dichroism (VCD) and density functional theory (DFT) (B3LYP/6-31G*) calculations. This work further reinforces the capability of VCD to determine unambiguously the absolute configuration of structurally complex molecules in solution, without crystallization or derivatization, and demonstrates the sensitivity of VCD to specify the absolute configuration for just one among a number of chiral centers. We also demonstrate the sufficiency of using the so-called inexpensive basis set 6-31G* compared to the triple-ζ basis set TZVP for absolute configuration analysis of larger molecules using VCD. Overall, this work extends our knowledge of secondary metabolites in plants and provides a straightforward way to determine the absolute configuration of complex natural products involving a chiral parent moiety combined with a chiral terpene adduct.

  20. 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.

  1. 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)

  2. 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,…

  3. 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,…

  4. 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)

  5. 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.…

  6. 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.…

  7. 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.

  8. Total Synthesis, Assignment of the Relative and Absolute Stereochemistry, and Structural Reassignment of Phostriecin (aka Sultriecin)

    PubMed Central

    Burke, Christopher P.; Haq, Nadia; Boger, Dale L.

    2010-01-01

    A total synthesis of phostriecin (2) previously known as sultriecin (1), its structural reassignment as a phosphate versus sulfate monoester, and the assignment of its relative and absolute stereochemistry are disclosed herein. Key elements of the work, which provided first the originally assigned sulfate monoester 1 and then the reassigned and renamed phosphate monoester 2, relied on diagnostic 1H NMR spectroscopic properties of the natural product for the assignment of relative and absolute stereochemistry as well as the subsequent structural reassignment, and a convergent asymmetric total synthesis to provide the unequivocal authentic materials. Key steps of the synthetic approach include a Brown allylation for diastereoselective introduction of the C9 stereochemistry, an asymmetric CBS reduction to establish the lactone C5-stereochemistry, diastereoselective oxidative ring expansion of an α-hydroxyfuran to access the pyran lactone precursor, and single-step installation of the sensitive Z,Z,E-triene unit through a chelation-controlled cuprate addition with installation of the C11 stereochemistry. The approach allows ready access to analogues that can now be used to probe important structural features required for PP2A inhibition, the mechanism of action defined herein. PMID:20108904

  9. Total synthesis, assignment of the relative and absolute stereochemistry, and structural reassignment of phostriecin (aka Sultriecin).

    PubMed

    Burke, Christopher P; Haq, Nadia; Boger, Dale L

    2010-02-24

    A total synthesis of phostriecin (2), previously known as sultriecin (1), its structural reassignment as a phosphate versus sulfate monoester, and the assignment of its relative and absolute stereochemistry are disclosed herein. Key elements of the work, which provided first the originally assigned sulfate monoester 1 and then the reassigned and renamed phosphate monoester 2, relied on diagnostic (1)H NMR spectroscopic properties of the natural product for the assignment of relative and absolute stereochemistry as well as the subsequent structural reassignment, and a convergent asymmetric total synthesis to provide the unequivocal authentic materials. Key steps of the synthetic approach include a Brown allylation for diastereoselective introduction of the C9 stereochemistry, an asymmetric CBS reduction to establish the lactone C5-stereochemistry, diastereoselective oxidative ring expansion of an alpha-hydroxyfuran to access the pyran lactone precursor, and single-step installation of the sensitive Z,Z,E-triene unit through a chelation-controlled cuprate addition with installation of the C11 stereochemistry. The approach allows ready access to analogues that can now be used to probe important structural features required for protein phosphatase 2A inhibition, the mechanism of action defined herein.

  10. 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…

  11. 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:…

  12. 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…

  13. 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…

  14. Navigating through virtual environments: visual realism improves spatial cognition.

    PubMed

    Meijer, Frank; Geudeke, Branko L; van den Broek, Egon L

    2009-10-01

    Recent advances in computer technology have significantly facilitated the use of virtual environments (VE) for small and medium enterprises (SME). However, achieving visual realism in such VE requires high investments in terms of time and effort, while its usefulness has not yet become apparent from research. Other qualities of VE, such as the use of large displays, proved its effectiveness in enhancing the individual user's spatial cognition. The current study assessed whether the same benefits apply for visual realism in VE. Thirty-two participants were divided into two groups, who explored either a photorealistic or a nonrealistic supermarket presented on a large screen. The participants were asked to navigate through the supermarket on a predetermined route. Subsequently, spatial learning was tested in four pen-and-paper tests that assessed how accurately they had memorized the route and the environment's spatial layout. The study revealed increased spatial learning from the photorealistic compared to the nonrealistic supermarket. Specifically, participants performed better on tests that involved egocentric spatial knowledge. The results suggest visual realism is useful because it increases the user's spatial knowledge in the VE. Therefore, the current study provides clear evidence that it is worthwhile for SME to invest in achieving visual realism in VE.

  15. 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:…

  16. The role of testing realism on experimentally obtained stereotype strength.

    PubMed

    Hoffmann, Errol R; Whitfield, Richard C

    2011-01-01

    It has been shown (Hoffmann 2009) that pencil-and-paper tests, when used to determine stereotype strength, may yield data quite different to that obtained from hardware tests. The purpose of this research was to determine the level of realism required in order to have stereotypes that are consistent with real-world values. It is surprising that there does not appear to be any published research addressing this problem; all previous researches have considered either paper/pencil or hardware tests or sometimes both, but no level of simulation in between these techniques. In order to determine the effect of level of testing realism, a specific example was chosen to test, that of water tap operation stereotypes. Tests used verbal questioning, photographs of tap arrangements, a partial hardware arrangement and finally a full hardware setup. The results of these four levels of realism were very different and illustrated that, only with a full realistic simulation, did participants respond as might be expected in a real-world environment, illustrating the importance of testing realism when determining population stereotypes. This result has strong implications for product designers when selecting appropriate layouts of displays and controls and the linkages relating these.

  17. 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.

  18. Still Playing It Safe: Restricted Realism in Teen Novels

    ERIC Educational Resources Information Center

    Abramson, Jane

    1976-01-01

    The restrictions on teen fiction result in books that succeed only in mirroring a slick surface realism that too often acts as a cover-up. It disguises the fact that, at their core, most realistic novels are unrealistic and, far worse, dishonest. (Author)

  19. A New Sort of Realism in Poetry--Part 2.

    ERIC Educational Resources Information Center

    Livingston, Myra Cohn

    1995-01-01

    Discusses challenges to realistic poetry in school libraries. Addresses what New Realism is being accepted today in the world of poetry. Discusses the author's experiences in dealing with a publisher who wanted a book of poetry about jolly parents and patient grandparents, not a book about families as they really are. (RS)

  20. 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…

  1. 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…

  2. 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)

  3. 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.

  4. 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)

  5. 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)

  6. Critical Realism: An Emancipatory Philosophy for Applied Linguistics.

    ERIC Educational Resources Information Center

    Corson, David

    1997-01-01

    Presents six areas in applied linguistics that might be reformed: (1) the hegemonic nature of theories; (2) dictionary-making; (3) language planning; (4) linguistic nomenclatures; (5) the treatment of standard and non-standard varieties; and (6) the delivery of second language programs. Argues that if critical realism guided applied linguistics,…

  7. Evaluating Ketoreductase Exchanges as a Means of Rationally Altering Polyketide Stereochemistry.

    PubMed

    Annaval, Thibault; Paris, Cédric; Leadlay, Peter F; Jacob, Christophe; Weissman, Kira J

    2015-06-15

    Modular polyketide synthases (PKSs) are multidomain multienzymes responsible for the biosynthesis in bacteria of a wide range of polyketide secondary metabolites of clinical value. The stereochemistry of these molecules is an attractive target for genetic engineering in attempts to produce analogues exhibiting novel therapeutic properties. The exchange of ketoreductase (KR) domains in model PKSs has been shown in several cases to predictably alter the configuration of the β-hydroxy functionalities but not of the α-methyl groups. By systematic screening of a broad panel of KR domains, we have identified two donor KRs that afford modification of α-methyl group stereochemistry. To the best of our knowledge, this provides the first direct in vivo evidence of KR-catalyzed epimerization. However, none of the introduced KRs afforded simultaneous alteration of methyl and hydroxy configurations in high yield. Therefore, swapping of whole modules might be necessary to achieve such changes in stereochemistry.

  8. Revision of the stereochemistry of elisabethatriene, a putative biosynthetic intermediate of pseudopterosins.

    PubMed

    Nasuda, Masayuki; Ohmori, Miho; Ohyama, Kiyoshi; Fujimoto, Yoshinori

    2012-01-01

    In the past, we have questioned the accuracy of the stereochemistry of elisabethatriene, a putative biosynthetic intermediate of pseudopterosins, in light of the configuration of elisabethatrienol isolated from Pseudopterogorgia elisabethae, which was represented as 1S,4R,9S,11S. We have reinvestigated the stereochemistry of elisabethatriene. Elisabethatriene with the reported 1S,4R,9R,11S configuration was synthesized starting from (-)-isopulegol in its enantiomeric form. The (1)H- and (13)C-NMR data of the synthesized compound differed from those reported for elisabethatriene. In addition to the fact that elisabethatriene is converted into pseudopterosins, this finding has allowed us to propose that elisabethatriene should have the 1S,4R,9S,11S stereochemistry, which is identical to that of elisabethatrienol.

  9. Quantum Realism, Information, and Epistemological Modesty

    NASA Astrophysics Data System (ADS)

    Grinbaum, Alexei

    2014-03-01

    It is usually asserted that physical theories, in particular quantum mechanics, support a certain view of what the world really is. To such claims I oppose an attitude of epistemological modesty. Ontological statements on the nature of reality, when made on the basis of quantum mechanics, appear unwarranted. I suggest that an epistemic loop connects physical theory grounded in informational notions, and a theory of information developed through a theoretical account of the physical support of information.

  10. Bringing critical realism to nursing practice: Roy Bhaskar's contribution.

    PubMed

    Williams, Lynne; Rycroft-Malone, Jo; Burton, Christopher R

    2017-04-01

    In the context of modern nursing practice that is embedded within complex social situations, critical discussions about the contribution of major philosophers are relevant and important. Whilst nurse theorists have advanced and shaped nursing as a discipline, other major philosophers can offer much to advance nursing enquiry. In this paper, we focus on philosopher Roy Bhaskar who, amongst others, developed critical realism, a philosophy for social science which connects with how many of us think about the world. Bhaskar's work focuses our attention on the interplay between structure and agency and on the search for the causative or generative mechanisms that explain the social world. Bhaskar was interested in human emancipation, and we suggest his work is of great importance to advance understanding of complex social situations. Critical realism has already been endorsed by a range of disciplines, especially in research which focuses on real problems and acknowledges the complexities of the social world. In recent evidence from healthcare literature, there has been a surge in research using realist methodology (realist evaluation and realist synthesis), which is underpinned by the philosophy of critical realism and which offers a different perspective to understanding nursing and healthcare problems through the realist lens. However, we suggest that sufficient attention is not always paid to the philosophical roots of this methodology. In this paper, we provide insight into Bhaskar's work and demonstrate how research positioned within critical realism and realist methodology can advance nursing and healthcare-related knowledge. Through shining a light on Bhaskar, we illustrate how critical realism philosophy is a natural fit with human and health science enquiry, including nursing. © 2016 John Wiley & Sons Ltd.

  11. Determination of the absolute stereochemistry of limonene and alpha-santalol by Raman optical activity spectroscopy.

    PubMed

    Sakamoto, Akira; Ohya, Nao; Hasegawa, Toshio; Izumi, Hiroaki; Tokita, Nakako; Hamada, Yoshiaki

    2012-04-01

    Determining the absolute stereochemistry of organic compounds in solution remains a challenge. We investigated the use of Raman optical activity (ROA) spectroscopy to address this problem. The absolute configurations of (+)-(R)- and (-)-(S)-limonene were determined by ROA spectroscopy, which can be applied to smaller amounts of sample as compared with vibrational circular dichroism (VCD) spectroscopy. This ROA method was also applied to (+)-(E)-alpha-santalol and shown to be successful in the determination of the absolute configuration of this compound. ROA spectroscopy shows promise as a useful tool for determining the absolute stereochemistry of many natural compounds.

  12. Determination of absolute stereochemistry, total synthesis, and evaluation of peptides from the myxomycete Physarum melleum.

    PubMed

    Hanazawa, Shuwa; Arai, Midori A; Li, Xiaofan; Ishibashi, Masami

    2008-01-01

    The absolute stereochemistry of melleumin A (1) and B (2), novel peptide compounds isolated from the myxomycete Physarum melleum, was determined by synthesis of their segments and by a modified Mosher's method. Total synthesis of melleumin B (2) was achieved by a stereoselective method, which provided further evidence for all the absolute stereochemistries of melleumin B (2). The Wnt signal inhibitory activities of 2 and its 10R-epimer 19 were evaluated. Compound 19 showed moderate inhibition of Wnt signal transcription, which suggests that melleumin analogues might be useful as Wnt signal inhibitors.

  13. 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.

  14. The effects of visual realism on search tasks in mixed reality simulation.

    PubMed

    Lee, Cha; Rincon, Gustavo A; Meyer, Greg; Höllerer, Tobias; Bowman, Doug A

    2013-04-01

    In this paper, we investigate the validity of Mixed Reality (MR) Simulation by conducting an experiment studying the effects of the visual realism of the simulated environment on various search tasks in Augmented Reality (AR). MR Simulation is a practical approach to conducting controlled and repeatable user experiments in MR, including AR. This approach uses a high-fidelity Virtual Reality (VR) display system to simulate a wide range of equal or lower fidelity displays from the MR continuum, for the express purpose of conducting user experiments. For the experiment, we created three virtual models of a real-world location, each with a different perceived level of visual realism. We designed and executed an AR experiment using the real-world location and repeated the experiment within VR using the three virtual models we created. The experiment looked into how fast users could search for both physical and virtual information that was present in the scene. Our experiment demonstrates the usefulness of MR Simulation and provides early evidence for the validity of MR Simulation with respect to AR search tasks performed in immersive VR.

  15. Biosynthesis of isoprenoids in Escherichia coli: stereochemistry of the reaction catalyzed by farnesyl diphosphate synthase.

    PubMed

    Leyes, A E; Baker, J A; Poulter, C D

    1999-10-07

    [formula: see text] Farnesyl diphosphate (FPP) synthase from Escherichia coli catalyzes the condensation of isopentenyl diphosphate (IPP) and geranyl diphosphate (GPP) with selective removal of the pro-R hydrogen at C2 of IPP, the same stereochemistry observed for the pig liver, yeast, and avian enzymes.

  16. 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…

  17. 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…

  18. Hexuronic acid stereochemistry determination in chondroitin sulfate glycosaminoglycan oligosaccharides by electron detachment dissociation.

    PubMed

    Leach, Franklin E; Ly, Mellisa; Laremore, Tatiana N; Wolff, Jeremy J; Perlow, Jacob; Linhardt, Robert J; Amster, I Jonathan

    2012-09-01

    Electron detachment dissociation (EDD) has previously provided stereo-specific product ions that allow for the assignment of the acidic C-5stereochemistry in heparan sulfate glycosaminoglycans (GAGs), but application of the same methodology to an epimer pair in the chondroitin sulfate glycoform class does not provide the same result. A series of experiments have been conducted in which glycosaminoglycan precursor ions are independently activated by electron detachment dissociation (EDD), electron induced dissociation (EID), and negative electron transfer dissociation (NETD) to assign the stereochemistry in chondroitin sulfate (CS) epimers and investigate the mechanisms for product ion formation during EDD in CS glycoforms. This approach allows for the assignment of electronic excitation products formed by EID and detachment products to radical pathways in NETD, both of which occur simultaneously during EDD. The uronic acid stereochemistry in electron detachment spectra produces intensity differences when assigned glycosidic and cross-ring cleavages are compared. The variations in the intensities of the doubly deprotonated (0,2)X(3) and Y(3) ions have been shown to be indicative of CS-A/DS composition during the CID of binary mixtures. These ions can provide insight into the uronic acid composition of binary mixtures in EDD, but the relative abundances, although reproducible, are low compared with those in a CID spectrum acquired on an ion trap. The application of principal component analysis (PCA) presents a multivariate approach to determining the uronic acid stereochemistry spectra of these GAGs by taking advantage of the reproducible peak distributions produced by electron detachment.

  19. 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.…

  20. 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.…

  1. 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…

  2. 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.

  3. [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.

  4. Adding computationally efficient realism to Monte Carlo turbulence simulation

    NASA Technical Reports Server (NTRS)

    Campbell, C. W.

    1985-01-01

    Frequently in aerospace vehicle flight simulation, random turbulence is generated using the assumption that the craft is small compared to the length scales of turbulence. The turbulence is presumed to vary only along the flight path of the vehicle but not across the vehicle span. The addition of the realism of three-dimensionality is a worthy goal, but any such attempt will not gain acceptance in the simulator community unless it is computationally efficient. A concept for adding three-dimensional realism with a minimum of computational complexity is presented. The concept involves the use of close rational approximations to irrational spectra and cross-spectra so that systems of stable, explicit difference equations can be used to generate the turbulence.

  5. Strong Loophole-Free Test of Local Realism*

    NASA Astrophysics Data System (ADS)

    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

    2015-12-01

    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.

  6. Stereochemistry of 1,2-elimination and proton-transfer reactions: toward a unified understanding.

    PubMed

    Mohrig, Jerry R

    2013-07-16

    Many mechanistic and stereochemical studies have focused on the breaking of the C-H bond through base-catalyzed elimination reactions. When we began our research, however, chemists knew almost nothing about the stereospecificity of addition-elimination reactions involving conjugated acyclic carbonyl compounds, even though the carbonyl group is a pivotal functional group in organic chemistry. Over the last 25 years, we have studied the addition-elimination reactions of β-substituted acyclic esters, thioesters, and ketones in order to reach a comprehensive understanding of how electronic effects influence their stereochemistry. This Account brings together our understanding of the stereochemistry of 1,2-elimination and proton-transfer reactions, describing how each study has built upon previous work and contributed to our understanding of this field. When we began, chemists thought that anti stereospecificity in base-catalyzed 1,2-elimination reactions occurred via concerted E2 mechanisms, which provide a smooth path for anti elimination. Unexpectedly, we discovered that some E1cBirrev reactions produce the same anti stereospecificity as E2 reactions even though they proceed through diffusionally equilibrated, "free" enolate-anion intermediates. This result calls into question the conventional wisdom that anti stereochemistry must result from a concerted mechanism. While carrying out our research, we developed insights ranging from the role of historical contingency in the evolution of hydratase-dehydratase enzymes to the influence of buffers on the stereochemistry of H/D exchange in D2O. Negative hyperconjugation is the most important concept for understanding our results. This idea provides a unifying view for the largely anti stereochemistry in E1cBirrev elimination reactions and a basis for understanding the stereoelectronic influence of electron-withdrawing β-substituents on proton-transfer reactions.

  7. The normativity of clinical health care: perspectives on moral realism.

    PubMed

    Nortvedt, Per

    2012-06-01

    The paper argues that a particular version of moral realism constitutes an important basis for ethics in medicine and health care. Moral realism is the position that moral value is a part of the fabric of relational and interpersonal reality. But even though moral values are subject to human interpretations, they are not themselves the sole product of these interpretations. Moral values are not invented but discovered by the subject. Moral realism argues that values are open to perception and experience and that moral subjectivity must be portrayed in how moral values are discovered and perceived by the human subject. Moral values may exist independent of the particular subject's interpretative evaluations as a part of reality. This epistemological point about normativity is particularly significant in medical care and in health care. The clinician perceives moral value in the clinical encounter in a way that is important for competent clinical understanding. Clinical understanding in medical care and health care bears on the encounter with moral values in the direct and embodied relations to patients, with their experiences of illness and their vulnerabilities. Good clinical care is then partly conditioned upon adequate understanding of such moral realities.

  8. Beyond the realism debate: The metaphysics of 'racial' distinctions.

    PubMed

    Lemeire, Olivier

    2016-10-01

    The current metaphysical race debate is very much focused on the realism question whether races exist. In this paper I argue against the importance of this question. Philosophers, biologists and anthropologists expect that answering this question will tell them something substantive about the metaphysics of racial classifications, and will help them to decide whether it is justified to use racial categories in scientific research and public policy. I argue that there are two reasons why these expectations are not fulfilled. First of all, the realism question about race leads to a very broad philosophical debate about the semantics of general terms and the criteria for real kinds, rather than to a debate about the metaphysics of racial categories specifically. Secondly, there is a type of race realism that is so toothless that it is almost completely uninformative about the metaphysics of race. In response to these worries, I argue that the metaphysical race debate should rather be focused on the question in what way and to what extent 'racial' distinctions can ground the epistemic practices of various scientific disciplines. I spell out what I mean by this, and go on to demonstrate that trying to answer this question leads to a more fruitful metaphysical debate.

  9. Critical Realism and Empirical Bioethics: A Methodological Exposition.

    PubMed

    McKeown, Alex

    2015-02-26

    This paper shows how critical realism can be used to integrate empirical data and philosophical analysis within 'empirical bioethics'. The term empirical bioethics, whilst appearing oxymoronic, simply refers to an interdisciplinary approach to the resolution of practical ethical issues within the biological and life sciences, integrating social scientific, empirical data with philosophical analysis. It seeks to achieve a balanced form of ethical deliberation that is both logically rigorous and sensitive to context, to generate normative conclusions that are practically applicable to the problem, challenge, or dilemma. Since it incorporates both philosophical and social scientific components, empirical bioethics is a field that is consistent with the use of critical realism as a research methodology. The integration of philosophical and social scientific approaches to ethics has been beset with difficulties, not least because of the irreducibly normative, rather than descriptive, nature of ethical analysis and the contested relation between fact and value. However, given that facts about states of affairs inform potential courses of action and their consequences, there is a need to overcome these difficulties and successfully integrate data with theory. Previous approaches have been formulated to overcome obstacles in combining philosophical and social scientific perspectives in bioethical analysis; however each has shortcomings. As a mature interdisciplinary approach critical realism is well suited to empirical bioethics, although it has hitherto not been widely used. Here I show how it can be applied to this kind of research and explain how it represents an improvement on previous approaches.

  10. 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.

  11. Magnitude, precision, and realism of depth perception in stereoscopic vision.

    PubMed

    Hibbard, Paul B; Haines, Alice E; Hornsey, Rebecca L

    2017-01-01

    Our perception of depth is substantially enhanced by the fact that we have binocular vision. This provides us with more precise and accurate estimates of depth and an improved qualitative appreciation of the three-dimensional (3D) shapes and positions of objects. We assessed the link between these quantitative and qualitative aspects of 3D vision. Specifically, we wished to determine whether the realism of apparent depth from binocular cues is associated with the magnitude or precision of perceived depth and the degree of binocular fusion. We presented participants with stereograms containing randomly positioned circles and measured how the magnitude, realism, and precision of depth perception varied with the size of the disparities presented. We found that as the size of the disparity increased, the magnitude of perceived depth increased, while the precision with which observers could make depth discrimination judgments decreased. Beyond an initial increase, depth realism decreased with increasing disparity magnitude. This decrease occurred well below the disparity limit required to ensure comfortable viewing.

  12. Ways of knowing: realism, non-realism, nominalism and a typology revisited with a counter perspective for nursing science.

    PubMed

    Garrett, Bernard M; Cutting, Roger L

    2015-06-01

    In this paper, we reconsider the context of Barbara Carper's alternative ways of knowing, a prominent discourse in modern nursing theory in North America. We explore this relative to the concepts of realism, non-realism and nominalism, and investigate the philosophical divisions behind the original typology, particularly in relationship to modern scientific enquiry. We examine forms of knowledge relative to realist and nominalist positions and make an argument ad absurdum against relativistic interpretations of knowledge using the example of Borge's Chinese Emporium of Benevolent Knowledge. We propose a contentious postpositivist practical classification for nursing knowledge that demonstrates and supports the idea that knowledge has both individual and subjective components. This classification supports the practical application of nursing knowledge within the paradigm of realist postpositivist science.

  13. Hope Less: How a Healthy Dose of Realism Can Help in the ICU.

    PubMed

    Reis, Elizabeth

    2014-01-01

    The author's father died recently after a sudden heart attack. This essay discusses how the family's experiences in the cardiac intensive care unit surprised her, even though she is a member of the Ethics Committee and the Ethics Consult Team at her local hospital, and how this led her to reconsider the ways in which families and hospital physicians communicate about the process of dying. How should doctors balance their messages of hope and realism when the situation is grim? Important judgment calls needed to be made, yet the family did not fully understand what they needed to know to make good decisions, especially the importance of the timing of their decisions. A conversation early on about what would happen if the patient became physically stable--no matter how impaired--while all options remained on the table might usefully (and mercifully) transform hope at the end.

  14. On the realism of the re-engineered simple point charge water model

    SciTech Connect

    Chialvo, A.A. |

    1996-04-01

    The realism of the recently proposed high-temperature reparameterization of the simple point charge (SPC) water model [C. D. Berweger, W. F. van Gunsteren, and F. M{umlt u}ller-Plathe, Chem. Phys. Lett. {bold 232}, 429 (1995)] is tested by comparing the simulated microstructure and dielectric properties to the available experimental data. The test indicates that the new parameterization fails dramatically to describe the microstructural and dielectric properties of water at high temperature; it predicts rather strong short-range site{endash}site pair correlations, even stronger than those for water at ambient conditions, and a threefold smaller dielectric constant. Moreover, the resulting microstructure suggests that the high-temperature force-field parameters would predict a twofold higher critical density. The failure of the high-temperature parameterization is analyzed and some suggestions on alternative choices of the target properties for the weak-coupling are discussed. {copyright} {ital 1996 American Institute of Physics.}

  15. 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.

  16. Time Perception and Depressive Realism: Judgment Type, Psychophysical Functions and Bias

    PubMed Central

    Kornbrot, Diana E.; Msetfi, Rachel M.; Grimwood, Melvyn J.

    2013-01-01

    The effect of mild depression on time estimation and production was investigated. Participants made both magnitude estimation and magnitude production judgments for five time intervals (specified in seconds) from 3 sec to 65 sec. The parameters of the best fitting psychophysical function (power law exponent, intercept, and threshold) were determined individually for each participant in every condition. There were no significant effects of mood (high BDI, low BDI) or judgment (estimation, production) on the mean exponent, n = .98, 95% confidence interval (.96–1.04) or on the threshold. However, the intercept showed a ‘depressive realism’ effect, where high BDI participants had a smaller deviation from accuracy and a smaller difference between estimation and judgment than low BDI participants. Accuracy bias was assessed using three measures of accuracy: difference, defined as psychological time minus physical time, ratio, defined as psychological time divided by physical time, and a new logarithmic accuracy measure defined as ln (ratio). The ln (ratio) measure was shown to have approximately normal residuals when subjected to a mixed ANOVA with mood as a between groups explanatory factor and judgment and time category as repeated measures explanatory factors. The residuals of the other two accuracy measures flagrantly violated normality. The mixed ANOVAs of accuracy also showed a strong depressive realism effect, just like the intercepts of the psychophysical functions. There was also a strong negative correlation between estimation and production judgments. Taken together these findings support a clock model of time estimation, combined with additional cognitive mechanisms to account for the depressive realism effect. The findings also suggest strong methodological recommendations. PMID:23990960

  17. Clinical realism: a new literary genre and a potential tool for encouraging empathy in medical students.

    PubMed

    McDonald, Paula; Ashton, Katy; Barratt, Rachel; Doyle, Simon; Imeson, Dorrie; Meir, Amos; Risser, Gregoire

    2015-07-03

    Empathy has been re-discovered as a desirable quality in doctors. A number of approaches using the medical humanities have been advocated to teach empathy to medical students. This paper describes a new approach using the medium of creative writing and a new narrative genre: clinical realism. Third year students were offered a four week long Student Selected Component (SSC) in Narrative Medicine and Creative Writing. The creative writing element included researching and creating a character with a life-changing physical disorder without making the disorder the focus of the writing. The age, gender, social circumstances and physical disorder of a character were randomly allocated to each student. The students wrote repeated assignments in the first person, writing as their character and including details of living with the disorder in all of their narratives. This article is based on the work produced by the 2013 cohort of students taking the course, and on their reflections on the process of creating their characters. Their output was analysed thematically using a constructivist approach to meaning making. This preliminary analysis suggests that the students created convincing and detailed narratives which included rich information about living with a chronic disorder. Although the writing assignments were generic, they introduced a number of themes relating to illness, including stigma, personal identity and narrative wreckage. Some students reported that they found it difficult to relate to "their" character initially, but their empathy for the character increased as the SSC progressed. Clinical realism combined with repeated writing exercises about the same character is a potential tool for helping to develop empathy in medical students and merits further investigation.

  18. Macroscopic realism of quantum work fluctuations

    NASA Astrophysics Data System (ADS)

    Blattmann, Ralf; Mølmer, Klaus

    2017-07-01

    We study the fluctuations of the work performed on a driven quantum system, defined as the difference between subsequent measurements of energy eigenvalues. These work fluctuations are governed by statistical theorems with similar expressions in classical and quantum physics. We show that we can distinguish quantum and classical work fluctuations, as the latter can be described by a macrorealistic theory and hence obey Leggett-Garg inequalities. We show that these inequalities are violated by quantum processes in a driven two-level system and in a harmonic oscillator subject to a squeezing transformation.

  19. Stereochemistry of the tadalafil diastereoisomers: a critical assessment of vibrational circular dichroism, electronic circular dichroism, and optical rotatory dispersion.

    PubMed

    Qiu, Shi; De Gussem, Ewoud; Tehrani, Kourosch Abbaspour; Sergeyev, Sergey; Bultinck, Patrick; Herrebout, Wouter

    2013-11-14

    The stereochemistry of all four stereoisomers of tadalafil is determined using vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotatory dispersion (ORD) spectroscopy. By comparing experimentally obtained VCD spectra to computationally simulated ones, the absolute configuration of the enantiomeric pair (6R, 12aR)/(6S, 12aS) can be confidently assigned without prior knowledge of their relative stereochemistry. IR and NMR spectra are used to aid the assignment of the relative stereochemistry. The IR and VCD difference spectra further confirm the assignment of all stereoisomers. ECD and ORD spectra are used to investigate the complementarity of the three chiroptical techniques. VCD spectroscopy itself is found to have the ability to identify diastereoisomers, and simultaneous use of these chiroptical spectroscopic methods and NMR chemical shifts aids in increasing the reliability of stereochemistry assignment of diastereoisomers.

  20. Correction: Absolute stereochemistry and preferred conformations of urate degradation intermediates from computed and experimental circular dichroism spectra.

    PubMed

    Pipolo, Silvio; Percudani, Riccardo; Cammi, Roberto

    2016-04-14

    Correction for 'Absolute stereochemistry and preferred conformations of urate degradation intermediates from computed and experimental circular dichroism spectra' by Silvio Pipolo et al., Org. Biomol. Chem., 2011, 9, 5149-5155.

  1. 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.

  2. DAG tales: the multiple faces of diacylglycerol--stereochemistry, metabolism, and signaling.

    PubMed

    Eichmann, Thomas Oliver; Lass, Achim

    2015-10-01

    The neutral lipids diacylglycerols (DAGs) are involved in a plethora of metabolic pathways. They function as components of cellular membranes, as building blocks for glycero(phospho)lipids, and as lipid second messengers. Considering their central role in multiple metabolic processes and signaling pathways, cellular DAG levels require a tight regulation to ensure a constant and controlled availability. Interestingly, DAG species are versatile in their chemical structure. Besides the different fatty acid species esterified to the glycerol backbone, DAGs can occur in three different stereo/regioisoforms, each with unique biological properties. Recent scientific advances have revealed that DAG metabolizing enzymes generate and distinguish different DAG isoforms, and that only one DAG isoform holds signaling properties. Herein, we review the current knowledge of DAG stereochemistry and their impact on cellular metabolism and signaling. Further, we describe intracellular DAG turnover and its stereochemistry in a 3-pool model to illustrate the spatial and stereochemical separation and hereby the diversity of cellular DAG metabolism.

  3. 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.

  4. Chemical synthesis of the lantibiotic lacticin 481 reveals the importance of lanthionine stereochemistry.

    PubMed

    Knerr, Patrick J; van der Donk, Wilfred A

    2013-05-15

    Lantibiotics are a family of antibacterial peptide natural products characterized by the post-translational installation of the thioether-containing amino acids lanthionine and methyllanthionine. Until recently, only a single naturally occurring stereochemical configuration for each of these cross-links was known. The discovery of lantibiotics with alternative lanthionine and methyllanthionine stereochemistry has prompted an investigation of its importance to biological activity. Here, solid-supported chemical synthesis enabled the total synthesis of the lantibiotic lacticin 481 and analogues containing cross-links with non-native stereochemical configurations. Biological evaluation revealed that these alterations abolished the antibacterial activity in all of the analogues, revealing the critical importance of the enzymatically installed stereochemistry for the biological activity of lacticin 481.

  5. Synthesis and dynamic stereochemistry of 4-aryl-thiomorpholine-3,5-dione derivatives

    NASA Astrophysics Data System (ADS)

    Szawkało, Joanna; Maurin, Jan K.; Pluciński, Franciszek; Czarnocki, Zbigniew

    2015-01-01

    A series of new N-aryl-substituted thiomorpholine-3,5-diones were synthesized. Crystal structures of seven compounds were established on the basis of X-ray crystallography. Stable at room temperature diastereomers were detected for (2-phenyl)-substituted derivatives using 1H NMR. The dynamic stereochemistry of compound 36 was studied with variable-temperature 1H NMR and the mechanism of diastereomers interconversion was proposed on the basis of quantum chemical calculations.

  6. 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.

  7. Hexuronic Acid Stereochemistry Determination in Chondroitin Sulfate Glycosaminoglycan Oligosaccharides by Electron Detachment Dissociation

    PubMed Central

    Leach, Franklin E.; Ly, Mellisa; Laremore, Tatiana N.; Wolff, Jeremy J.; Perlow, Jacob; Linhardt, Robert J.; Amster, I. Jonathan

    2013-01-01

    Electron detachment dissociation (EDD) has previously provided stereo-specific product ions that allow for the assignment of the acidic C-5stereochemistry in heparan sulfate glycosaminoglycans (GAGs), but application of the same methodology to an epimer pair in the chondroitin sulfate glycoform class does not provide the same result. A series of experiments have been conducted in which glycosaminoglycan precursor ions are independently activated by electron detachment dissociation (EDD), electron induced dissociation (EID), and negative electron transfer dissociation (NETD) to assign the stereochemistry in chondroitin sulfate (CS) epimers and investigate the mechanisms for product ion formation during EDD in CS glycoforms. This approach allows for the assignment of electronic excitation products formed by EID and detachment products to radical pathways in NETD, both of which occur simultaneously during EDD. The uronic acid stereochemistry in electron detachment spectra produces intensity differences when assigned glycosidic and cross-ring cleavages are compared. The variations in the intensities of the doubly deprotonated 0,2X3 and Y3 ions have been shown to be indicative of CS-A/DS composition during the CID of binary mixtures. These ions can provide insight into the uronic acid composition of binary mixtures in EDD, but the relative abundances, although reproducible, are low compared with those in a CID spectrum acquired on an ion trap. The application of principal component analysis (PCA) presents a multivariate approach to determining the uronic acid stereochemistry spectra of these GAGs by taking advantage of the reproducible peak distributions produced by electron detachment. PMID:22825742

  8. Cp* Iridium Complexes Give Catalytic Alkane Hydroxylation with Retention of Stereochemistry

    SciTech Connect

    Zhou, Meng; Schley, Nathan D; Crabtree, Robert H

    2010-08-23

    A series of Cp*Ir complexes can catalyze C-H oxidation, with ceric ammonium nitrate as the terminal oxidant and water as the source of oxygen. Remarkably the hydroxylation of cis-decalin and 1,4-dimethylcyclohexane proceeds with retention of stereochemistry. With H2O18, cis-decalin oxidation gave 18O incorporation into the product cis-decalol.

  9. 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.

  10. Extreme Violation of Local Realism in Quantum Hypergraph States.

    PubMed

    Gachechiladze, Mariami; Budroni, Costantino; Gühne, Otfried

    2016-02-19

    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.

  11. Mediated realism and the representation of a health care controversy.

    PubMed

    Petraglia, J

    1994-01-01

    Psychologists have recently identified "situated cognition" as an important issue for educators across disciplines. Accordingly, instructional technologists have been working on ways to make classroom materials more true-to-life and affectively engaging. In this article I review a study designed to investigate the ways in which differing realism conditions (delivered through interactive video) influenced users' understanding of the issue of euthanasia and the case of Dax Cowart. Based on the study's findings, I raise the issue of a possible trade-off between traditional values of objectivity and authenticity.

  12. 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.

  13. 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

  14. 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

  15. Stereochemistry of coordination compounds. From alfred werner to the 21st century.

    PubMed

    von Zelewsky, Alex

    2014-01-01

    As a contribution to the scientific symposium, November 22nd, 2013, commemorating the Nobel Prize awarded to Alfred Werner in 1913, a presentation of the development of stereochemistry of coordination compounds during the past 120 years was given. Stereochemistry was fundamental to Werner's theory of coordination compounds. After Werner's death in 1919, stereochemistry in this field did not progress much further for almost 20 years, but then developed continuously. It was realized that stereochemical features of elements showing coordination numbers larger than four are responsible for an almost unlimited number of stereochemical possibilities, thus opening a molecular world of new structures. In the beginning of the 21st century, interest in the field rose again considerably, mainly due to the potential of stereoselective catalysis, and the self-assembly of supramolecular structures. An end of these developments is not in sight. Here an abbreviated version of the lecture is given. A PowerPoint(®) file, or a video of the presentation, can be downloaded.

  16. Reality check: the role of realism in stress reduction using media technology.

    PubMed

    de Kort, Y A W; Ijsselsteijn, W A

    2006-04-01

    There is a growing interest in the use of virtual and other mediated environments for therapeutic purposes. However, in the domain of restorative environments, virtual reality (VR) technology has hardly been used. Here the tendency has been to use mediated real environments, striving for maximum visual realism. This use of photographic material is mainly based on research in aesthetics judgments that has demonstrated the validity of this type of simulations as representations of real environments. Thus, restoration therapy is developing under the untested assumption that photorealistic images have the optimal level of realism, while in therapeutic applications 'experiential realism' seems to be the key rather than visual realism. The present paper discusses this contrast and briefly describes data of three studies aimed at exploring the importance and meaning of realism in the context of restorative environments.

  17. 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

  18. Keeping it real! Enhancing realism in standardised patient OSCE stations.

    PubMed

    Gormley, Gerry; Sterling, Margaret; Menary, Allison; McKeown, Gary

    2012-12-01

    Objective structured clinical examinations (OSCEs) are a commonly used method of assessing clinical competency in health care education. They can provide an opportunity to observe candidates interacting with patients. There are many challenges in using real patients in OSCEs, and increasingly standardised patients are being used as a preference. However, by using standardised patients there is a risk of making the encounter artificial and removed from actual clinical practice. Efforts made in terms of cognitive, auditory, visual, tactile, psychological and emotional cues can minimise the differences between a simulated and real clinical scenario. However, a number of factors, including feasibility, cost and usability, need to be considered if such techniques are to be practicable within an OSCE framework. This article describes a series of techniques that have been used in our institution to enhance the realism of a standardised patient encounter in an OSCE. Efforts in preparing standardised patient roles, and how they portray these roles, will be considered. A wide variety of equipment can also be used in combination with a patient and the surrounding environment, which can further enhance the authenticity of the simulated scenario. By enhancing the realism in simulated patient OSCE encounters, there is potential to trigger more authentic conscious responses from candidates and implicit reactions that the candidates themselves may be less aware of. Furthermore, using such techniques may allow faculty members to select scenarios that were previously not thought possible in an OSCE. © Blackwell Publishing Ltd 2012.

  19. Ecological Realism of US EPA Experimental Stream Facility ...

    EPA Pesticide Factsheets

    The USEPA’s Experimental Stream Facility (ESF) conducts meso-scale ecotoxicology studies that account for both structural and functional responses of whole stream communities to contaminants or other stressors. The 16 mesocosms of ESF are indoors and consist of a tiled run section (0.152 m W x 4.268 m L x 0.105 m D) that widens to a gravel riffle section (0.305 m W x 4.268 m L x 0.19 m D). They are intermediate size among studies reporting stream mesocosm results. Their set-up is unique for their size, with a high degree of engineering controls for continuous flow-through dose-response designs, yet fixed, chronic exposures to contaminants under conditions that quantifiably mimic real stream riffle/run habitat with consistent upstream renewal. With fifty standard operating procedures serving ESF studies, the background and boundary condition information is collected to determine the realism critical to the field relevance of the results. Parallel ex situ and in situ single species exposure formats including fish survival and fecundity metrics are also included. With this framework studies at ESF provide scientifically defensible evaluation of proposed aquatic life criteria. This presentation discusses the relevance and realism of USEPA's mesocosms studies conducted using the Experimental Stream Facility in Milford, OH within the context of understanding the role meso-scale results can play in validating aquatic life criteria for streams and, more generally, man

  20. Using critical realism as a framework in pharmacy education and social pharmacy research.

    PubMed

    Oltmann, Carmen; Boughey, Chrissie

    2012-01-01

    This article challenges the idea that positivism is capable of representing the complexity of social pharmacy and pharmacy education. It is argued that critical realism provides a framework that allows researchers to look at the nature of reality and at mechanisms that produce, or have the tendency to produce, events and experiences of those events. Critical realism is a framework, not a method. It allows researchers to make observations about phenomena and explain the relationships and connections involved. The researcher has to look for mechanisms and structures that could explain why the phenomena, the connections, and the relationships exist (or do not) and then try to show that these mechanisms do exist. This article first contextualizes critical realism, then briefly describes it, and lastly exemplifies the use of critical realism in a discussion of a research project conducted in pharmacy education. Critical realism may be particularly useful in interdisciplinary research, for example, where practitioners and researchers are working together in a social pharmacy or pharmacy education setting. Critical realism requires the practitioners and the researchers to question and make known their assumptions about their own realities and to think of a complex problem or phenomenon in terms of a stratified reality, generative mechanisms, and tendencies. Critical realism may make research more rigorous and also allow researchers to conceive of a greater breadth of research designs for their work.

  1. Get real: how current behavior influences perceptions of realism and behavioral intent for public service announcements.

    PubMed

    Nelson, Michelle R; Zhu, Xuan; Li, Yingying; Fiese, Barbara; Koester, Brenda

    2015-01-01

    This research examined how realism and current behavior influence message reception and processing for public service announcements (PSAs) designed to help parents with meal planning. Findings from 19 in-depth interviews revealed that the perceived realism of the message, the similarity, and the wishful identification with informants' lives influenced message acceptance, in line with the Message Interpretation Process (MIP) model. Results of an online survey with mothers show that realism matters more for those individuals who already engage in the featured behavior. In line with theory, "experts" (meal planners) show increased behavioral intent of the featured behaviors when viewing the more realistic PSA.

  2. Critical realism: a philosophical framework for the study of gender and mental health.

    PubMed

    Bergin, Michael; Wells, John S G; Owen, Sara

    2008-07-01

    This paper explores gender and mental health with particular reference to the emerging philosophical field of critical realism. This philosophy suggests a shared ontology and epistemology for the natural and social sciences. Until recently, most of the debate surrounding gender and mental health has been guided either implicitly or explicitly within a positivist or constructivist philosophy. With this in mind, key areas of critical realism are explored in relation to gender and mental health, and contrasted with the positions of positivism and constructivism. It is argued that critical realism offers an alternative philosophical framework for the exploration of gender issues within mental health care.

  3. Modeling Heliospheric Plasma Turbulence: A Critique of the Effects of Completeness, Realism and Size

    NASA Astrophysics Data System (ADS)

    Matthaeus, W. H.; Wan, M.; Parashar, T.; Shay, M. A.

    2015-12-01

    With the Solar Probe and Solar Orbiter missions approaching, and the highly capable instruments of MMS already in orbit, there is an upwelling of interest in understanding plasma turbulence and related effects at kinetic scales. Accordingly a variety of methods have been employed to study kinetic turbulence and in particular dissipation and cascade processes and their effects on protons, electrons and minor ions. Here we discuss the influence of system size, and the completeness and realism of the several kinetic physics models that are employed. One important issue is whether coherent structures such as current sheets can be properly represented and evolved in smaller systems; this is particular important when turbulence is intermittent and non-self similar, so that couplings become nonlocal in scale. Another factor is resolution, both spatial and statistical - what are the effects of counting statistics in PIC and velocity filamentation in Vlasov models? Also discussed is the efficacy and strategic use of models with reduced physics and/or dimensionality - hybrid, Reduced MHD and gyrokinetics, for example. It is suggested, using several example problems, how the cross comparison of models in the context of a framework such as Turbochallenge may have wide ranging conceptual impact.

  4. 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.

  5. Design of interactive health drama built on social realism.

    PubMed

    Graspemo, Gabriella; Hassling, Linda; Nordfeldt, Sam; Eriksson, Hendrik; Timpka, Toomas

    2004-01-01

    There are many psychosocial aspects of chronic diseases, such as diabetes. Educational multimedia can support patients with chronic diseases and their families by communicating narratives based on social realism. The production of such socio-realistic interactive health dramas requires systematic methods, especially for the identification of significant stories. The aim of this study is to explore the use of self-documentary video in the design of an Interactive Health Drama environment to support diabetic adolescents and their families. In particular, the potential of the self-documentary video for story development in combination with qualitative interviews were explored. The proposed approach, when further developed, is intended to enable all types of chronic disease patients to work with their specific psychosocial problems in a supportive and stimulating environment adapted to their personality and preferences.

  6. 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.

  7. 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.

  8. Improving the realism of hydrologic model through multivariate parameter estimation

    NASA Astrophysics Data System (ADS)

    Rakovec, Oldrich; Kumar, Rohini; Attinger, Sabine; Samaniego, Luis

    2017-04-01

    Increased availability and quality of near real-time observations should improve understanding of predictive skills of hydrological models. Recent studies have shown the limited capability of river discharge data alone to adequately constrain different components of distributed model parameterizations. In this study, the GRACE satellite-based total water storage (TWS) anomaly is used to complement the discharge data with an aim to improve the fidelity of mesoscale hydrologic model (mHM) through multivariate parameter estimation. The study is conducted in 83 European basins covering a wide range of hydro-climatic regimes. The model parameterization complemented with the TWS anomalies leads to statistically significant improvements in (1) discharge simulations during low-flow period, and (2) evapotranspiration estimates which are evaluated against independent (FLUXNET) data. Overall, there is no significant deterioration in model performance for the discharge simulations when complemented by information from the TWS anomalies. However, considerable changes in the partitioning of precipitation into runoff components are noticed by in-/exclusion of TWS during the parameter estimation. A cross-validation test carried out to assess the transferability and robustness of the calibrated parameters to other locations further confirms the benefit of complementary TWS data. In particular, the evapotranspiration estimates show more robust performance when TWS data are incorporated during the parameter estimation, in comparison with the benchmark model constrained against discharge only. This study highlights the value for incorporating multiple data sources during parameter estimation to improve the overall realism of hydrologic model and its applications over large domains. Rakovec, O., Kumar, R., Attinger, S. and Samaniego, L. (2016): Improving the realism of hydrologic model functioning through multivariate parameter estimation. Water Resour. Res., 52, http://dx.doi.org/10

  9. 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

  10. Inhibition of O-GlcNAcase by PUGNAc is dependent upon the oxime stereochemistry.

    PubMed

    Perreira, Melissa; Kim, Eun Ju; Thomas, Craig J; Hanover, John A

    2006-02-01

    The potent O-GlcNAcase inhibitor PUGNAc was synthesized and two isomers based on the E and Z stereochemistry of the oxime moiety were separated, defined, and tested for activity. Several lines of evidence were examined in an effort to define the correct stereochemical assignments of each form of PUGNAc. The ability of the Z stereoisomer to undergo the Beckmann rearrangement was ultimately the most definitive proof. It was determined via both in vitro and intact cell experiments that the Z form of PUGNAc was vastly more potent an inhibitor of O-GlcNAcase than the E form.

  11. Impact of Absolute Stereochemistry on the Antiangiogenic and Antifungal Activities of Itraconazole

    PubMed Central

    2010-01-01

    Itraconazole is used clinically as an antifungal agent and has recently been shown to possess antiangiogenic acitivity. Itraconazole has three chiral centers that give rise to eight stereoisomers. The complete role of stereochemistry in the two activities of itraconazole, however, has not been addressed adequately. For the first time, all eight stereoisomers of itraconazole (1a−h) have been synthesized and evaluated for activity against human endothelial cell proliferation and for antifungal activity against five fungal strains. Distinct antiangiogenic and antifungal activity profiles of the trans stereoisomers, especially 1e and 1f, suggest different molecular mechanisms underlying the antiangiogenic and antifungal activities of itraconazole. PMID:21892383

  12. 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.

  13. The use of J-coupling as a sole criterion to assign the total absolute stereochemistry of new pyrrolidinone class synthetic analogs, derived from S-pyroglutamic acid

    NASA Astrophysics Data System (ADS)

    Kellici, Tahsin F.; Ntountaniotis, Dimitrios; Vanioti, Marianna; Golic Grdadolnik, Simona; Simcic, Mihael; Michas, Georgios; Moutevelis-Minakakis, Panagiota; Mavromoustakos, Thomas

    2017-02-01

    During the synthesis of new pyrrolidinone analogs possessing biological activity it is intriguing to assign their absolute stereochemistry as it is well known that drug potency is influenced by the stereochemistry. The combination of J-coupling information with theoretical results was used in order to establish their total stereochemistry when the chiral center of the starting material has known absolute stereochemistry. The J-coupling can be used as a sole criterion for novel synthetic analogs to identify the right stereochemistry. This approach is extremely useful especially in the case of analogs whose 2D NOESY spectra cannot provide this information. Few synthetic examples are given to prove the significance of this approach.

  14. Reducing consistency in human realism increases the uncanny valley effect; increasing category uncertainty does not.

    PubMed

    MacDorman, Karl F; Chattopadhyay, Debaleena

    2016-01-01

    Human replicas may elicit unintended cold, eerie feelings in viewers, an effect known as the uncanny valley. Masahiro Mori, who proposed the effect in 1970, attributed it to inconsistencies in the replica's realism with some of its features perceived as human and others as nonhuman. This study aims to determine whether reducing realism consistency in visual features increases the uncanny valley effect. In three rounds of experiments, 548 participants categorized and rated humans, animals, and objects that varied from computer animated to real. Two sets of features were manipulated to reduce realism consistency. (For humans, the sets were eyes-eyelashes-mouth and skin-nose-eyebrows.) Reducing realism consistency caused humans and animals, but not objects, to appear eerier and colder. However, the predictions of a competing theory, proposed by Ernst Jentsch in 1906, were not supported: The most ambiguous representations-those eliciting the greatest category uncertainty-were neither the eeriest nor the coldest.

  15. 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.

  16. Naïve realism: folk fallacies in the design and use of visual displays.

    PubMed

    Smallman, Harvey S; Cook, Maia B

    2011-07-01

    Often implicit in visual display design and development is a gold standard of photorealism. By approximating direct perception, photorealism appeals to users and designers by being both attractive and apparently effortless. The vexing result from numerous performance evaluations, though, is that increasing realism often impairs performance. Smallman and St. John (2005) labeled misplaced faith in realistic information display Naïve Realism and theorized it resulted from a triplet of folk fallacies about perception. Here, we illustrate issues associated with the wider trend towards realism by focusing on a specific current trend for high-fidelity perspective view (3D) geospatial displays. In two experiments, we validated Naïve Realism for different terrain understanding tasks, explored whether certain individuals are particularly prone to Naïve Realism, and determined the ability of task feedback to mitigate Naïve Realism. Performance was measured for laying and judging a concealed route across realistic terrain shown in different display formats. Task feedback was either implicit, in Experiment 1, or explicit in Experiment 2. Prospective and retrospective intuitions about the best display formats for the tasks were recorded and then related to task performance and participant spatial ability. Participants generally intuited they would perform tasks better with more realism than they actually required. For example, counter to intuitions, lowering fidelity of the terrain display revealed the gross scene layout needed to lay a well-concealed route. Individuals of high spatial ability calibrated their intuitions with only implicit task feedback, whereas those of low spatial ability required salient, explicit feedback to calibrate their intuitions about display realism. Results are discussed in the wider context of applying perceptual science to display design, and combating folk fallacies.

  17. Stereochemistry at the forefront in the design and discovery of novel anti-tuberculosis agents.

    PubMed

    Huang, Qingqing; He, Rong; Kozikowski, Alan P

    2011-01-01

    Today, 75% of new drugs introduced to the market are single enantiomers and new techniques in asymmetric synthesis and chiral separation expedites chiral drug discovery and development worldwide. The enantiomers of a chiral drug present unique chemical and pharmacological behaviors in a chiral environment, such as the human body, in which the stereochemistry of chiral drugs determines their pharmacokinetic, pharmacodynamic, and toxicological actions. Thus, it is imperative that only the pure and therapeutically active isomer be prepared and marketed. Tuberculosis (TB), a highly contagious and airborne disease that is caused by infection with Mycobacterium tuberculosis (Mtb), currently represents one of the most threatening health problems globally. The emergence of multidrug-resistant TB (MDR-TB) and extensively drug-resistant TB (XDR-TB), as well as HIV co-infection along with a lengthy treatment regimen, highlights an urgent need for the development of new anti-TB agents. Currently, new chiral anti-TB agents are being developed from some well-known anti-TB agents, high throughput screening (HTS) hits, and natural products. This review will focus on the reported chiral anti-TB agents together with the clinical importance of their chirality and stereochemistry.

  18. Stereochemistry and conformation of skyllamycin, a non-ribosomally synthesized peptide from Streptomyces sp. Acta 2897.

    PubMed

    Schubert, Vivien; Di Meo, Florent; Saaidi, Pierre-Loïc; Bartoschek, Stefan; Fiedler, Hans-Peter; Trouillas, Patrick; Süssmuth, Roderich D

    2014-04-22

    Skyllamycin is a non-ribosomally synthesized cyclic depsipeptide from Streptomyces sp. Acta 2897 that inhibits PDGF-signaling. The peptide scaffold contains an N-terminal cinnamoyl moiety, a β-methylation of aspartic acid, three β-hydroxylated amino acids and one rarely occurring α-hydroxy glycine. With the exception of α-hydroxy glycine, the stereochemistry of the amino acids was assigned by comparison to synthetic reference amino acids applying chiral GC-MS and Marfey-HPLC analysis. The stereochemistry of α-hydroxy glycine, which is unstable under basic and acidic conditions, was determined by conformational analysis, employing a combination of data from NOESY-NMR spectroscopy, simulated annealing and free MD simulations. The simulation procedures were applied for both R- and S-configured α-hydroxy glycine of the skyllamycin structure and compared to the NOESY data. Both methods, simulated annealing and free MD simulations independently support S-configured α-hydroxy glycine thus enabling the assignment of all stereocenters in the structure of skyllamycin and devising the role of two-component flavin dependent monooxygenase (Sky39) as S-selective.

  19. Probing the stereochemistry of successive sulfoxidation of the insecticide fenamiphos in soils.

    PubMed

    Cai, Xiyun; Xiong, Weina; Xia, Tingting; Chen, Jingwen

    2014-10-07

    Successive sulfoxidation is widely recognized as a general characteristic of the metabolism of chiral or prochiral thioethers, producing sulfoxides, and sulfones. However, information related to the stereochemistry of this process in soils is rare. In this study, the biotic transformation of the insecticide fenamiphos (a model thioether) was followed over two months in three soils, through separate incubations with fenamiphos parent, the sulfoxide intermediate (FSO), the sulfone intermediate (FSO2), and their respective stereoisomers. The results showed that the successive sulfoxidation involved oxidation of fenamiphos to FSO and subsequently to FSO2 as well as diastereomerization/enantiomerization of FSO, all of which were primarily biotic and stereoselective. The concomitant hydrolysis of fenamiphos, FSO, and FSO2 to phenols that occurred at lower rates was biotically favorable, but not stereoselective. The stereochemistry of this successive sulfoxidation transferred principally through two parallel systems, R(+)-fenamiphos → SRPR(+)-/SSPR(-)-FSO → R(+)-FSO2 and S(-)-fenamiphos → SRPS(+)-/SSPS(-)-FSO → S(-)-FSO2, between which unidirectional intersystem crossing occurred at FSO via isomeric conversions and created a system of S(-)-fenamiphos → SRPR(+)-/SSPR(-)-FSO → R(+)-FSO2. This pattern accounts for the enrichment of the intermediates SSPR(-)-/SSPS(-)-FSO and R(+)-FSO2 that are toxicologically close to the highly toxic S(-)-fenamiphos, associated with soil application of fenamiphos. Selective formation/depletion of these intermediate stereoisomers leads to dramatic variations in the ecotoxicological effects of the thioether insecticide.

  20. The effect of fenoterol stereochemistry on the β2 adrenergic receptor system: ligand directed chiral recognition

    PubMed Central

    Jozwiak, Krzysztof; Plazinska, Anita; Toll, Lawrence; Jimenez, Lucita; Woo, Anthony Yiu-Ho; Xiao, Rui-Ping; Wainer, Irving W.

    2011-01-01

    The β2 adrenergic receptor (β2-AR) is a model system for studying the ligand recognition process in G-protein coupled receptors. Fenoterol (FEN) is a β2-AR selective agonist that has two centers of chirality and exists as four stereoisomers. Radioligand binding studies determined that stereochemistry greatly influences the binding affinity. Subsequent Van’t Hoff analysis shows very different thermodynamics of binding depending on the stereoconfiguration of the molecule. The binding of (S,x’)-isomers is almost entirely enthalpy controlled whereas binding of (R,x’)-isomers is purely entropy driven. Stereochemistry of FEN molecule also affects the coupling of the receptor to different G proteins. In a rat cardiomyocyte contractility model, (R,R’)-FEN was shown to selectively activate Gs protein signaling while the (S,R’)- isomer activated both Gi and Gs protein. The overall data demonstrate that the chirality at the two chiral centers of the FEN molecule influences the magnitude of binding affinity, thermodynamics of local interactions within the binding site and the global mechanism of β2-AR activation. Differences in thermodynamic parameters and non-uniform G-protein coupling suggest a mechanism of chiral recognition in which observed enantioselectivities arise from the interaction of the (R,x’)-FEN stereoisomers with a different receptor conformation than the one with which the (S,x’)-isomer interacts. PMID:21618615

  1. How stereochemistry influences the taste of wine: Isolation, characterization and sensory evaluation of lyoniresinol stereoisomers.

    PubMed

    Cretin, Blandine N; Sallembien, Quentin; Sindt, Lauriane; Daugey, Nicolas; Buffeteau, Thierry; Waffo-Teguo, Pierre; Dubourdieu, Denis; Marchal, Axel

    2015-08-12

    Wine expresses its beauty by sending a sensory message to the taster through molecules coming from grapes, yeast metabolism or oak wood. Among the compounds released during barrel aging, lyoniresinol has been recently reported as a relevant contributor to wine bitterness. As this lignan contains three stereogenic carbons, this work aimed at investigating the influence of stereochemistry on wine taste by combining analytical and sensorial techniques. First, an oak wood extract was screened by Liquid Chromatography-High Resolution Mass Spectrometry to target isomers separable in a symmetric environment and a diastereoisomer called epi-lyoniresinol was isolated for the first time. Then, an original racemic resolution based on natural xylose-derivatives was carried out to obtain lyoniresinol enantiomers. Chiroptical spectroscopic measurements associated with theoretical calculations allowed the unambiguous determination of their absolute configuration. The taste properties of all these stereoisomers revealed that only one lyoniresinol enantiomer is strongly bitter whereas the other one is tasteless and the diastereoisomer is slightly sweet. The presence of these three compounds was established in an oaked Bordeaux wine by chiral and non-chiral chromatography, suggesting the significant influence of stereochemistry on wine taste.

  2. Stereochemistry analysis and comparison of two C(3)-alkyl substituted cyclohexonedicarboxylates with their C(3)-aryl substituted analogues

    NASA Astrophysics Data System (ADS)

    Chen, Chao-Yue; Wang, Qi; Zhu, Bing-Long; Zhao, Wen-Jie; Hu, Jin-Song

    2016-03-01

    Two representative C(3)-alkyl substituted cyclohexonedicarboxylates (4a and 4b) were synthesized and their conformational features were investigated by single crystal X-ray crystallography for the first time. These stereochemistry results of 4a and 4b were compared with those obtained from the earlier research of C(3)-aryl substituted analogues (1-3).

  3. 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.

  4. Nanoscale amphiphilic macromolecules with variable lipophilicity and stereochemistry modulate inhibition of oxidized low-density lipoprotein uptake.

    PubMed

    Poree, Dawanne E; Zablocki, Kyle; Faig, Allison; Moghe, Prabhas V; Uhrich, Kathryn E

    2013-08-12

    Amphiphilic macromolecules (AMs) based on carbohydrate domains functionalized with poly(ethylene glycol) can inhibit the uptake of oxidized low density lipoprotein (oxLDL) and counteract foam cell formation, a key characteristic of early atherogenesis. To investigate the influence of lipophilicity and stereochemistry on the AMs' physicochemical and biological properties, mucic acid-based AMs bearing four aliphatic chains (2a) and tartaric acid-based AMs bearing two (2b and 2l) and four aliphatic chains (2g and 2k) were synthesized and evaluated. Solution aggregation studies suggested that both the number of hydrophobic arms and the length of the hydrophobic domain impact AM micelle sizes, whereas stereochemistry impacts micelle stability. 2l, the meso analogue of 2b, elicited the highest reported oxLDL uptake inhibition values (89%), highlighting the crucial effect of stereochemistry on biological properties. This study suggests that stereochemistry plays a critical role in modulating oxLDL uptake and must be considered when designing biomaterials for potential cardiovascular therapies.

  5. 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)

  6. 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)

  7. Topological Stereochemistry.

    DTIC Science & Technology

    1988-01-29

    Perry, A.E.; Richards, R.M.; Homan, T.C.; Haltiwanger, R.C. "The THYME Polyethers: An Approach to the Synthesis of a Molecular Knotted Ring...4. Walba, D.M.; Richards, R.M.; Hermsmeier, M.; Haltiwanger, R.C. "Conformational Properties of the THYME Polyethers: The Bis- THYME Cylinder-a 3...strips, linked rings, and knotted rings, using the tetrahydroxymethyl- ethylene ( THYME ) fused crown ether strategy illustrated by our synthesis of the

  8. Mediating role of activity level in the depressive realism effect.

    PubMed

    Blanco, Fernando; Matute, Helena; A Vadillo, Miguel

    2012-01-01

    Several classic studies have concluded that the accuracy of identifying uncontrollable situations depends heavily on depressive mood. Nondepressed participants tend to exhibit an optimistic illusion of control, whereas depressed participants tend to better detect a lack of control. Recently, we suggested that the different activity levels (measured as the probability of responding during a contingency learning task) exhibited by depressed and nondepressed individuals is partly responsible for this effect. The two studies presented in this paper provide further support for this mediational hypothesis, in which mood is the distal cause of the illusion of control operating through activity level, the proximal cause. In Study 1, the probability of responding, P(R), was found to be a mediator variable between the depressive symptoms and the judgments of control. In Study 2, we intervened directly on the mediator variable: The P(R) for both depressed and nondepressed participants was manipulated through instructions. Our results confirm that P(R) manipulation produced differences in the participants' perceptions of uncontrollability. Importantly, the intervention on the mediator variable cancelled the effect of the distal cause; the participants' judgments of control were no longer mood dependent when the P(R) was manipulated. This result supports the hypothesis that the so-called depressive realism effect is actually mediated by the probability of responding.

  9. Mediating Role of Activity Level in the Depressive Realism Effect

    PubMed Central

    Blanco, Fernando; Matute, Helena; A. Vadillo, Miguel

    2012-01-01

    Several classic studies have concluded that the accuracy of identifying uncontrollable situations depends heavily on depressive mood. Nondepressed participants tend to exhibit an optimistic illusion of control, whereas depressed participants tend to better detect a lack of control. Recently, we suggested that the different activity levels (measured as the probability of responding during a contingency learning task) exhibited by depressed and nondepressed individuals is partly responsible for this effect. The two studies presented in this paper provide further support for this mediational hypothesis, in which mood is the distal cause of the illusion of control operating through activity level, the proximal cause. In Study 1, the probability of responding, P(R), was found to be a mediator variable between the depressive symptoms and the judgments of control. In Study 2, we intervened directly on the mediator variable: The P(R) for both depressed and nondepressed participants was manipulated through instructions. Our results confirm that P(R) manipulation produced differences in the participants’ perceptions of uncontrollability. Importantly, the intervention on the mediator variable cancelled the effect of the distal cause; the participants’ judgments of control were no longer mood dependent when the P(R) was manipulated. This result supports the hypothesis that the so-called depressive realism effect is actually mediated by the probability of responding. PMID:23029435

  10. Ontological Realism for the Research Domain Criteria for Mental Disorders.

    PubMed

    Ceusters, Werner; Jensen, Mark; Diehl, Alexander D

    2017-01-01

    At the heart of the Research Domain Criteria for Mental Disorders is a matrix in which functional aspects of behavior are related to genotypic and (endo-)phenotypic research findings, and the various techniques through which they can been observed. The matrix is work in progress. As such it currently suffers from several shortcomings, the resolution of which, we contend, are essential to success of NIMH's goal of fostering translational science on mental disorders. Using well-established criteria for assessing the terminological and ontological quality of biomedical representations we identified the major problems to be (1) the abundant presence of terms that lack face value, (2) the absence of what the exact nature of the represented relationships are, and (3) referential imprecision with respect to the intended granularity of what the terms denote. We propose to eliminate these shortcomings by resorting to definitions and formal representations under the umbrella of Ontological Realism as they already have been developed in the areas of mental health, anatomy and biological functions.

  11. '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.

  12. 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'.

  13. Antibacterial adhesion of borneol-based polymer via surface chiral stereochemistry.

    PubMed

    Luo, Lingqiong; Li, Guofeng; Luan, Di; Yuan, Qipeng; Wei, Yen; Wang, Xing

    2014-01-01

    During its adhesion on external surfaces, a cell exhibits obvious inclination to different molecular chirality, which encourages us to develop a new type of antibacterial material catering to the "chiral taste" of bacteria. On the basis of the natural product borneol (a camphane-type bicyclic monoterpene), a series of borneol-based polymer, polyborneolacrylate (PBA), was successfully prepared and showed superior antibacterial adhesion properties resulting from the borneol isomers on material surface. The results of this study reveal that bacteria simply dislike this type of stubborn surface of PBA, and the PBA surface stereochemistry contributes to the interfacial antibacterial activities. The PBA polymers were evaluated as noncytotoxic and can be simply synthesized, demonstrating their great potential for biomedical applications.

  14. Total Syntheses of (+)-Grandilodine C and (+)-Lapidilectine B and Determination of their Absolute Stereochemistry.

    PubMed

    Nakajima, Masaya; Arai, Shigeru; Nishida, Atsushi

    2016-03-01

    Enantioselective total syntheses of the Kopsia alkaloids (+)-grandilodine C and (+)-lapidilectine B were accomplished. A key intermediate, spirodiketone, was synthesized in 3 steps and converted into the chiral enone by enantioselective deprotonation followed by oxidation with up to 76 % ee. Lactone formation was achieved through stereoselective vinylation followed by allylation and ozonolysis. The total synthesis of (+)-grandilodine C was achieved by palladium-catalyzed intramolecular allylic amination and ring-closing metathesis to give 8- and 5-membered heterocycles, respectively. Selective reduction of a lactam carbonyl gave (+)-lapidilectine B. The absolute stereochemistry of both natural products was thereby confirmed. These syntheses enable the scalable preparation of the above alkaloids for biological studies.

  15. Total synthesis and revision of C6 stereochemistry of (+)-amphidinolide W.

    PubMed

    Ghosh, Arun K; Gong, Gangli

    2006-02-03

    An enantioselective first total synthesis and structural revision of the cytotoxic natural product amphidinolide W is described. We initially investigated a ring-closing metathesis based synthetic strategy to form the 12-membered macrocycle. This strategy was unsuccessful as it led to formation of a 17-membered macrocycle. Subsequently, we explored an alternative strategy that involved cross-metathesis followed by a Yamaguchi macrolactonization reaction sequence utilizing the same key intermediates. This strategy led to the synthesis of amphidinolide W. The synthesis was carried out in a convergent manner, and four of the five stereogenic centers in amphidinolide W were set by asymmetric synthesis. The synthesis features Sharpless asymmetric dihydroxylation, diastereoselective alkylation, efficient cross-metathesis of functionalized substrates, and novel functional group transformations using selective lipase-catalyzed hydrolysis of the primary acetate group. Of particular note, the C6 absolute stereochemistry of amphidinolide W has now been revised through our synthesis.

  16. The effect of stereochemistry on the biological activity of natural phytotoxins, fungicides, insecticides and herbicides.

    PubMed

    Evidente, Antonio; Cimmino, Alessio; Andolfi, Anna

    2013-02-01

    Phytotoxins are secondary microbial metabolites that play an essential role in the development of disease symptoms induced by fungi on host plants. Although phytotoxins can cause extensive-and in some cases devastating-damage to agricultural crops, they can also represent an important tool to develop natural herbicides when produced by fungi and plants to inhibit the growth and spread of weeds. An alternative strategy to biologically control parasitic plants is based on the use of plant and fungal metabolites, which stimulate seed germination in the absence of the host plant. Nontoxigenic fungi also produce bioactive metabolites with potential fungicide and insecticide activity, and could be applied for crop protection. All these metabolites represent important tools to develop eco-friendly pesticides. This review deals with the relationships between the biological activity of some phytotoxins, seed germination stimulants, fungicides and insecticides, and their stereochemistry.

  17. Plasmodium falciparum: role of absolute stereochemistry in the antimalarial activity of synthetic amino alcohol antimalarial agents.

    PubMed

    Karle, J M; Olmeda, R; Gerena, L; Milhous, W K

    1993-06-01

    The (+)-isomers of mefloquine and its threo analog are 1.69 to 1.95 times more active than the (-)-isomers against chloroquine-sensitive and chloroquine-resistant Plasmodium falciparum in vitro. This large a differential between the activity of (+)- and (-)-isomers was not observed for other synthetic amino alcohol antimalarial agents containing a piperidine ring. The enantiomers of amino alcohol antimalarial agents in which the amine is part of an acyclic group, such as in halofantrine, displayed little, if any, differential antimalarial activity. Thus, the effect of absolute stereochemistry of the amino alcohol antimalarial agents on antimalarial activity appears to depend upon both the flexibility of the amine portion of the molecule and the structure of the aromatic portion of the molecule.

  18. 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.

  19. Enantiomeric HPLC resolution and absolute stereochemistry assignment of a new poligamain derivative.

    PubMed

    Pistolozzi, M; Royo, V; Pereira, A C; Silva, M L A; Silva, R; Cunha, W R; Vaconcelos, K; Cass, Q B; Martins, C H G; Bastos, J K; Varchi, G; Guerrini, A; Bertucci, C

    2013-03-05

    A new aryltetralin lignan derivative, 1, was obtained by reacting dimethyl succinate and piperonal, furnishing the lactone 4-(3',4'-methylenedioxybenzyl)-4,5-dihydro-2(3H)-furanone, which was reacted once again with piperonal and LDA to give the dibenzylbutirolactone 7-hydroxyhinokinin. The cyclization of 7-hydroxyhinokinin into polygamain occurred in the presence of trifluoroacetic acid. The reduction of the furanic ring of polygamain was done by its reaction with DIBAL in THF, furnishing the diol functionalized lignin derivative 1 as single diastereomer. The enantiomeric fractions of 1 were obtained by preparative enantioselective HPLC. The absolute stereochemistry was assigned by electronic circular dichroism (ECD) and nuclear magnetic resonance (NMR) spectroscopy. An all-trans relative configuration was determined by NMR on the bases of ¹H coupling constants and nuclear Overhauser effect (n.O.e.) experiments. The absolute configuration at C1 was assigned on the basis of the ECD sign at 296 nm by comparison to the ECD spectra of structural analogues with defined stereochemistry. The assignment of the absolute configuration was confirmed by applying the exciton chirality method to the well-defined ECD couplets at 285 and 200 nm allied to the two electronic transitions L(b) and B(b) of the aromatic moieties, respectively. Rac-1 and its enantiomeric isomers were evaluated against important bacteria responsible for dental caries. The best results obtained for the (1R,2S,3S) isomer were against Streptococcus mutans (250 μM), Streptococcus salivarius (250 μM), Streptococcus sobrinus (280 μM) and Streptococcus mitis (280 μM). The (1S,2R,3R) isomer was active only against Streptococcus sanguinis (280 μM). The enantiomeric mixture was less active than the (1R,2S,3S) isomer. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    PubMed

    Shefrin, Allan; Khazei, Afshin; Cheng, Adam

    2015-01-01

    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. 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. 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. 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.

  1. 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

  2. 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.

  3. Metacognition and depressive realism: evidence for the level-of-depression account.

    PubMed

    Soderstrom, Nicholas C; Davalos, Deana B; Vázquez, Susana M

    2011-09-01

    Introduction. The present study examined the relationship between metacognition (i.e., "thinking about thinking") and depression. More specifically, the depressive realism hypothesis (Alloy & Abramson, 1979), which posits that depressed people have a more accurate view of reality than nondepressed people, was tested. Methods. Nondepressed, mildly depressed, and moderately depressed individuals predicted their memory performance by making judgements of learning after each studied item. These predictions were then compared with actual performance on a free recall task to assess calibration, an index of metacognitive accuracy. Results and conclusions. Consistent with the depressive realism hypothesis, mild depression was associated with better calibration than nondepression. However, this "sadder but wiser" phenomenon appears to only exist to point, as moderate depression and nondepression showed no calibration differences. Thus, the level-of-depression account of depressive realism is supported.

  4. A DSC investigation on the influence of gemini surfactant stereochemistry on the organization of lipoplexes and on their interaction with model membranes.

    PubMed

    Aleandri, S; Bonicelli, M G; Giansanti, L; Giuliani, C; Ierino, M; Mancini, G; Martino, A; Scipioni, A

    2012-12-01

    Previous investigations showed that the extent of DNA condensation and the efficiency in the transfection of liposomes formulated with 1,2-dimyristoyl-sn-glycero-phosphocholine and cationic stereomeric gemini surfactants depend heavily on the stereochemistry of the gemini. The influence of the stereochemistry on the interaction of lipoplexes with zwitterionic and anionic cell membrane models was investigated by differential scanning calorimetry to rationalize their different biological behavior. Further, the thermotropic behavior of the corresponding liposomes and of the spontaneous self-assemblies of gemini surfactants in the presence and in the absence of DNA was evaluated to correlate the physicochemical properties of lipoplexes and the stereochemistry of the cationic component. The obtained results show that the stereochemistry of the gemini surfactant controls lipoplexes organization and their mode and kinetic of interaction with different cell membrane models.

  5. Three Forms of Neuro-Realism: Explaining the Persistence of the "Uncritically Real" in Popular Neuroscience News

    ERIC Educational Resources Information Center

    Gruber, David R.

    2017-01-01

    Neuro-realism is a widely cited concept describing a textual phenomenon in popular science news wherein brain research uncritically validates or invalidates the "realness" of particular beliefs or practices. Currently, no research on neuro-realism examines the variable rhetorical roles of such statements, that is, how they support…

  6. 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. Copyright © 2015. Published by Elsevier Ltd.

  7. Perceived realism and role attractiveness in movie portrayals of alcohol drinking.

    PubMed

    Mo Bahk, C

    2001-01-01

    To explore the role of perceived realism and role attractiveness in dramatized alcohol portrayals. A total of 158 college students watched 1 of 2 movie versions that portray alcohol drinking either positively or negatively. Role attractiveness of the drinking character increased favorableness in alcohol-related attitudes and dispositions in Positive Condition, whereas perceived realism acted as a significant mediator in Negative Condition. Health educators and policymakers are alerted to the fact that the entertainment media too often portray glamorous characters as enjoying alcoholic beverages without facing negative consequences, which may particularly affect the viewers who feel attracted to the role characters.

  8. Objective realism and freedom of choice in relativistic quantum field theory

    NASA Astrophysics Data System (ADS)

    Bednorz, Adam

    2016-10-01

    Traditional Bell's argument shows that freedom of choice is inconsistent with quantum realism if lack of signaling and sufficiently fast choices and readouts are assumed. While no-signaling alone is a consequence of special relativity, this is not the case of spacetime location of choice and readout. Here we attempt to incorporate freedom of choice into quantum objective realism relying solely on relativistic quantum field theory. We conclude that this is impossible without breaking relativistic invariance and put forward the possibility of signaling faster than light, which cannot be excluded if an ultimate theory violates relativity.

  9. Effect of stereochemistry, chain length and sequence pattern on antimicrobial properties of short synthetic β-sheet forming peptide amphiphiles.

    PubMed

    Ong, Zhan Yuin; Cheng, Junchi; Huang, Yuan; Xu, Kaijin; Ji, Zhongkang; Fan, Weimin; Yang, Yi Yan

    2014-01-01

    In the face of mounting global antibiotics resistance, the identification and development of membrane-active antimicrobial peptides (AMPs) as an alternative class of antimicrobial agent have gained significant attention. The physical perturbation and disruption of microbial membranes by the AMPs have been proposed to be an effective means to overcome conventional mechanisms of drug resistance. Recently, we have reported the design of a series of short synthetic β-sheet folding peptide amphiphiles comprised of recurring (X1Y1X2Y2)n-NH2 sequences where X: hydrophobic amino acids, Y: cationic amino acids and n: number of repeat units. In efforts to investigate the effects of key parameters including stereochemistry, chain length and sequence pattern on antimicrobial effects, systematic d-amino acid substitutions of the lead peptides (IRIK)2-NH2 (IK8-all L) and (IRVK)3-NH2 (IK12-all L) were performed. It was found that the corresponding D-enantiomers exhibited stronger antimicrobial activities with minimal or no change in hemolytic activities, hence translating very high selectivity indices of 407.0 and >9.8 for IK8-all D and IK12-all D respectively. IK8-all D was also demonstrated to be stable to degradation by broad spectrum proteases trypsin and proteinase K. The membrane disrupting bactericidal properties of IK8-all D effectively prevented drug resistance development and inhibited the growth of various clinically isolated MRSA, VRE, Acinetobacter baumanni, Pseudomonas aeruginosa, Cryptococcus. neoformans and Mycobacterium tuberculosis. Significant reduction in intracellular bacteria counts was also observed following treatment with IK8-all D in the Staphylococcus. aureus infected mouse macrophage cell line RAW264.7 (P < 0.01). These results suggest that the d-amino acids substituted β-sheet forming peptide IK8-all D with its enhanced antimicrobial activities and improved protease stability, is a promising therapeutic candidate with potential to combat

  10. Cohaerins G-K, azaphilone pigments from Annulohypoxylon cohaerens and absolute stereochemistry of cohaerins C-K.

    PubMed

    Surup, Frank; Mohr, Kathrin I; Jansen, Rolf; Stadler, Marc

    2013-11-01

    Four azaphilones, for which the trivial names cohaerins G, H, I and K are proposed, were isolated from the methanolic stromatal extract of Annulohypoxylon cohaerens together with the known metabolites cohaerins C-F and 4,5,4',5'-tetrahydroxy-1,1'-binaphthyl (BNT). Their planar structures were determined by NMR spectroscopy and by mass spectrometry. While their core structure is identical with cohaerin C and F, respectively, subgroups 2-hydroxy-6-methylphenyl and (1R,2R,4S)-4-hydroxy-2-methyl-6-oxocyclohexyl account for the structural diversity as substituents at C-3 of the azaphilone core. The absolute stereochemistry was assigned by NOE NMR experiments, CD spectroscopy and derivatisation with Mosher's acid; in addition, the stereochemistry of cohaerins C-F was revised. The metabolites showed cytotoxic effects besides a weak antimicrobial activity.

  11. A new enzyme involved in the control of the stereochemistry in the decalin formation during equisetin biosynthesis.

    PubMed

    Kato, Naoki; Nogawa, Toshihiko; Hirota, Hiroshi; Jang, Jae-Hyuk; Takahashi, Shunji; Ahn, Jong Seog; Osada, Hiroyuki

    2015-05-01

    Tetramic acid containing a decalin ring such as equisetin and phomasetin is one of the characteristic scaffolds found in fungal bioactive secondary metabolites. Polyketide (PKS)-nonribosomal peptide synthetase (NRPS) hybrid enzyme is responsible for the synthesis of the polyketide scaffold conjugated with an amino acid. PKS-NRPS hybrid complex programs to create structural diversity in the polyketide backbone have begun to be investigated, yet mechanism of control of the stereochemistry in a decalin formation via a Diels-Alder cycloaddition remains uncertain. Here, we demonstrate that fsa2, which showed no homology to genes encoding proteins of known function, in the fsa cluster responsible for equisetin and fusarisetin A biosynthesis in Fusarium sp. FN080326, is involved in the control of stereochemistry in decalin formation via a Diels-Alder reaction in the equisetin biosynthetic pathway.

  12. 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)

  13. 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)

  14. 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.

  15. Assignment of the C5′ Relative Stereochemistry in (+)-Lepadin F and (+)-Lepadin G and Absolute Configuration of (+)-Lepadin G

    PubMed Central

    Li, Gang; Hsung, Richard P.

    2010-01-01

    Concise assignments of the C5′ stereochemistry in (+)-lepadin F and (+)-lepadin G, and the absolute configuration of (+)-lepadin G via the first total syntheses of (+)-5′-epi-lepadin F, (+)-lepadin G, and (+)-5′epi-lepadin G are described. This work represents an illustrative example in which a diastereomeric pair can possess sufficient spectroscopic difference for clear assignment despite differing only at a highly insulated acyclic stereocenter. PMID:19775165

  16. Use of a methoxy substituent in controlling the stereochemistry of intramolecular iron-mediated diene/olefin cyclocoupling.

    PubMed

    Pearson, A J; Dorange, I B

    2001-05-04

    A methodology for stereocontrol during the intramolecular coupling between cyclohexadiene--Fe(CO)(3) complexes and pendant alkenes is presented. Introduction of a methoxy group at the C(3) position of the diene moiety controls pre- and postcyclization rearrangements of the diene Fe(CO)(3) unit, allowing the preparation of spirolactams with defined relative stereochemistry and with a cyclohexenone framework, thus making this reaction a potentially valuable tool for the construction of quaternary carbon centers.

  17. 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.

  18. ELECTRON DETACHMENT DISSOCIATION OF SYNTHETIC HEPARAN SULFATE GLYCOSAMINOGLYCAN TETRASACCHARIDES VARYING IN DEGREE OF SULFATION AND HEXURONIC ACID STEREOCHEMISTRY.

    PubMed

    Leach, Franklin E; Arungundram, Sailaja; Al-Mafraji, Kanar; Venot, Andre; Boons, Geert-Jan; Amster, I Jonathan

    2012-12-15

    Glycosaminoglycan (GAG) carbohydrates provide a challenging analytical target for structural determination due to their polydisperse nature, non-template biosynthesis, and labile sulfate modifications. The resultant structures, although heterogeneous, contain domains which indicate a sulfation pattern or code that correlates to specific function. Mass spectrometry, in particular electron detachment dissociation Fourier transform ion cyclotron resonance (EDD FT-ICR MS), provides a highly sensitive platform for GAG structural analysis by providing cross-ring cleavages for sulfation location and product ions specific to hexuronic acid stereochemistry. To investigate the effect of sulfation pattern and variations in stereochemistry on EDD spectra, a series of synthetic heparan sulfate (HS) tetrasaccharides are examined. Whereas previous studies have focused on lowly sulfated compounds (0.5-1 sulfate groups per disaccharide), the current work extends the application of EDD to more highly sulfated tetrasaccharides (1-2 sulfate groups per disaccharide) and presents the first EDD of a tetrasaccharide containing a sulfated hexuronic acid. For these more highly sulfated HS oligomers, alternative strategies are shown to be effective for extracting full structural details. These strategies inlcude sodium cation replacement of protons, for determining the sites of sulfation, and desulfation of the oligosaccharides for the generation of product ions for assigning uronic acid stereochemistry.

  19. ELECTRON DETACHMENT DISSOCIATION OF SYNTHETIC HEPARAN SULFATE GLYCOSAMINOGLYCAN TETRASACCHARIDES VARYING IN DEGREE OF SULFATION AND HEXURONIC ACID STEREOCHEMISTRY

    PubMed Central

    Leach, Franklin E.; Arungundram, Sailaja; Al-Mafraji, Kanar; Venot, Andre; Boons, Geert-Jan; Amster, I. Jonathan

    2012-01-01

    Glycosaminoglycan (GAG) carbohydrates provide a challenging analytical target for structural determination due to their polydisperse nature, non-template biosynthesis, and labile sulfate modifications. The resultant structures, although heterogeneous, contain domains which indicate a sulfation pattern or code that correlates to specific function. Mass spectrometry, in particular electron detachment dissociation Fourier transform ion cyclotron resonance (EDD FT-ICR MS), provides a highly sensitive platform for GAG structural analysis by providing cross-ring cleavages for sulfation location and product ions specific to hexuronic acid stereochemistry. To investigate the effect of sulfation pattern and variations in stereochemistry on EDD spectra, a series of synthetic heparan sulfate (HS) tetrasaccharides are examined. Whereas previous studies have focused on lowly sulfated compounds (0.5–1 sulfate groups per disaccharide), the current work extends the application of EDD to more highly sulfated tetrasaccharides (1–2 sulfate groups per disaccharide) and presents the first EDD of a tetrasaccharide containing a sulfated hexuronic acid. For these more highly sulfated HS oligomers, alternative strategies are shown to be effective for extracting full structural details. These strategies inlcude sodium cation replacement of protons, for determining the sites of sulfation, and desulfation of the oligosaccharides for the generation of product ions for assigning uronic acid stereochemistry. PMID:23230388

  20. 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.

  1. Assignment of the stereochemistry and anomeric configuration of structurally informative product ions derived from disaccharides: infrared photodissociation of glycosyl-glycolaldehydes in the negative ion mode.

    PubMed

    Bendiak, Brad; Fang, Tammy T

    2010-11-02

    Using mass spectrometry in the negative ion mode, m/z 221 ions are frequently observed as product ion substructures derived from reducing disaccharides having 2, 4, or 6 linkages. The ions have been shown to be glycosyl-glycolaldehydes. All 16 stereochemical variants of their pyranosides were prepared and evaluated by infrared photodissociation, in addition to HexNAc-glycolaldehyde variants (m/z 262) of 2-acetamido-2-deoxy-d-glucose and 2-acetamido-2-deoxy-d-galactose. The stereochemistry and anomeric configuration of these ions were differentiated in the gas phase using a Fourier transform ion cyclotron resonance spectrometer with infrared multiphoton dissociation at 10.6 μm. Results were compared to those obtained by collision-induced dissociation. In some cases, differentiation was far preferable using infrared photodissociation; in others, collision-induced dissociation was preferred. Using an instrument that interfaced a linear trap with a Fourier transform ion cyclotron resonance spectrometer, either dissociation technique could be used to optimally discriminate between isomers. With infrared photodissociation, spectral differences were highly statistically significant, even between pairs of isomers having spectra that appeared to be visually somewhat similar (p<1×10⁻⁹, student's t-test for key discriminatory ions). Comparisons among different instruments suggest that physical standards of the stereochemical variants of these ions will be required for their detailed structural assignments in unknowns, as some variation was observed among instruments, both using infrared photodissociation and collision-induced dissociation.

  2. 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)…

  3. 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…

  4. 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)…

  5. 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…

  6. 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…

  7. The Effects of Talking-Head with Various Realism Levels on Students' Emotions in Learning

    ERIC Educational Resources Information Center

    Mohamad Ali, Ahmad Zamzuri; Hamdan, Mohd Najib

    2017-01-01

    The aim of this study was to evaluate the effects of various realistic levels of talking-head on students' emotions in pronunciation learning. Four talking-head characters with varying levels of realism were developed and tested: a nonrealistic three-dimensional character, a realistic three-dimensional character, a two-dimensional character, and…

  8. 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…

  9. Sociological, Postmodern, and New Realism Perspectives in Social Constructionism: Implications for Literacy Research.

    ERIC Educational Resources Information Center

    Hruby, George G.

    2001-01-01

    Offers an historical definition of social constructionism, a review of its conceptual bases, and an exploration of its epistemological implications. Describes a history comprised of three paradigmatically distinct waves: a sociological, a postmodern, and an emerging third wave grounded in new realism or neonaturalism. Suggests potential uses of…

  10. 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…

  11. 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…

  12. Labs and slabs: television crime drama and the quest for forensic realism.

    PubMed

    Jermyn, Deborah

    2013-03-01

    This essay examines how crime dramas produced during, and since, the 1990s became marked by the quest for 'forensic realism'. In particular, the essay traces a landmark shift in the development of forensic realism in the form of the ground-breaking British police drama Prime Suspect in 1991. It is argued that this television series not only represents a turning point in television history, but that it also constitutes a key text in the broader cultural turn towards forensic fascination. Prime Suspect vividly revealed and displayed corpses, crime scenes and post-mortem photos in an unprecedented fashion for television. This essay shows how in the process it established new standards and expectations regarding the aesthetics and thematic content of the perceived 'realism' of the crime genre. Through an analysis of the reception and impact of Prime Suspect the essay also demonstrates how crime drama's increasing fascination with forensic realism has driven debate over just what kinds of stories and images constitute acceptable or appropriate subject matter for popular entertainment, and for the medium of television itself.

  13. Sex differences in visual realism in drawings of animate and inanimate objects.

    PubMed

    Lange-Küttner, Chris

    2011-10-01

    Sex differences in a visually realistic drawing style were examined using the model of a curvy cup as an inanimate object, and the Draw-A-Person test (DAP) as a task involving animate objects, with 7- to 12-year-old children (N = 60; 30 boys). Accurately drawing the internal detail of the cup--indicating interest in a depth feature--was not dependent on age in boys, but only in girls, as 7-year-old boys were already engaging with this cup feature. However, the age effect of the correct omission of an occluded handle--indicating a transition from realism in terms of function (intellectual realism) to one of appearance (visual realism)--was the same for both sexes. The correct omission of the occluded handle was correlated with bilingualism and drawing the internal cup detail in girls, but with drawing the silhouette contour of the cup in boys. Because a figure's silhouette enables object identification from a distance, while perception of detail and language occurs in nearer space, it was concluded that boys and girls may differ in the way they conceptualize depth in pictorial space, rather than in visual realism as such.

  14. The accuracy of meta-metacognitive judgments: regulating the realism of confidence.

    PubMed

    Buratti, Sandra; Allwood, Carl Martin

    2012-08-01

    Can people improve the realism of their confidence judgments about the correctness of their episodic memory reports by deselecting the least realistic judgments? An assumption of Koriat and Goldsmith's (Psychol Rev 103:490-517, 1996) model is that confidence judgments regulate the reporting of memory reports. We tested whether this assumption generalizes to the regulation of the realism (accuracy) of confidence judgments. In two experiments, 270 adults in separate conditions answered 50 recognition and recall questions about the contents of a just-seen video. After each answer, they made confidence judgments about the answer's correctness. In Experiment 1, the participants in the recognition conditions significantly increased their absolute bias when they excluded 15 questions. In Experiment 2, the participants in the recall condition significantly improved their calibration. The results indicate that recall, more than recognition, offers valid cues for participants to increase the realism of their report. However, the effects were small with only weak support for the conclusion that people have some ability to regulate the realism in their confidence judgments.

  15. 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...

  16. 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…

  17. 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…

  18. 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…

  19. 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…

  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. Quantum mechanics versus macroscopic realism: Is the flux there when nobody looks

    SciTech Connect

    Leggett, A.J.; Garg, A.

    1985-03-04

    It is shown that, in the contect of an idealized ''macroscopic quantum coherence'' experiment, the prediction of quantum mechanics are incompattible with the conjunction of two general assimptions which are designated ''macroscopic realism'' and ''noninvasive measurability at the macroscopiclevel.'' The conditions under which quantum mechanics can be tested against these assumptions in a realistic experiment are discussed.

  2. Perceived learning outcome: the relationship between experience, realism and situation awareness during simulator training.

    PubMed

    Saus, Evelyn-Rose; Johnsen, Bjørn Helge; Eid, Jarle

    2010-01-01

    Navigation errors are a frequent cause of serious accidents and work-related injuries among seafarers. The present study investigated the effects of experience, perceived realism, and situation awareness (SA) on the perceived learning outcome of simulator-based navigation training. Thirty-two Norwegian Navy officer cadets were assigned to a low and a high mental workload conditions based on previous educational and navigational experience. In the low mental workload condition, experience (negatively associated), perceived realism, and subjective SA explained almost half of the total variance in perceived learning outcome. A hierarchical regression analysis showed that only subjective SA made a unique contribution to the learning outcome. In the high mental workload condition, perceived realism and subjective SA together explained almost half of the variance in perceived learning outcome. Furthermore, both perceived realism and subjective SA were shown to make an independent contribution to perceived learning outcomes. The results of this study show that in order to enhance the learning outcomes from simulator training it is necessary to design training procedures and scenarios that enable students to achieve functional fidelity and to generate and maintain SA during training. This can further improve safety and reduce the risk of maritime disasters.

  3. 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…

  4. A plea for a touch of realism: reply to P Whitaker

    PubMed Central

    Lamb, David

    1990-01-01

    This reply to P Whitaker's `Resource allocation: a plea for a touch of realism' acknowledges that health-care ethics should be relevant to events in the real world, but questions the extent to which philosophical inquiry should be confined to parameters determined by existing sociopolitical forces. The reading of the daily paper is the morning prayer of the realist. PMID:2231637

  5. 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…

  6. 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…

  7. 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...

  8. 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…

  9. 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.

  10. A mismatch in the human realism of face and voice produces an uncanny valley.

    PubMed

    Mitchell, Wade J; Szerszen, Kevin A; Lu, Amy Shirong; Schermerhorn, Paul W; Scheutz, Matthias; Macdorman, Karl F

    2011-01-01

    The uncanny valley has become synonymous with the uneasy feeling of viewing an animated character or robot that looks imperfectly human. Although previous uncanny valley experiments have focused on relations among a character's visual elements, the current experiment examines whether a mismatch in the human realism of a character's face and voice causes it to be evaluated as eerie. The results support this hypothesis.

  11. Controlling the stereochemistry and regularity of butanethiol self-assembled monolayers on au(111).

    PubMed

    Yan, Jiawei; Ouyang, Runhai; Jensen, Palle S; Ascic, Erhad; Tanner, David; Mao, Bingwei; Zhang, Jingdong; Tang, Chunguang; Hush, Noel S; Ulstrup, Jens; Reimers, Jeffrey R

    2014-12-10

    The rich stereochemistry of the self-assembled monolayers (SAMs) of four butanethiols on Au(111) is described, the SAMs containing up to 12 individual C, S, or Au chiral centers per surface unit cell. This is facilitated by synthesis of enantiomerically pure 2-butanethiol (the smallest unsubstituted chiral alkanethiol), followed by in situ scanning tunneling microscopy (STM) imaging combined with density functional theory molecular dynamics STM image simulations. Even though butanethiol SAMs manifest strong headgroup interactions, steric interactions are shown to dominate SAM structure and chirality. Indeed, steric interactions are shown to dictate the nature of the headgroup itself, whether it takes on the adatom-bound motif RS(•)Au(0)S(•)R or involves direct binding of RS(•) to face-centered-cubic or hexagonal-close-packed sites. Binding as RS(•) produces large, organizationally chiral domains even when R is achiral, while adatom binding leads to rectangular plane groups that suppress long-range expression of chirality. Binding as RS(•) also inhibits the pitting intrinsically associated with adatom binding, desirably producing more regularly structured SAMs.

  12. 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.

  13. Methods for the comprehensive structural elucidation of constitution and stereochemistry of lipopeptides.

    PubMed

    Gerhardt, Heike; Sievers-Engler, Adrian; Jahanshah, Ghazaleh; Pataj, Zoltán; Ianni, Federica; Gross, Harald; Lindner, Wolfgang; Lämmerhofer, Michael

    2016-01-08

    A panel of methods of general suitability for complete structural elucidation of the stereochemistry of cyclopeptides, depsipeptides and lipopeptides is presented and described in detail. The suitability of the proposed methods was exemplified on the lipopeptide poaeamide from Pseudomonas poae. Amino acid configurations have been assigned by direct LC enantiomer separation with Chiralpak ZWIX(+) and were confirmed by GC enantiomer separation on Chirasil L-Val. 3-Hydroxydecanoic acid absolute configuration was analyzed on Chiralpak ZWIX(+) and confirmed by injection on ZWIX(-) which showed opposite elution order. Plenty of d-amino acids have been found in this lipopeptide. It contained in total 5 Leu residues of which one had d-configuration. The position of the d-Leu in the peptide sequence was determined by pepsin and chemical digestions in combination with isolation of diagnostic peptide-fragments and subsequent identification of absolute configurations of the Leu residues. This allowed pinpointing the position of the d-amino acid. The complementarity of the peptide retention profiles on Chiralpak ZWIX column as compared to both RPLC and HILIC suggests its great utility as an alternative peptide separation tool.

  14. Absolute Stereochemistry of the β-Hydroxy Acid Unit in Hantupeptins and Trungapeptins.

    PubMed

    Gupta, Deepak Kumar; Ding, Gary Chi Ying; Teo, Yong Chua; Tan, Lik Tong

    2016-01-01

    The β-hydroxy/amino acid unit is a common structural feature of many bioactive marine cyanobacterial depsipeptides. In this study, the absolute stereochemistry of the β-hydroxy acid moieties in hantupeptins and trungapeptins were determined through their synthesis and HPLC analysis of the Mosher ester derivatives. Synthesis of two3-hydroxy-2-methyloctanoic acid (Hmoa) stereoisomers, (2S,3R)-Hmoa and (2S,3S)-Hmoa, were achieved using diastereoselective asymmetric method and the retention times of all four Hmoa isomers were established indirectly by RPLC-MS analysis of their Mosher ester derivative standards. Based on the retention times of the standards, the absolute configuration of the Hmoa unit in hantupeptin C (3) and trungapeptin C (6) was assigned as (2R,3S)- and (2S,3R)-Hmoa, respectively. The use of the Mosher's reagents, coupled with HPLC analysis, provided a viable alternative to the absolute stereochemical determination of β-hydroxy acid units in depsipeptides.

  15. 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.

  16. Study of the Stereochemistry and Oxidation Mechanism of Plant Polyphenols, Assisted by Computational Chemistry.

    PubMed

    Matsuo, Yosuke

    2017-01-01

     In recent years, plant polyphenols have attracted great attention due to their wide range of biological activities. Certain kinds of polyphenols have complex structures; therefore, it is difficult to elucidate their total structure, including stereochemistry. In this study, we reinvestigated the stereostructures of two major C-glycosidic ellagitannins contained in Quercus plants, vescalagin and castalagin, and revised their stereostructures based on theoretical calculations of spectroscopic data. We also determined the structures of quercusnins A and B, isolated from the sapwood of Quercus crispula, based on theoretical calculations of NMR data. The oxidation mechanism of polyphenols has not been entirely elucidated. Therefore, we have also studied the oxidation mechanism of tea catechins during black tea production. Our investigation of the oxidation mechanism of black tea pigment theaflavins revealed that the difference in the position of the galloyl ester affords different oxidation products of theaflavins. In addition, oxidation products of pyrogallol-type catechins could be classified into three types-dehydrotheasinensins, theacitrins, and proepitheaflagallins; their detailed production and degradation mechanisms were also examined.

  17. 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.

  18. Stereochemistry and Position-Dependent Effects of Carcinogens on TATA/TBP Binding

    PubMed Central

    Zhang, Qing; Schlick, Tamar

    2006-01-01

    The TATA-box binding protein (TBP) is required by eukaryotic RNA polymerases to bind to the TATA box, an eight-basepair DNA promoter element, to initiate transcription. Carcinogen adducts that bind to the TATA box can hamper this important process. Benzo[a]pyrene (BP) is a representative chemical carcinogen that can be metabolically converted to highly reactive benzo[a]pyrene diol epoxides (BPDE), which in turn can form chemically stereoisomeric BP-DNA adducts. Depending on the TATA-bound adduct's location and stereochemistry, TATA/TBP binding can be decreased or increased. Our previous study interpreted the location-dependent effect in terms of conformational freedom and major-groove space available to BP. Here we further explore specific structural changes of the TATA/TBP complex to help interpret the stereochemical effect in terms of the flexibility of the TATA bases that frame the intercalated adduct. Thermodynamic analyses using molecular mechanics Poisson-Boltzmann surface area (MM-PBSA) yield large standard deviations, which make the computed binding free energies the same within the error bars and point to current limitations of free energy calculations of large and highly charged systems like DNA/protein complexes. PMID:16387764

  19. 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.

  20. 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. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

  1. 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.

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

    PubMed Central

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

    2008-01-01

    Regioselective opening of ring E of solasodine under various conditions afforded (25R)-22,26-epimino­cholesta-5,22(N)-di­ene-3β,16β-diyl diacetate (previously known as 3,16-diacetyl pseudosolasodine B), C31H47NO4, or (22S,25R)-16β-hydr­oxy-22,26-epimino­cholesta-5-en-3β-yl acetate (a derivative of the naturally occurring alkaloid oblonginine), C29H47NO3. 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. PMID:18391392

  3. 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…

  4. 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…

  5. Synthesis, stereochemistry determination, pharmacological studies and quantum chemical analyses of bisthiazolidinone derivative

    NASA Astrophysics Data System (ADS)

    Mushtaque, Md.; Avecilla, Fernando; Hafeez, Zubair Bin; Jahan, Meriyam; Khan, Md. Shahzad; Rizvi, M. Moshahid A.; Khan, Mohd. Shahid; Srivastava, Anurag; Mallik, Anwesha; Verma, Saurabh

    2017-01-01

    A new compound (3) bisthaizolidinone derivative was synthesized by Knoevenagel condensation reaction. The structure of synthesized compound was elucidated by different spectral techniques and X-ray diffraction studies. The stereochemistry of the compound (3) was determined by 1Hsbnd 1H NOESY, 1Hsbnd 1H NMR COSY and single crystal X-ray diffraction studies as (Z, Z)-configuration. The computational quantum chemical studies of compound(3) like, IR, UV, NBO analysis were performed by DFT with Becke-3-Lee-Yang-Parr (B3LYP) exchange-correlation functional in combination with 6-311++G(d,p) basis sets. The DNA-binding of compound (3) exhibited a moderate binding constant (Kb = 1 × 105 Lmol-1) with hypochromic shift. The molecular docking displayed good binding affinity -7.18 kcal/mol. The MTT assay of compound (3) was screened against different cancerous cell lines, HepG2, Siha, Hela and MCF-7. Studies against these cell lines depicted that the screened compound (3) showed potent inhibitory activity against HepG2 cell (IC50 = 7.5 μM) followed by MCF-7 (IC50 = 52.0 μM), Siha (IC50 = 66.98 μM), Hela (IC50 = 74.83 μM) cell lines, and non-toxic effect against non-cancerous HEK-293 cells (IC50 = 287.89 μM) at the concentration range (0-300) μM. Furthermore, cell cycle perturbation was performed on HepG2 & Siha cell lines and observed that cells were arrested in G2/M in HepG2, and G0/G1 in Siha cell lines with respect to untreated control. Hence, compound (3) possesses potent anti-cancerous activity against HepG2 cell line.

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

    PubMed Central

    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.; de Groot, Raoul J.

    2016-01-01

    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

  7. 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.

  8. Effect of stereochemistry on the transport of Aca-linked beta-turn peptidomimetics across a human intestinal cell line.

    PubMed

    Tamura, K; Agrios, K A; Vander Velde, D; Aubé, J; Borchardt, R T

    1997-09-01

    Transcellular transport is one of the most important barriers facing the development of new therapeutic agents. However, little is known about the specific effects of structure and particularly stereochemistry on cell permeability. An attractive in vitro model has been developed for the direct assessment of cell transport, using the immortalized human epithelial cell line, Caco-2. The present study assesses the effects of stereochemistry on transport in a commonly used beta-turn model system. Thus, L,L- and L,D-Ala-Ala were cyclized with aminocaproic acid, resulting in macrocycles in which the dipeptides correspond to the i + 1 and i + 2 positions of a beta-turn. The transport of these dipeptides across a Caco-2 cell monolayer was determined, along with corresponding acyclic models (L,L- and L,D-CH3CH2C(O)-Ala-Ala-n-Pr). The transport studies were carried out in the presence and absence of verapamil, a known inhibitor of the apically polarized efflux system present in Caco-2 cells. Both apical-->basolateral and basolateral-->apical transport were measured. Measurements made in the presence of verapamil showed that the cyclic peptides experienced a ca. 4-5-fold difference in intrinsic flux depending on stereochemistry, with the L,D isomer being transported at a higher rate. These differences disappeared in the acyclic cases examined (permeability coefficient ratios of the L,D/L,L isomers were 1.04-1.13). These observations are discussed in terms of the conformations and hydrogen-bonding characteristics of the compounds as determined by NMR spectroscopy.

  9. Design, synthesis and in vitro evaluation of a series of α-substituted phenylpropanoic acid PPARγ agonists to further investigate the stereochemistry-activity relationship.

    PubMed

    Ohashi, Masao; Nakagome, Izumi; Kasuga, Jun-Ichi; Nobusada, Hiromi; Matsuno, Kenji; Makishima, Makoto; Hirono, Shuichi; Hashimoto, Yuichi; Miyachi, Hiroyuki

    2012-11-01

    We previously demonstrated that the α-benzylphenylpropanoic acid-type PPARγ-selective agonist 6 exhibited a reversed stereochemistry-activity relationship, that is, the (R)-enantiomer is a more potent PPARγ agonist than the (S)-enantiomer, compared with structurally similar α-ethylphenylpropanoic acid-type PPAR agonists. Here, we designed, synthesized and evaluated the optically active α-cyclohexylmethylphenylpropanoic acid derivatives 7 and α-phenethylphenylpropanoic acid derivatives 8, respectively. Interestingly, α-cyclohexylmethyl derivatives showed reversal of the stereochemistry-activity relationship [i.e., (R) more potent than (S)], like α-benzyl derivatives, whereas α-phenethyl derivatives showed the 'normal' relationship [(S) more potent than (R)]. These results suggested that the presence of a branched carbon atom at the β-position with respect to the carboxyl group is a critical determinant of the reversed stereochemistry-activity relationship.

  10. Multivariate analysis of electron detachment dissociation and infrared multiphoton dissociation mass spectra of heparan sulfate tetrasaccharides differing only in hexuronic acid stereochemistry.

    PubMed

    Oh, Han Bin; Leach, Franklin E; Arungundram, Sailaja; Al-Mafraji, Kanar; Venot, Andre; Boons, Geert-Jan; Amster, I Jonathan

    2011-03-01

    The structural characterization of glycosaminoglycan (GAG) carbohydrates by mass spectrometry has been a long-standing analytical challenge due to the inherent heterogeneity of these biomolecules, specifically polydispersity, variability in sulfation, and hexuronic acid stereochemistry. Recent advances in tandem mass spectrometry methods employing threshold and electron-based ion activation have resulted in the ability to determine the location of the labile sulfate modification as well as assign the stereochemistry of hexuronic acid residues. To facilitate the analysis of complex electron detachment dissociation (EDD) spectra, principal component analysis (PCA) is employed to differentiate the hexuronic acid stereochemistry of four synthetic GAG epimers whose EDD spectra are nearly identical upon visual inspection. For comparison, PCA is also applied to infrared multiphoton dissociation spectra (IRMPD) of the examined epimers. To assess the applicability of multivariate methods in GAG mixture analysis, PCA is utilized to identify the relative content of two epimers in a binary mixture.

  11. Enantiomeric separation and determination of absolute stereochemistry of asymmetric molecules in drug discovery: building chiral technology toolboxes.

    PubMed

    McConnell, Oliver; Bach, Alvin; Balibar, Carl; Byrne, Neal; Cai, Yanxuan; Carter, Guy; Chlenov, Michael; Di, Li; Fan, Kristi; Goljer, Igor; He, Yanan; Herold, Don; Kagan, Michael; Kerns, Edward; Koehn, Frank; Kraml, Christina; Marathias, Vasilios; Marquez, Brian; McDonald, Leonard; Nogle, Lisa; Petucci, Christopher; Schlingmann, Gerhard; Tawa, Gregory; Tischler, Mark; Williamson, R Thomas; Sutherland, Alan; Watts, William; Young, Mairead; Zhang, Mei-Yi; Zhang, Yingru; Zhou, Dahui; Ho, Douglas

    2007-09-01

    The application of Chiral Technology, or the (extensive) use of techniques or tools for the determination of absolute stereochemistry and the enantiomeric or chiral separation of racemic small molecule potential lead compounds, has been critical to successfully discovering and developing chiral drugs in the pharmaceutical industry. This has been due to the rapid increase over the past 10-15 years in potential drug candidates containing one or more asymmetric centers. Based on the experiences of one pharmaceutical company, a summary of the establishment of a Chiral Technology toolbox, including the implementation of known tools as well as the design, development, and implementation of new Chiral Technology tools, is provided.

  12. Application of chiral gas chromatography with electroantennographic detection to the determination of the stereochemistry of a cockroach sex pheromone.

    PubMed

    Leal, W S; Shi, X; Liang, D; Schal, C; Meinwald, J

    1995-02-14

    The coupling of an electroantennographic detector to a chiral capillary gas chromatographic system provides a highly sensitive technique for the determination of pheromone stereochemistry. Electronic modification of the usual electroantennographic detector enables the detector to respond to the relatively broad peaks produced by chiral gas chromatographic systems. By using this methodology, supellapyrone, a female sex pheromone of the brownbanded cockroach Supella longipalpa (Orthoptera: Blattellidae), is shown to be 5-(2'R,4'R-dimethylheptanyl)-3-methyl-2H-pyran-2-one.

  13. Application of chiral gas chromatography with electroantennographic detection to the determination of the stereochemistry of a cockroach sex pheromone.

    PubMed Central

    Leal, W S; Shi, X; Liang, D; Schal, C; Meinwald, J

    1995-01-01

    The coupling of an electroantennographic detector to a chiral capillary gas chromatographic system provides a highly sensitive technique for the determination of pheromone stereochemistry. Electronic modification of the usual electroantennographic detector enables the detector to respond to the relatively broad peaks produced by chiral gas chromatographic systems. By using this methodology, supellapyrone, a female sex pheromone of the brownbanded cockroach Supella longipalpa (Orthoptera: Blattellidae), is shown to be 5-(2'R,4'R-dimethylheptanyl)-3-methyl-2H-pyran-2-one. PMID:7862628

  14. Cartographic continuum rendering based on color and texture interpolation to enhance photo-realism perception

    NASA Astrophysics Data System (ADS)

    Hoarau, Charlotte; Christophe, Sidonie

    2017-05-01

    Graphic interfaces of geoportals allow visualizing and overlaying various (visually) heterogeneous geographical data, often by image blending: vector data, maps, aerial imagery, Digital Terrain Model, etc. Map design and geo-visualization may benefit from methods and tools to hybrid, i.e. visually integrate, heterogeneous geographical data and cartographic representations. In this paper, we aim at designing continuous hybrid visualizations between ortho-imagery and symbolized vector data, in order to control a particular visual property, i.e. the photo-realism perception. The natural appearance (colors, textures) and various texture effects are used to drive the control the photo-realism level of the visualization: color and texture interpolation blocks have been developed. We present a global design method that allows to manipulate the behavior of those interpolation blocks on each type of geographical layer, in various ways, in order to provide various cartographic continua.

  15. 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. © 2011 Blackwell Publishing Ltd.

  16. Cognitive components of naming in children: effects of referential uncertainty and stimulus realism.

    PubMed

    Johnson, C J

    1992-02-01

    The ease of picture naming in children was assessed as a function of two stimulus characteristics: (a) the number of available correct names for a picture (referential uncertainty) and (b) the degree to which a picture realistically represents the depicted object (stimulus realism). Two experiments employing different methods demonstrated that: (a) children named low uncertainty objects (those with a single dominant name, e.g., key, elephant) faster than high uncertainty objects (those with multiple possible correct names, e.g., lamp/light, stove/oven) and (b) this uncertainty effect arose at a stage of naming subsequent to object identification. Possible underlying mechanisms for the uncertainty effect include passive diffusion of activation over multiple object-name pathways or active inhibition among competing candidate names. Stimulus realism (colored photographs vs uncolored line drawings) did not consistently influence naming performance. Implications for understanding children's naming behavior are discussed.

  17. Decoherence-free emergence of macroscopic local realism for entangled photons in a cavity

    SciTech Connect

    Portolan, S.; Rossi, F.; Di Stefano, O.; Savasta, S.; Girlanda, R.

    2006-02-15

    We investigate the influence of environmental noise on polarization entangled light generated by parametric emission in a cavity. By adopting a recent separability criterion, we show that (i) self-stimulation may suppress the detrimental influence of noise on entanglement, but (ii) once it becomes effective, a noise-equipped classical model of parametric emission provides the same results of quantum theory with respect to the separability criterion. More generally we also show that, in the macroscopic limit, it is not possible to observe violations of local realism with measurements of finite order n-particle correlations only. These results provide a prototypical case of the emergence of macroscopic local realism in the presence of strong entanglement even in the absence of decoherence.

  18. The Relationship Between Realism in Air Force Exercises and Combat Readiness

    DTIC Science & Technology

    1994-09-01

    units. Military Exercise . Any activity involving the operation of actual military forces in an artificial or simulated hostile environment (11:9). R...obstacles that may reduce exercise realism are presented. Types of Exercises An exercise is "any activity involving the operation of actual military forces...summarized and provided to you with the next round of the survey. Thanks for your participation! Definition of Key Terms A. Exercise . Any activity

  19. Experimental violation of the local realism for four-qubit Dicke state.

    PubMed

    Zhao, Yuan-Yuan; Wu, Yu-Chun; Xiang, Guo-Yong; Li, Chuan-Feng; Guo, Guang-Can

    2015-11-16

    Dicke state is an widely used type of multi-particle entangled state in quantum information. However, very few works have been done on its nonlocality. Here we prepare a four-photon symmetric Dicke state, whose fidelity is as high as 0.904 ± 0.004, and devise a simple Bell-type inequality to demonstrate that it violates the local realism with 12 standard deviation.

  20. A mismatch in the human realism of face and voice produces an uncanny valley

    PubMed Central

    Mitchell, Wade J; Szerszen, Kevin A; Lu, Amy Shirong; Schermerhorn, Paul W; Scheutz, Matthias; MacDorman, Karl F

    2011-01-01

    The uncanny valley has become synonymous with the uneasy feeling of viewing an animated character or robot that looks imperfectly human. Although previous uncanny valley experiments have focused on relations among a character's visual elements, the current experiment examines whether a mismatch in the human realism of a character's face and voice causes it to be evaluated as eerie. The results support this hypothesis. PMID:23145223

  1. 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

  2. Confidence judgment in depression and dysphoria: the depressive realism vs. negativity hypotheses.

    PubMed

    Szu-Ting Fu, Tiffany; Koutstaal, Wilma; Poon, Lucia; Cleare, Anthony J

    2012-06-01

    According to the negativity hypothesis, depressed individuals are over-pessimistic due to negative self-concepts. In contrast, depressive realism suggests that depressed persons are realistic compared to their nondepressed controls. However, evidence supporting depressive realism predominantly comes from judgment comparisons between controls and nonclinical dysphoric samples when the controls showed overconfident bias. This study aimed to test the validity of the two accounts in clinical depression and dysphoria. Sixty-eight participants, including healthy controls (n = 32), patients with DSM-IV major depression (n = 20), and dysphoric participants with CDC-defined chronic fatigue syndrome (n = 16) performed an adjective recognition task and reported their item-by-item confidence judgments and post-test performance estimate (PTPE). Compared to realistic PTPE made by the controls, patients with major depression showed significant underconfidence. The PTPE of the dysphoric participants was relatively accurate. Both the depressed and dysphoric participants displayed less item-by-item overconfidence as opposed to significant item-by-item overconfidence shown by the controls. The judgment-accuracy patterns of the three groups need to be replicated with larger samples using non-memory task domains. The present study confirms depressive realism in dysphoric individuals. However, toward a more severe depressive emotional state, the findings did not support depressive realism but are in line with the prediction of the negativity hypothesis. It is not possible to determine the validity of the two hypotheses when the controls are overconfident. Dissociation between item-by-item and retrospective confidence judgments is discussed. Copyright © 2011 Elsevier Ltd. All rights reserved.

  3. 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.

  4. What does optimization theory actually predict about crown profiles of photosynthetic capacity when models incorporate greater realism?

    PubMed

    Buckley, Thomas N; Cescatti, Alessandro; Farquhar, Graham D

    2013-08-01

    Measured profiles of photosynthetic capacity in plant crowns typically do not match those of average irradiance: the ratio of capacity to irradiance decreases as irradiance increases. This differs from optimal profiles inferred from simple models. To determine whether this could be explained by omission of physiological or physical details from such models, we performed a series of thought experiments using a new model that included more realism than previous models. We used ray-tracing to simulate irradiance for 8000 leaves in a horizontally uniform canopy. For a subsample of 500 leaves, we simultaneously optimized both nitrogen allocation (among pools representing carboxylation, electron transport and light capture) and stomatal conductance using a transdermally explicit photosynthesis model. Few model features caused the capacity/irradiance ratio to vary systematically with irradiance. However, when leaf absorptance varied as needed to optimize distribution of light-capture N, the capacity/irradiance ratio increased up through the crown - that is, opposite to the observed pattern. This tendency was counteracted by constraints on stomatal or mesophyll conductance, which caused chloroplastic CO(2) concentration to decline systematically with increasing irradiance. Our results suggest that height-related constraints on stomatal conductance can help to reconcile observations with the hypothesis that photosynthetic N is allocated optimally. © 2013 John Wiley & Sons Ltd.

  5. Physics.

    PubMed

    Bromley, D A

    1980-07-04

    From massive quarks deep in the hearts of atomic nuclei to the catastrophic collapse of giant stars in the farthest reaches of the universe, from the partial realization of Einstein's dream of a unified theory of the forces of nature to the most practical applications in technology, medicine, and throughout contemporary society, physics continues to have a profound impact on man's view of the universe and on the quality of life. The author argues that the past few years, in terms of new discoveries, new insight-and the new questions-have been among the most productive in the history of the field and puts into context his selection of some of the most important new developments in this fundamental science.

  6. Understanding health decisions using critical realism: home-dialysis decision-making during chronic kidney disease.

    PubMed

    Harwood, Lori; Clark, Alexander M

    2012-03-01

    Understanding health decisions using critical realism: home-dialysis decision-making during chronic kidney disease This paper examines home-dialysis decision making in people with Chronic Kidney Disease (CKD) from the perspective of critical realism. CKD programmes focus on patient education for self-management to delay the progression of kidney disease and the preparation and support for renal replacement therapy e.g.) dialysis and transplantation. Home-dialysis has clear health, societal and economic benefits yet service usage is low despite efforts to realign resources and educate individuals. Current research on the determinants of modality selection is superficial and insufficient to capture the complexities embedded in the process of dialysis modality selection. Predictors of home-dialysis selection and the effect of chronic kidney disease educational programmes provide a limited explanation of this experience. A re-conceptualization of the problem is required in order to fully understand this process. The epistemology and ontology of critical realism guides our knowledge and methodology particularly suited for examination of these complexities. This approach examines the deeper mechanisms and wider determinants associated with modality decision making, specifically who chooses home dialysis and under what circumstances. Until more is known regarding dialysis modality decision making service usage of home dialysis will remain low as interventions will be based on inadequate epistemology.

  7. 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.

  8. Low vs. high fidelity: the importance of 'realism' in the simulation of a stone treatment procedure.

    PubMed

    Sarmah, Piyush; Voss, Jim; Ho, Adrian; Veneziano, Domenico; Somani, Bhaskar

    2017-07-01

    Simulation training for stone surgery is now increasingly used as part of training curricula worldwide. A combination of low and high fidelity simulators has been used with varying degrees of 'realism' provided by them. In this review, we discuss low and high fidelity simulators used for ureteroscopy (URS) and percutaneous nephrolithotomy (PCNL) stone procedures with their advantages, disadvantages and future direction for endourological simulation surgery. The final goal will be to understand whether or not 'realism' has to be considered as a critical element in simulation for this field. There is a wide range of simulators available for URS and PCNL training ranging from basic bench-type model to advanced virtual reality and cadaveric models, all providing various levels of realism. Although basic models might be more useful to novices, advanced models allow for complex and more realistic simulation training. With a wide variety of simulators now available and given the latest novelties in modular training curriculums, combination of low and high fidelity simulators that provide a realistic and cost-effective option seems to be the way forward. It is unavoidable that simulators will play an increasing role in endourological training.

  9. 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.

  10. Synthesis, determination of stereochemistry, and evaluation of new bisindole alkaloids from the myxomycete Arcyria ferruginea: an approach for Wnt signal inhibitor.

    PubMed

    Kaniwa, Kouken; Arai, Midori A; Li, Xiaofan; Ishibashi, Masami

    2007-08-01

    To determine the stereochemistry of dihydroarcyriarubin C (1), new bisindole alkaloid isolated from the myxomycete Arcyria ferruginea, cis- (2) and trans-dihydroarcyriarubin C (3) were synthesized. Comparison of their NMR characteristics allowed the trans stereochemistry of the natural product to be confirmed. Moreover, the Wnt signal inhibitory activities of 2 and 3 were compared with that of arcyriaflavin C (4), which is a natural product containing a bond between C-2 and C-2'. The cis-dihydroarcyriarubin C (2) showed moderate inhibition of Wnt signal transcription, which suggests that bisindole frameworks might be useful as small-molecule Wnt signal inhibitors.

  11. 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.

  12. Structure-activity relationship studies on acremomannolipin A, the potent calcium signal modulator with a novel glycolipid structure 2: Role of the alditol side chain stereochemistry.

    PubMed

    Tsutsui, Nozomi; Tanabe, Genzoh; Gotoh, Genki; Morita, Nao; Nomura, Naohisa; Kita, Ayako; Sugiura, Reiko; Muraoka, Osamu

    2014-02-01

    Five alditol analogs 1b-1f of a novel glycolipid acremomannolipin A (1a), the potential Ca(2+) signal modulator isolated from Acremonium strictum, were synthesized by employing a stereoselective β-mannosylation of appropriately protected mannose with five hexitols with different stereochemistry, and their potential on modulating Ca(2+) signaling were evaluated. All these analogs were more potent compared to the original compound 1a, and proved that mannitol stereochemistry of 1a was not critical for the potent calcium signal modulating.

  13. Stereochemistry of N-Benzoyl-5-substituted-1-benzazepines Revisited: Synthesis of the Conformationally Biased Derivatives and Revision of the Reported Structure.

    PubMed

    Tabata, Hidetsugu; Yoneda, Tetsuya; Tasaka, Tomohiko; Ito, Shigekazu; Oshitari, Tetsuta; Takahashi, Hideyo; Natsugari, Hideaki

    2016-04-15

    The syn (aR*,5R*) and anti (aS*,5R*) diastereomers of N-benzoyl-C5-substituted-1-benzazepines originating in the chiralities at C5 and the Ar-N(C═O) axis were first stereoselectively synthesized by biasing the conformation with a substituent at C6 and C9, respectively. Detailed examination of the stereochemistry (i.e., conformation and configuration) of these N-benzoyl-1-benzazepines by X-ray crystallographic analysis, VT NMR, and DFT calculations revealed new physicochemical aspects of these heterocycles including revision of the stereochemistry previously reported.

  14. 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.

  15. Analysis of stereochemistry and biosynthesis of epicatechin in tea plants by chiral phase high performance liquid chromatography.

    PubMed

    Qian, Yumei; Zhao, Xianqian; Zhao, Lei; Cui, Lilan; Liu, Li; Jiang, Xiaolan; Liu, Yajun; Gao, Liping; Xia, Tao

    2015-12-01

    Tea (Camellia sinensis) is rich in flavan-3-ols (catechins), especially epicatechin (EC), which is the predominant extension unit of polymeric proanthocyanidins (PAs). However, studies assessing EC's stereochemistry are scarce. Here, a high performance liquid chromatography column using amylose tris-(3, 5-dimethylphenylcarbamate) immobilized on silica-gel as chiral stationary phases (CSPs) was applied to explore its stereochemistry and biosynthetic pathway in tea plants. The results revealed (-)-epicatechin [(-)-EC] was the predominant di-hyroxy-non-galloylated-catechins, while (+)-epicatechin [(+)-EC] was not detected. Interestingly, (-)-EC was the only product obtained from cyanidin using the partially purified native C. sinensis anthocyanidin reductase (CsANR) in the presence of reduction nicotinamide adenine dinucleotide phosphate (NADPH); meanwhile, (+)-EC was the main product using recombinant CsANR in the same conditions. In addition, (-)-EC could be obtained from (+)-catechin [(+)-C] using recombinant CsANR, which displayed C3-epimerase activity in the presence of oxidation nicotinamide adenine dinucleotide phosphate (NADP(+)). But the partially purified native CsANR did not possess this function. Finally, (-)-EC could result from the de-gallate acid reaction of epicatechin gallate (ECG) catalyzed by a novel partially purified native galloylated catechins hydrolase (GCH) from tea leaves. In summary, (-)-EC is likely the product of native protein from the tea plants, and (+)-EC is only produced in a reaction catalyzed by recombinant CsANR in vitro. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

  16. Theoretical study on the mechanism and stereochemistry of the cinchona-thiourea organocatalytic hydrophosphonylation of an α-ketoester.

    PubMed

    Li, Weiyi; Huang, Dongfeng; Lv, Yajing

    2013-11-21

    The mechanism and stereochemistry of the hydrophosphonylation of an α-ketoester with dimethylphosphonate (DMHP) catalyzed by a thiourea-cinchona organocatalyst have been studied by the ONIOM method. The calculations show that the catalytic cycle is a three-step process, including the deprotonation of DMHP, C-P bond formation via nucleophilic addition and proton transfer with the regeneration of the catalyst. The deprotonation of DMHP mediated by the basicity of the quinuclidine nitrogen atom is the rate-determining step for the entire reaction. The activation of the α-ketoester by the thiourea or protonated cinchona moiety of the bifunctional catalyst is comparatively investigated, and the former is energy-preferred. AIM combined with NBO analysis indicate that the multiple hydrogen bonds play essential roles in activating substrates, facilitating charge transfer and stabilizing transition states and intermediates. The stereochemistry of the reaction is controlled by the C-P bond formation step and originated from the chiral induction of the multiple hydrogen-bonding interactions. The bulkier substituent groups on the chiral scaffold of the catalyst may increase rigidity of the catalyst and the asymmetric induction to the substrates. The calculations predict that alkyl substituted α-ketoesters might also be converted to chiral α-hydroxyl phosphonates with high enantioselectivity.

  17. From peptides to their alternating ester-urea analogues: synthesis and influence of hydrogen bonding motif and stereochemistry on aggregation.

    PubMed

    Hartwig, Sebastian; Schwarz, Jutta; Hecht, Stefan

    2010-02-05

    Peptide-mimicking scaffolds with an incorporated ester-urea motif, replacing two adjacent amide residues, were synthesized and their aggregation behavior was studied in dependence of hydrogen bonding sites as well as backbone stereochemistry. Two oligomer series containing either 50% or 100% ester-urea units and either all-(l) or (d)-alt-(l) backbone configuration were prepared via ester and amide couplings, using a divergent/convergent exponential growth strategy. Their aggregation behavior in organic solution was investigated by means of concentration-dependent NMR spectroscopy and compared to the parent peptide series. Interestingly, the naturally occurring peptide scaffold exhibits the largest tendency to associate in combination with the strongest difference in aggregation behavior between all-(l) and (d)-alt-(l) backbone stereochemistry. With increasing incorporation of the ester-urea motif the aggregation strength decreases and become much less dependent on the backbone configuration. The obtained structure-aggregation relationships reveal the importance of the commensurability and multivalency of hydrogen bonding sites as well as conformational restriction for peptide association and should hence aid the design of peptide mimics, such as beta-sheet breakers or gelators.

  18. Composition and stereochemistry of ephedrine alkaloids accumulation in Ephedra sinica Stapf.

    PubMed

    Krizevski, Raz; Bar, Einat; Shalit, Or; Sitrit, Yaron; Ben-Shabat, Shimon; Lewinsohn, Efraim

    2010-06-01

    Ephedra sinica Stapf (Ephedraceae) is a widely used Chinese medicinal plant (Chinese name: Ma Huang). The main active constituents of E. sinica are the unique and taxonomically restricted adrenergic agonists phenylpropylamino alkaloids, also known as ephedrine alkaloids: (1R,2S)-norephedrine (1S,2S)-norpseudoephedrine, (1R,2S)-ephedrine, (1S,2S)-pseudoephedrine, (1R,2S)-N-methylephedrine and (1S,2S)-N-methylpseudoephedrine. GC-MS analysis of freshly picked young E. sinica stems enabled the detection of 1-phenylpropane-1,2-dione and (S)-cathinone, the first two putative committed biosynthetic precursors to the ephedrine alkaloids. These metabolites are only present in young E. sinica stems and not in mature stems or roots. The related Ephedra foemina and Ephedra foliata also lack ephedrine alkaloids and their metabolic precursors in their aerial parts. A marked diversity in the ephedrine alkaloids content and stereochemical composition in 16 different E. sinica accessions growing under the same environmental conditions was revealed, indicating genetic control of these traits. The accessions can be classified into two groups according to the stereochemistry of the products accumulated: a group that displayed only 1R stereoisomers, and a group that displayed both 1S and 1R stereoisomers. (S)-cathinone reductase activities were detected in E. sinica stems capable of reducing (S)-cathinone to (1R,2S)-norephedrine and (1S,2S)-norpseudoephedrine in the presence of NADH. The proportion of the diastereoisomers formed varied according to the accession tested. A (1R,2S)-norephedrine N-methyltransferase capable of converting (1R,2S)-norephedrine to (1R,2S)-ephedrine in the presence of S-adenosylmethionine (SAM) was also detected in E. sinica stems. Our studies further support the notion that 1-phenylpropane-1,2-dione and (S)-cathinone are biosynthetic precursors of the ephedrine alkaloids in E. sinica stems and that the activity of (S)-cathinone reductases directs and

  19. Z-sinapinic acid: the change of the stereochemistry of cinnamic acids as rational synthesis of a new matrix for carbohydrate MALDI-MS analysis.

    PubMed

    Salum, María L; Itovich, Lucia M; Erra-Balsells, Rosa

    2013-11-01

    Successful application of matrix-assisted laser desorption/ionization (MALDI) MS started with the introduction of efficient matrices such as cinnamic acid derivatives (i.e. 3,5-dimethoxy-4-hydroxycinnamic acid, SA; α-cyano-4-hydroxycinnamic acid). Since the empirical founding of these matrices, other commercial available cinnamic acids with different nature and location of substituents at benzene ring were attempted. Rational design and synthesis of new cinnamic acids have been recently described too. Because the presence of a rigid double bond in its molecule structure, cinnamic acids can exist as two different geometric isomers, the E-form and Z-form. Commercial available cinnamic acids currently used as matrices are the geometric isomers trans or E (E-cinnamic and trans-cinnamic acids). As a new rational design of MALDI matrices, Z-cinnamic acids were synthesized, and their properties as matrices were studied. Their performance was compared with that of the corresponding E-isomer and classical crystalline matrices (3,5-dihydroxybenzoic acid; norharmane) in the analysis of neutral/sulfated carbohydrates. Herein, we demonstrate the outstanding performance for Z-SA. Sulfated oligosaccharides were detected in negative ion mode, and the dissociation of sulfate groups was almost suppressed. Additionally, to better understand the quite different performance of each geometric isomer as matrix, the physical and morphological properties as well as the photochemical stability in solid state were studied. The influence of the E/Z photoisomerization of the matrix during MALDI was evaluated. Finally, molecular modeling (density functional theory study) of the optimized geometry and stereochemistry of E-cinnamic and Z-cinnamic acids revealed some factors governing the analyte-matrix interaction.

  20. Assessing the realism of colonoscopy simulation: the development of an instrument and systematic comparison of 4 simulators.

    PubMed

    Hill, Andrew; Horswill, Mark S; Plooy, Annaliese M; Watson, Marcus O; Karamatic, Rozemary; Basit, Tabinda A; Wallis, Guy M; Riek, Stephan; Burgess-Limerick, Robin; Hewett, David G

    2012-03-01

    No useful comparative data exist on the relative realism of commercially available devices for simulating colonoscopy. To develop an instrument for quantifying realism and provide the first wide-ranging empiric comparison. Repeated measures, observational study. Nineteen experienced colonoscopists completed cases on 4 colonoscopy simulators (AccuTouch, GI Mentor II, Koken, and Kyoto Kagaku) and evaluated each device. A medical simulation center in a large tertiary hospital. For each device, colonoscopists completed the newly developed Colonoscopy Simulator Realism Questionnaire (CSRQ), which contains 58 items grouped into 10 subscales measuring the realism of different aspects of the simulation. Subscale scores are weighted and combined into an aggregated score, and there is also a single overall realism item. Overall, current colonoscopy simulators were rated as only moderately realistic compared with real human colonoscopy (mean aggregated score, 56.28/100; range, 48.39-60.45, where 0 = "extremely unrealistic" and 100 = "extremely realistic"). On both overall realism measures, the GI Mentor II was rated significantly less realistic than the AccuTouch, Kyoto Kagaku, and Koken (P < .001). There were also significant differences between simulators on 9 subscales, and the pattern of results varied between subscales. The study was limited to commercially available simulators, excluding ex-vivo models. The CSRQ does not assess simulated therapeutic procedures. The CSRQ is a useful instrument for quantifying simulator realism. There is no clear "first choice" simulator among those assessed. Each has unique strengths and weaknesses, reflected in the differing results observed across 9 subscales. These findings may facilitate the targeted selection of simulators for various aspects of colonoscopy training. Copyright © 2012 American Society for Gastrointestinal Endoscopy. Published by Mosby, Inc. All rights reserved.

  1. 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…

  2. 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…

  3. Assignment Of Hexuronic Acid Stereochemistry In Synthetic Heparan Sulfate Tetrasaccharides With 2-O-Sulfo Uronic Acids Using Electron Detachment Dissociation.

    PubMed

    Agyekum, Isaac; Patel, Anish B; Zong, Chengli; Boons, Geert-Jan; Amster, Jonathan

    2015-11-15

    The present work focuses on the assignment of uronic acid stereochemistry in heparan sulfate (HS) oligomers. The structural elucidation of HS glycosaminoglycans is the subject of considerable importance due to the biological and biomedical significance of this class of carbohydrates. They are highly heterogeneous due to their non-template biosynthesis. Advances in tandem mass spectrometry activation methods, particularly electron detachment dissociation (EDD), has led to the development of methods to assign sites of sulfo modification in glycosaminoglycan oligomers, but there are few reports of the assignment of uronic acid stereochemistry, necessary to distinguish glucuronic acid (GlcA) from iduronic acid (IdoA). Whereas preceding studies focused on uronic acid epimers with no sulfo modification, the current work extends the assignment of the hexuronic acid stereochemistry to 2-O-sulfo uronic acid epimeric tetrasaccharides. The presence of a 2-O-sulfo group on the central uronic acid was found to greatly influence the formation of B3, C2, Z2, and Y1 ions in glucuronic acid and Y2 and (1,5)X2 for iduronic acid. The intensity of these peaks can be combined to yield a diagnostic ratios (DR), which can be used to confidently assign the uronic acid stereochemistry.

  4. Prediction and determination of the stereochemistry of the 1,3,5-trimethyl-substituted alkyl chain in verucopeptin, a microbial metabolite.

    PubMed

    Yoshimura, Aya; Kishimoto, Shinji; Nishimura, Shinichi; Otsuka, Saori; Sakai, Yuki; Hattori, Akira; Kakeya, Hideaki

    2014-08-01

    For the prediction of the relative stereochemistry of 1,3-dimethyl substitution in alkyl chains, a simple approach based on (1)H NMR data was recently proposed; Δδ values of methylene protons located between methyl-substituted methine carbons can be diagnostic for predicting it. Here we applied this empirical "geminal proton rule" to verucopeptin, a lipopeptide from Streptomyces sp. To determine the absolute stereochemistry of the 1,3,5-trimethyl-substituted alkyl chain in verucopeptin, we converted the corresponding alkyl chain to a carboxylic acid by oxidative cleavage. The geminal proton rule clearly predicted the relative stereochemistry as 31S*,33S*,35R*. This prediction was definitely confirmed by synthesizing four possible diastereomers and comparing their NMR spectra. Furthermore, we reinvestigated the geminal proton rule using reported compounds and our synthesized compounds. Our result strongly suggests that the rule was solid, at least for predicting the stereochemistry of 2,4-dimethylated and 2,4,6-trimethylated fatty acids.

  5. Woodward-Hoffmann's Stereochemistry of Electrocyclic Reactions: From Day 1 to the JACS Receipt Date (May 5, 1964 to November 30, 1964).

    PubMed

    Seeman, Jeffrey I

    2015-12-04

    The publication in January 1965 of the first Woodward-Hoffmann paper, The Stereochemistry of Electrocyclic Reactions, ushered into organic chemistry both an explanation of the stereochemistry and "allowedness" or "forbiddenness" of concerted reactions and an impetus for untold numbers of research projects. In the current paper, details of the collaboration between R. B. Woodward and R. Hoffmann, from when they first met to discuss the solution to the "no-mechanism problem" to the date their first paper was received in the offices of the Journal of the American Chemical Society, will be discussed and analyzed. The primary focus will be on the historically relevant extant documents from the early 1960s. These include Hoffmann's laboratory notebooks describing his research, including his extended Hückel calculations used to explain and predict the stereochemistry of electrocyclic reactions. Drafts of the Stereochemistry of Electrocyclic Reactions paper and letters and notes by Woodward, Jerome Berson, and others will further illuminate the development of this first Woodward-Hoffmann paper.

  6. Representational Realism, Closed Theories and the Quantum to Classical Limit

    NASA Astrophysics Data System (ADS)

    de Ronde, Christian

    In this chapter, we discuss the representational realist stance as a pluralistontic approach to inter-theoretic relationships. Our stance stresses the fact that physical theories require the necessary consideration of a conceptual level of discourse which determines and configures the specific field of phenomena discussed by each particular theory. We will criticize the orthodox line of research which has grounded the analysis about QM in two (Bohrian) metaphysical presuppositions - accepted in the present as dogmas that all interpretations must follow. We will also examine how the orthodox project of "bridging the gap" between the quantum and the classical domains has constrained the possibilities of research, producing only a limited set of interpretational problems which only focus in the justification of "classical reality" and exclude the possibility of analyzing the possibilities of non-classical conceptual representations of QM. The representational realist stance introduces two new problems, namely, the superposition problem and the contextuality problem, which consider explicitly the conceptual representation of orthodox QM beyond the mere reference to mathematical structures and measurement outcomes. In the final part of the chapter, we revisit, from representational realist perspective, the quantum to classical limit and the orthodox claim that this inter-theoretic relation can be explained through the principle of decoherence.

  7. Optimization of the simulation parameters for improving realism in anthropomorphic breast phantoms

    NASA Astrophysics Data System (ADS)

    Imran, Abdullah-Al-Zubaer; Bakic, Predrag R.; Maidment, Andrew D. A.; Pokrajac, David D.

    2017-03-01

    Virtual clinical trials (VCTs) were introduced as a preclinical alternative to clinical imaging trials, and for the evaluation of breast imaging systems. Realism in computer models of breast anatomy (software phantoms), critical for VCT performance, can be improved by optimizing simulation parameters based on the analysis of clinical images. We optimized the simulation to improve the realism of simulated tissue compartments, defined by the breast Cooper's ligaments. We utilized the anonymized, previously acquired CT images of a mastectomy specimen to manually segment 205 adipose compartments. We generated 1,440 anthropomorphic breast phantoms based on octree recursive partitioning. These phantoms included variations of simulation parameters—voxel size, number of compartments, percentage of dense tissue, and shape and orientation of the compartments. We compared distributions of the compartment volumes in segmented CT images and phantoms using Kolmogrov-Smirnov (KS) distance, Kullback-Leibler (KL) divergence and a novel distance metric (based on weighted sum of distribution descriptors differences). We identified phantoms with the size distributions closest to CT images. For example, KS resulted in the phantom with 1000 compartments, ligament thickness of 0.4 mm and skin thickness of 12 mm. We applied multilevel analysis of variance (ANOVAN) to these distance measures to identify parameters that most significantly influence the simulated compartment size distribution. We have demonstrated an efficient method for the optimization of phantom parameters to achieve realistic distribution of adipose compartment size. The proposed methodology could be extended to other phantom parameters (e.g., ligaments and skin thicknesses), to further improve realism of the simulation and VCTs.

  8. Mixed-realism simulation of adverse event disclosure: an educational methodology and assessment instrument.

    PubMed

    Matos, Francisco M; Raemer, Daniel B

    2013-04-01

    Physicians have an ethical duty to disclose adverse events to patients or families. Various strategies have been reported for teaching disclosure, but no instruments have been shown to be reliable for assessing them.The aims of this study were to report a structured method for teaching adverse event disclosure using mixed-realism simulation, develop and begin to validate an instrument for assessing performance, and describe the disclosure practice of anesthesiology trainees. Forty-two anesthesiology trainees participated in a 2-part exercise with mixed-realism simulation. The first part took place using a mannequin patient in a simulated operating room where trainees became enmeshed in a clinical episode that led to an adverse event and the second part in a simulated postoperative care unit where the learner is asked to disclose to a standardized patient who systematically moves through epochs of grief response. Two raters scored subjects using an assessment instrument we developed that combines a 4-element behaviorally anchored rating scale (BARS) and a 5-stage objective rating scale. The performance scores for elements within the BARS and the 5-stage instrument showed excellent interrater reliability (Cohen's κ = 0.7), appropriate range (mean range for BARS, 4.20-4.47; mean range for 5-stage instrument, 3.73-4.46), and high internal consistency (P < 0.05). We have demonstrated a comprehensive methodology using a mixed-realism simulation that engages learners in an adverse event and allows them to practice disclosure to a structured range of patient responses. We have developed a reliable 2-part instrument with strong psychometric properties for assessing disclosure performance.

  9. Realism, instrumentalism, and scientific symbiosis: psychological theory as a search for truth and the discovery of solutions.

    PubMed

    Cacioppo, John T; Semin, Gün 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 philosophical perspectives have different strengths and weaknesses and have been regarded as incommensurate: Scientific realism fosters theoretical rigor, verifiability, parsimony, and debate, whereas scientific instrumentalism fosters theoretical innovation, synthesis, generativeness, and scope. The authors review the evolution of scientific realism and instrumentalism in psychology and propose that the categorical distinction between the 2 is overstated as a prescription for scientific practice. The authors propose that the iterative deployment of these 2 perspectives, just as the iterative application of inductive and deductive reasoning in science, may promote more rigorous, integrative, cumulative, and useful scientific theories.

  10. 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.

  11. ["The end justifies the means." Historical realism and causality in modernity].

    PubMed

    Catteeuw, Laurie

    2014-01-01

    Perceived all along, from the beginning of the modern era, causality in history cannot be abstracted from a reflection on "the reason and uses of States". Such realism engages with the heart of the arts of governance, the practices which form the basis for the adage "the end justifies the means". In order to assess the implications of this maxim on the definition of causality, this article examines the modalities of the description of historical facts, its usages and censoring (understood as a necessary means to aspired ends), and the calculation of the aleatory dimensions of politics.

  12. Invited commentary: On the future of social epidemiology--a case for scientific realism.

    PubMed

    Muntaner, Carles

    2013-09-15

    In their article in this issue of the Journal (Am J Epidemiol. 2013;178(6):843-849), Galea and Link identify important heuristics for our discipline. In this commentary, I build upon their ideas by arguing that (1) social epidemiology has become an Asian, European, Latin American, and African rather than just North American endeavor, (2) realism is better suited to social epidemiology than positivism, (3) more work on social mechanisms (social class relations, racial discrimination) is needed to increase the explanatory power of social epidemiology, (4) increased attention on (social) causal models will generate more innovative social interventions, and (5) social interventions should be conducted in full partnerships with affected populations.

  13. A computer-generated face database with ratings on realism, masculinity, race, and stereotypy.

    PubMed

    Matheson, Heath E; McMullen, Patricia A

    2011-03-01

    Ratings of realism, masculinity, race, and racial stereotypy were collected on a set of computer-generated faces representing European, South East Asian, and African American ethnicities. To determine if these faces are processed in the same way as photographs of real faces, we demonstrated with these faces superior memory performance for upright faces over inverted faces (the face inversion effect). Further, in observers of European decent, we found both superior memory for European faces and a larger inversion effect for European than African American faces. Based on these results, we believe that this set of faces may be of use in perceptual investigations in which race is a critical manipulation.

  14. The Metaphysics of Morris R. Cohen: From Realism to Objective Relativism.

    PubMed

    Cahoone, Lawrence

    2017-01-01

    Morris Cohen is mainly remembered as a philosopher of history and law, a friend of jurists (Oliver Wendell Holmes, Felix Frankfurter), and a teacher of more prominent philosophers (e.g., Ernest Nagel, Paul Weiss, Morton White). But his unique position as a student of the work of Russell and Peirce led him to make a distinctive contribution to the debate over realism in in the 1910s. Largely ignored and completely uncited, his early papers formulated what would later be called "objective relativism," influencing the later work of Columbia naturalism, hence American philosophy, from the 1940s to the 1960s.

  15. Advancing renal education: hybrid simulation, using simulated patients to enhance realism in haemodialysis education.

    PubMed

    Dunbar-Reid, Kylie; Sinclair, Peter M; Hudson, Denis

    2015-06-01

    Simulation is a well-established and proven teaching method, yet its use in renal education is not widely reported. Criticisms of simulation-based teaching include limited realism and a lack of authentic patient interaction. This paper discusses the benefits and challenges of high-fidelity simulation and suggests hybrid simulation as a complementary model to existing simulation programmes. Through the use of a simulated patient, hybrid simulation can improve the authenticity of renal simulation-based education while simultaneously teaching and assessing technologically enframed caring. © 2015 European Dialysis and Transplant Nurses Association/European Renal Care Association.

  16. The effects of advice and "try more" instructions on improving realism of confidence.

    PubMed

    Buratti, Sandra; Allwood, Carl Martin

    2013-09-01

    This study investigated whether participants can improve the accuracy of their confidence judgments by making second-order judgments, and whether advice (attend both to correct and incorrect items and consider the remember/know quality of the item), and "try more" instructions can help increase participants' accuracy. The participants (n=220) made confidence judgments of their answers to 50 recall questions on a video clip. Next, all the participants were asked to try to increase the accuracy of their confidence judgments by modifying those they believed showed poor realism. Although the participants did increase the accuracy of their confidence judgments, neither the advice nor the "try more" instructions improved their accuracy.

  17. 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.

  18. Stereoselective Synthesis of 8,12-Furanoeudesmanes from Santonin. Absolute Stereochemistry of Natural Furanoeudesma-1,3-diene and Tubipofurane.

    PubMed

    Blay, Gonzalo; Cardona, Luz; García, Begoña; Pedro, José R.; Sánchez, Juan J.

    1996-05-31

    Ketobutenolide 3, easily obtained from santonin (1), has been transformed into two natural furanoeudesmanes 4 and 5, isolated from Commiphora molmol and Tubipora musica, respectively. trans- And cis-decalin systems were obtained by stereoselective reduction of the C(4)-C(5) double bond in 3 in the following way: hydrogenation of 3 over Pd/C followed by acidic treatment gave the cis isomer 10 as the major product; selective hydrogenation of the C(1)-C(2) double bond with the Wilkinson's catalyst followed by reduction with NaTeH yielded mainly the trans isomer 9. Compounds 9 and 10 were transformed into 4 and 5 in parallel sequences. Optical rotation and CD measurements of the synthetic products revealed that the stereochemistry of both natural products should be revised to their enantiomeric form.

  19. Synthesis and Structural Properties of Aza[n]helicene Platinum Complexes: Control of Cis and Trans Stereochemistry.

    PubMed

    Mendola, Daniele; Saleh, Nidal; Hellou, Nora; Vanthuyne, Nicolas; Roussel, Christian; Toupet, Loïc; Castiglione, Franca; Melone, Federica; Caronna, Tullio; Fontana, Francesca; Martí-Rujas, Javier; Parisini, Emilio; Malpezzi, Luciana; Mele, Andrea; Crassous, Jeanne

    2016-03-07

    The synthesis and structural characterization of azahelicene platinum complexes obtained from cis-PtCl2(NCEt)(PPh3) and from ligands that differ in terms of both the position of the nitrogen atom and the number of fused rings are reported. These square-planar complexes of the general formula PtCl2(nHm)(PPh3) (n = 4, 5; m = 5, 6) display mainly a cis configuration. However, by X-ray crystallographic analysis, we show that for both PtCl2(4H6)(PPh3) and PtCl2(5H6)(PPh3) there is chirality control of the cis/trans stereochemistry. Indeed, starting from a racemic mixture of aza[6]helicene, platinum complexes with a cis configuration are invariably obtained, and the more thermodynamically stable trans isomers are formed when using enantiopure ligands. We further corroborated these results by NMR analysis in solution.

  20. Acid catalyzed alcoholysis of sulfinamides: unusual stereochemistry, kinetics and a question of mechanism involving sulfurane intermediates and their pseudorotation.

    PubMed

    Bujnicki, Bogdan; Drabowicz, Józef; Mikołajczyk, Marian

    2015-02-11

    The synthesis of optically active sulfinic acid esters has been accomplished by the acid catalyzed alcoholysis of optically active sulfinamides. Sulfinates are formed in this reaction with a full or predominant inversion of configuration at chiral sulfur or with predominant retention of configuration. The steric course of the reaction depends mainly on the size of the dialkylamido group in the sulfinamides and of the alcohols used as nucleophilic reagents. It has been found that bulky reaction components preferentially form sulfinates with retention of configuration. It has been demonstrated that the stereochemical outcome of the reaction can be changed from inversion to retention and vice versa by adding inorganic salts to the acidic reaction medium. The unusual stereochemistry of this typical bimolecular nucleophilic substitution reaction, as confirmed by kinetic measurements, has been rationalized in terms of the addition-elimination mechanism, A-E, involving sulfuranes as intermediates which undergo pseudorotations.

  1. Anisotropy effect of three-membered rings in (1)H NMR spectra: quantification by TSNMRS and assignment of the stereochemistry.

    PubMed

    Kleinpeter, Erich; Krüger, Stefanie; Koch, Andreas

    2015-05-07

    The spatial magnetic properties (through space NMR shieldings, TSNMRSs) of cyclopropane; of the heteroanalogous oxirane, thiirane, and aziridine; and of various substituted mono-, dis-, and tris-cyclic analogues have been computed by the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSSs) of various size and direction. The TSNMRS values, thus obtained, can be employed to visualize the anisotropy (ring current) effect of the cyclopropane ring moiety. This approach has been employed to qualify and quantify substituent influences and contributions of appropriate ring heteroatoms O, NH, and S on the anisotropy (ring current) effect of three-membered ring moieties, and to assign the stereochemistry of mono-, bis-, and tris-cyclic structures containing cyclopropane as a structural element. Characteristic examples are included.

  2. 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.

  3. Structural investigations into the stereochemistry and activity of a phenylalanine-2,3-aminomutase from Taxus chinensis.

    PubMed

    Wybenga, Gjalt G; Szymanski, Wiktor; Wu, Bian; Feringa, Ben L; Janssen, Dick B; Dijkstra, Bauke W

    2014-05-20

    Phenylalanine-2,3-aminomutase (PAM) from Taxus chinensis, a 4-methylidene-imidazole-5-one (MIO)-dependent enzyme, catalyzes the reversible conversion of (S)-α-phenylalanine into (R)-β-phenylalanine via trans-cinnamic acid. The enzyme also catalyzes the direct addition of ammonia to trans-cinnamic acid, a reaction that can be used for the preparation of β-amino acids, which occur as frequent constituents of bioactive compounds. Different hypotheses have been formulated to explain the stereochemistry of the PAM-catalyzed reaction, but structural evidence for these hypotheses is lacking. Furthermore, it remains unclear how the PAM MIO group is formed from the three-amino acid (A-S-G) sequence motif. For these reasons, we elucidated PAM three-dimensional (3D) structures with a bound (R)-β-phenylalanine analogue and with bound trans-cinnamic acid. In addition, 3D structures of the (inactive) Y322A and N231A mutants of PAM were elucidated, which were found to be MIO-less. We conclude that the stereochemistry of the PAM-catalyzed reaction originates from the enzyme's ability to bind trans-cinnamic acid in two different orientations, with either the si,si face or the re,re face directed toward the MIO group, as evidenced by two distinct carboxylate binding modes. The results also suggest that the N231 side chain promotes MIO group formation by increasing the nucleophilicity of the G177 N atom through acidification of the amide proton.

  4. 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

    2016-06-03

    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.

  5. Can virtual reality increase the realism of role plays used to teach college women sexual coercion and rape-resistance skills?

    PubMed

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

    2009-12-01

    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 condition. A multimethod assessment strategy was used to evaluate the effects of VR on the experienced realism of sexually threatening role plays. Realism was assessed by participant self-reports of negative affect and perceptions of realism, direct observation of participants' verbal displays of negative affect during the role plays, and measurements of participant heart rate during the role plays. Results indicated that VR can indeed heighten the realism of sexually threatening role plays. Discussion focuses on issues regarding the use of VR-enhanced role plays for helping college women resist sexual attacks.

  6. Depressive realism and attributional style: implications for individuals at risk for depression.

    PubMed

    Moore, Michael T; Fresco, David M

    2007-06-01

    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 of a well-validated, cognitive diathesis-stress theory of the etiology of a subtype of depression: hopelessness theory (Abramson, L. Y., Metalsky, G. I., & Alloy, L. B. (1989). Hopelessness depression: A theory-based subtype of depression. Psychological Review, 96, 358-372). A sample of 239 college students, including groups of participants with depressogenic versus nondepressogenic attributional styles, recorded the causes they assigned to events; the extent to which their attributions were objectively realistic was evaluated. A comparison of the degree of objectivity was also made between dysphoric and nondysphoric individuals. Contrary to expectations derived from the depressive realism hypothesis, dysphoric individuals exhibited less realistic attributions as compared to nondysphoric individuals. Further, individuals at risk for depression evidenced a pessimistic bias, while individuals not at risk evidenced an optimistic bias.

  7. Perceived realism moderates the relation between sexualized media consumption and permissive sexual attitudes in Dutch adolescents.

    PubMed

    Baams, Laura; Overbeek, Geertjan; Dubas, Judith Semon; Doornwaard, Suzan M; Rommes, Els; van Aken, Marcel A G

    2015-04-01

    This study examined whether the development of sexualized media consumption and permissive sexual attitudes would be more strongly interrelated when adolescents perceived sexualized media images as highly realistic. We used data from a three-wave longitudinal sample of 444 Dutch adolescents aged 13-16 years at baseline. Results from parallel process latent growth modeling multigroup analyses showed that higher initial levels of sexualized media consumption were associated with higher initial level of permissive sexual attitudes. Moreover, increases of sexualized media consumption over time were associated with increases of permissive sexual attitudes over time. Considering the moderation by perceived realism, we found these effects only for those who perceived sexualized media as more realistic. Findings for male and female adolescents were similar except for the relations between initial levels and subsequent development. Among male adolescents who perceived sexualized media images to be realistic, higher initial levels of permissive sexual attitudes were related to subsequent less rapid development of sexualized media consumption. For male adolescents who perceived sexualized media to be less realistic, higher initial levels of sexualized media consumption were related to a subsequent less rapid development of permissive sexual attitudes. These relations were not found for female adolescents. Overall, our results suggest that, in male and female adolescents, those with a high level of perceived realism showed a correlated development of sexualized media consumption and permissive sexual attitudes. These findings point to a need for extended information on how to guide adolescents in interpreting and handling sexualized media in everyday life.

  8. 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"…

  9. 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…

  10. 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…

  11. 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"…

  12. 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…

  13. Women of ALA Youth Services and Professional Jurisdiction: Of Nightingales, Newberies, Realism, and the Right Books, 1937-1945.

    ERIC Educational Resources Information Center

    Jenkins, Christine A.

    1996-01-01

    Discussion of the female-intensive specialization of youth services librarianship and their role in the American Library Association focuses on their jurisdiction over the Newbery Medal. Topics include the question of realism in children's literature; the Sayers Institute; and evaluation criteria. Contains 65 references. (LRW)

  14. Bell-type equalities for SQUIDs on the assumptions of macroscopic realism and non-invasive measurability

    NASA Astrophysics Data System (ADS)

    Jaeger, Gregg; Viger, Chris; Sarkar, Sahotra

    1996-02-01

    Bell-type equalities are derived for the Leggett-Garg proposal for a SQUID experiment on the assumptions of macroscopic realism (MR) and non-invasive measurability (NIM). Equalities of this sort have not previously been presented. It is shown that there are 18 such equalities. These equalities put stronger constraints on the consequences of MR and NIM than the corresponding inequalities.

  15. 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,…

  16. 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…

  17. How to constrain multi-objective calibrations using water balance components for an improved realism of model results

    USDA-ARS?s Scientific Manuscript database

    Accurate discharge simulation is one of the most common objectives of hydrological modeling studies. However, a good simulation of discharge is not necessarily the result of a realistic simulation of hydrological processes within the catchment. To enhance the realism of model results, we propose an ...

  18. 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. Copyright © 2015 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.

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

    SciTech Connect

    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. The purpose of research is to 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.

  20. Computational and NMR Spectroscopic Evidence for Stereochemistry-Dependent Conformations of 2,2,6,6-Tetramethylpiperidinyl-Masked 1,2-Diols.

    PubMed

    Fought, Ellie L; Chatterjee, Shreyosree; Windus, Theresa L; Chen, Jason S

    2015-10-16

    2,2,6,6-Tetramethylpiperidinyl-masked 1,2-diols exhibited stereochemistry-dependent hydroxyl proton chemical shifts: ca. 7 ppm for the syn diastereomer and ca. 2 ppm for the anti diastereomer. A computational search for low energy geometries revealed that the syn isomer favors a six-membered ring hydrogen bond to nitrogen and the anti isomer favors a five-membered ring hydrogen bond to oxygen. The computed low energy conformations were found to have a large difference in hydroxyl proton shielding that was reflected in the experimental chemical shift difference. This chemical shift difference was observed in a broad range of solvents, and thus may be useful as a stereochemical probe. The stereochemistry-dependent conformation and chemical shift signature appeared to be due to a syn pentane interaction between the gem-dimethyl groups on the 2,2,6,6-tetramethylpiperidinyl moiety.

  1. Structures and absolute stereochemistry of dinapinones A1 and A2, inhibitors of triacylglycerol synthesis, produced by penicillium pinophilum FKI-3864.

    PubMed

    Uchida, Ryuji; Ohte, Satoshi; Kawamoto, Kyosuke; Yamazaki, Hiroyuki; Kawaguchi, Mio; Tomoda, Hiroshi

    2012-08-01

    During our screening program for microbial inhibitors of triacylglycerol synthesis in mammalian cells, four structurally related new compounds, dinapinones A1 (1) and A2 (2) and monapinones A (3) and B (4), were isolated from the culture broth of Penicillium pinophilum FKI-3864. Compounds 3 and 4 were produced by the fungus only when fermented in seawater-supplemented medium. The structures of 1 to 4 were elucidated by spectroscopic studies including various NMR experiments. Compounds 1 and 2 were atropisomers consisting of two monomers with the same planar structure of dihydronaphthopyranone as 3. The absolute stereochemistry of 3 was elucidated by NOE experiment and circular dichroism spectra. Furthermore, the stereochemistry of 1 and 2 was elucidated by in vitro conversion from the structure-defined 3 to its dimers 1 and 2.

  2. Determination of stereochemistry of bacteriochlorophyll gF and 8(1)-hydroxy-chlorophyll aF from Heliobacterium modesticaldum.

    PubMed

    Mizoguchi, Tadashi; Oh-oka, Hirozo; Tamiaki, Hitoshi

    2005-01-01

    The reaction center complex of heliobacteria contains three kinds of chlorophyll pigments, bacteriochlorophyll gF (BChl gF), its 13(2)-epimer BChl gF' and 8(1)-hydroxy-chlorophyll aF (8(1)-OH-Chl aF). Because the full stereochemistry of these naturally occurring chlorophyllous pigments has remained unknown, we determined the stereochemistry of both BChl gF and 8(1)-OH-Chl aF extracted from Heliobacterium modesticaldum. The configurations of the specific functional groups at ring-B as well as those at ring-D and -E were investigated by use of nuclear Overhauser effect correlations in their 1H-NMR spectra and circular dichroism spectra, as well as by modified Mosher's method in their chemical modification: (1) E-configuration was confirmed for the 8-ethylidene group at ring-B in BChl gF, (2) R-configuration was identified for the 1-hydroxyethyl group at ring-B in 8(1)-OH-Chl aF and (3) 13(2)-(R)-, 17-(S)- and 18-(S)-configurations at ring-D and -E in both BChl gF and 8(1)-OH-Chl aF were confirmed. These stereochemistries enabled us to discuss their biosynthesis and to propose possible routes for preparation of ethylidene and 1-hydroxyethyl groups at the 8-position.

  3. A strict experimental test of macroscopic realism in a superconducting flux qubit

    NASA Astrophysics Data System (ADS)

    Knee, George C.; Kakuyanagi, Kosuke; Yeh, Mao-Chuang; Matsuzaki, Yuichiro; Toida, Hiraku; Yamaguchi, Hiroshi; Saito, Shiro; Leggett, Anthony J.; Munro, William J.

    2016-11-01

    Macroscopic realism is the name for a class of modifications to quantum theory that allow macroscopic objects to be described in a measurement-independent manner, while largely preserving a fully quantum mechanical description of the microscopic world. Objective collapse theories are examples which aim to solve the quantum measurement problem through modified dynamical laws. Whether such theories describe nature, however, is not known. Here we describe and implement an experimental protocol capable of constraining theories of this class, that is more noise tolerant and conceptually transparent than the original Leggett-Garg test. We implement the protocol in a superconducting flux qubit, and rule out (by ~84 s.d.) those theories which would deny coherent superpositions of 170 nA currents over a ~10 ns timescale. Further, we address the `clumsiness loophole' by determining classical disturbance with control experiments. Our results constitute strong evidence for the superposition of states of nontrivial macroscopic distinctness.

  4. Trick or treat? Muslim Thangals, psychologisation and pragmatic realism in northern Kerala, India.

    PubMed

    Lang, Claudia

    2014-12-01

    Thangals are an endogamous community in Kerala, India, of Yemeni heritage who claim direct descent from the Prophet Muhammad's family. Due to their sacrosanct status, many thangals work as religious healers and thus are part of the informal mental health care system in Northern Kerala. Using the case of one thangal healer as an illustration of the many ritual healers in Kerala who engage the modern discourse of psychology in their practices, I argue that the psychologisation of ritual healing is part of a wider trend: the increasing rationalisation and scientification of traditional medical practices, whereby an increasing number of traditional healers negotiate science, modernity and religion and position their practice within these contested fields. Based on the analysis of this thangal's healing practice in the local context of Northern Kerala, I further argue that in order to understand "ritual" healing, scholars should emphasise pragmatic realism more than doctrinal purity.

  5. A strict experimental test of macroscopic realism in a superconducting flux qubit.

    PubMed

    Knee, George C; Kakuyanagi, Kosuke; Yeh, Mao-Chuang; Matsuzaki, Yuichiro; Toida, Hiraku; Yamaguchi, Hiroshi; Saito, Shiro; Leggett, Anthony J; Munro, William J

    2016-11-04

    Macroscopic realism is the name for a class of modifications to quantum theory that allow macroscopic objects to be described in a measurement-independent manner, while largely preserving a fully quantum mechanical description of the microscopic world. Objective collapse theories are examples which aim to solve the quantum measurement problem through modified dynamical laws. Whether such theories describe nature, however, is not known. Here we describe and implement an experimental protocol capable of constraining theories of this class, that is more noise tolerant and conceptually transparent than the original Leggett-Garg test. We implement the protocol in a superconducting flux qubit, and rule out (by ∼84 s.d.) those theories which would deny coherent superpositions of 170 nA currents over a ∼10 ns timescale. Further, we address the 'clumsiness loophole' by determining classical disturbance with control experiments. Our results constitute strong evidence for the superposition of states of nontrivial macroscopic distinctness.

  6. A Realism-Based View on Counts in OMOP's Common Data Model.

    PubMed

    Ceusters, Werner; Blaisure, Jonathan

    2017-01-01

    Correctly counting entities is a requirement for analytics tools to function appropriately. The Observational Medical Outcomes Partnership's (OMOP) Common Data Model (CDM) specifications were examined to assess the extent to which counting in OMOP CDM compatible data repositories would work as expected. To that end, constructs (tables, fields and attributes) defined in the OMOP CDM as well as cardinality constraints and other business rules found in its documentation and related literature were compared to the types of entities and axioms proposed in realism-based ontologies. It was found that not only the model itself, but also a proposed standard algorithm for computing condition eras may lead to erroneous counting of several sorts of entities.

  7. 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.

  8. Stronger Two-Observer All-Versus-Nothing Violation of Local Realism

    NASA Astrophysics Data System (ADS)

    Cabello, Adán

    2005-11-01

    We introduce a two-observer all-versus-nothing proof of Bell’s theorem which reduces the number of required quantum predictions from 9 [A. Cabello, Phys. Rev. Lett. 87, 010403 (2001);PRLTAO0031-900710.1103/PhysRevLett.87.010403 Z.-B. Chen , Phys. Rev. Lett. 90, 160408 (2003)PRLTAO0031-900710.1103/PhysRevLett.90.160408] to 4, provides a greater amount of evidence against local realism, reduces the detection efficiency requirements for a conclusive experimental test of Bell’s theorem, and leads to a Bell inequality which resembles Mermin’s inequality for three observers [N. D. Mermin, Phys. Rev. Lett. 65, 1838 (1990)PRLTAO0031-900710.1103/PhysRevLett.65.1838] but requires only two observers.

  9. 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.

  10. 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.

  11. Educational program in crisis management for cardiac surgery teams including high realism simulation.

    PubMed

    Stevens, Louis-Mathieu; Cooper, Jeffrey B; Raemer, Daniel B; Schneider, Robert C; Frankel, Allan S; Berry, William R; Agnihotri, Arvind K

    2012-07-01

    Cardiac surgery demands effective teamwork for safe, high-quality care. The objective of this pilot study was to develop a comprehensive program to sharpen performance of experienced cardiac surgical teams in acute crisis management. We developed and implemented an educational program for cardiac surgery based on high realism acute crisis simulation scenarios and interactive whole-unit workshop. The impact of these interventions was assessed with postintervention questionnaires, preintervention and 6-month postintervention surveys, and structured interviews. The realism of the acute crisis simulation scenarios gradually improved; most participants rated both the simulation and whole-unit workshop as very good or excellent. Repeat simulation training was recommended every 6 to 12 months by 82% of the participants. Participants of the interactive workshop identified 2 areas of highest priority: encouraging speaking up about critical information and interprofessional information sharing. They also stressed the importance of briefings, early communication of surgical plan, knowing members of the team, and continued simulation for practice. The pre/post survey response rates were 70% (55/79) and 66% (52/79), respectively. The concept of working as a team improved between surveys (P = .028), with a trend for improvement in gaining common understanding of the plan before a procedure (P = .075) and appropriate resolution of disagreements (P = .092). Interviewees reported that the training had a positive effect on their personal behaviors and patient care, including speaking up more readily and communicating more clearly. Comprehensive team training using simulation and a whole-unit interactive workshop can be successfully deployed for experienced cardiac surgery teams with demonstrable benefits in participant's perception of team performance. Copyright © 2012 The American Association for Thoracic Surgery. Published by Mosby, Inc. All rights reserved.

  12. Initial validation of a virtual-reality learning environment for prostate biopsies: realism matters!

    PubMed

    Fiard, Gaelle; Selmi, Sonia-Yuki; Promayon, Emmanuel; Vadcard, Lucile; Descotes, Jean-Luc; Troccaz, Jocelyne

    2014-04-01

    A virtual-reality learning environment dedicated to prostate biopsies was designed to overcome the limitations of current classical teaching methods. The aim of this study was to validate reliability, face, content, and construct of the simulator. The simulator is composed of (a) a laptop computer, (b) a haptic device with a stylus that mimics the ultrasound probe, (c) a clinical case database including three-dimensional (3D) ultrasound volumes and patient data, and (d) a learning environment with a set of progressive exercises including a randomized 12-core biopsy procedure. Both visual (3D biopsy mapping) and numerical (score) feedback are given to the user. The simulator evaluation was conducted in an academic urology department on 7 experts and 14 novices who each performed a virtual biopsy procedure and completed a face and content validity questionnaire. The overall realism of the biopsy procedure was rated at a median of 9/10 by nonexperts (7.1-9.8). Experts rated the usefulness of the simulator for the initial training of urologists at 8.2/10 (7.9-8.3), but reported the range of motion and force feedback as significantly less realistic than novices (P=0.01 and 0.03, respectively). Pearson r correlation coefficient between correctly placed biopsies on the right and left side of the prostate for each user was 0.79 (P<0.001). The 7 experts had a median score of 64% (59%-73%), and the 14 novices a median score of 52% (43%-67%), without reaching statistical significance (P=0.19). The newly designed virtual-reality learning environment proved its versatility and its reliability, face, and content were validated. Demonstrating the construct validity will necessitate improvements to the realism and scoring system used.

  13. The Effectiveness of Physical Models in Teaching Anatomy: A Meta-Analysis of Comparative Studies

    ERIC Educational Resources Information Center

    Yammine, Kaissar; Violato, Claudio

    2016-01-01

    There are various educational methods used in anatomy teaching. While three dimensional (3D) visualization technologies are gaining ground due to their ever-increasing realism, reports investigating physical models as a low-cost 3D traditional method are still the subject of considerable interest. The aim of this meta-analysis is to quantitatively…

  14. The Effectiveness of Physical Models in Teaching Anatomy: A Meta-Analysis of Comparative Studies

    ERIC Educational Resources Information Center

    Yammine, Kaissar; Violato, Claudio

    2016-01-01

    There are various educational methods used in anatomy teaching. While three dimensional (3D) visualization technologies are gaining ground due to their ever-increasing realism, reports investigating physical models as a low-cost 3D traditional method are still the subject of considerable interest. The aim of this meta-analysis is to quantitatively…

  15. Sequential oxygenation of linoleic acid in the fungus Gaeumannomyces graminis: stereochemistry of dioxygenase and hydroperoxide isomerase reactions.

    PubMed

    Hamberg, M; Zhang, L Y; Brodowsky, I D; Oliw, E H

    1994-02-15

    Linoleic acid is sequentially oxygenated to (7S,8S)-dihydroxylinoleic acid by dioxygenase and hydroperoxide isomerase activities present in the fungus Gaeumannomyces graminis (Brodowsky, I. D., Hamberg, M., and Oliw, E. H., J. Biol. Chem. 267, 14738-14745 (1992)). Linoleic acids stereospecifically deuterated at C-7 and C-8 were prepared by biological desaturation of the corresponding stearates and used to determine the stereochemistry of the hydrogen abstractions occurring in the dioxygenase- and hydroperoxide isomerase-catalyzed reactions. The dioxygenase reaction was found to involve stereospecific abstraction of the pro-S hydrogen from C-8 followed by antarafacial insertion of dioxygen to produce (8R)-hydroperoxylinoleic acid. The hydroperoxide isomerase reaction consisted of conversion of (8R)-hydroperoxylinoleic acid into (7S,8S)-dihydroxylinoleic acid by stereospecific elimination of the pro-S hydrogen from C-7 and intramolecular suprafacial insertion of oxygen at C-7. Accordingly, during the conversion of linoleic acid into (8R)-hydroperoxylinoleic acid, the absolute configuration of C-8 was inverted, while the conversion of (8R)-hydroperoxylinoleic acid into (7S,8S)-dihydroxylinoleic acid occurred with retention of absolute configuration at C-7.

  16. Effect of Stereochemistry on Directed Self-Assembly of Poly(styrene-b-lactide) Films on Chemical Patterns

    SciTech Connect

    Li, Xiao; Liu, Yadong; Wan, Lei; Li, Zhaolei; Suh, Hyoseon; Ren, Jiaxing; Ocola, Leonidas E.; Hu, Wenbing; Ji, Shengxiang; Nealey, Paul F.

    2016-03-15

    We demonstrated here for the first time that the stereochemistry of polylactide (PLA) blocks affected the assembly behaviors of PS-b-PLA on chemical patterns. Two PS-b-PLA block copolymers, where the PLA block is either racemic (PDLLA) or left-handed (PLLA), were synthesized and directed to assemble on chemical patterns with a wide range of L-s/L-o. PS-b-PDLLA was stretched up to 70% on chemical patterns, while PS-b-PLLA was only stretched by 20%. The assembly behavior of PS-b-PDLLA was different from AB diblock copolymer, but similar to that of ABA triblock copolymer. The high stretchability might be attributed to the formation of stereocomplexes in PDLLA blocks. Compared to ABA triblock copolymers, stereocomplexed diblock copolymers have much faster assembly kinetics. This observation provides a new concept to achieve large process windows by the introduction of specific interactions, for example, H-bonding, supramolecular interaction, and sterecomplexation, between polymer chains.

  17. Protochlorophyllide reductase. 1. Determination of the regiochemistry and the stereochemistry of the reduction of protochlorophyllide to chlorophyllide

    SciTech Connect

    Begley, T.P.; Young, H. )

    1989-04-12

    It has been estimated that over 1 billion tons of chlorophyll are synthesized in the biosphere each year. Although the chlorophyll biosynthetic pathway has been the subject of intense investigation over the 50 years, much remains to be discovered. One promising area of investigation is the remarkable color change, from yellow to green, that occurs when dark-grown plants are exposed to light. This greening reaction involves the reduction of protochlorophyllide to chlorophyllide and is a key regulatory step both in the biosynthesis of chlorophyll and in the development of the chloroplast. This reaction is catalyzed by the enzyme protochlorophyllide reductase and is of interest because it is one of only two known light-requiring enzymatic reactions. The enzyme has been purified from oats, barley, wheat, and squash. It is an unstable membrane-bound protein of 37,000 D molecular weight. The quantum yield for protochlorophyllide reduction in barley seedlings is 0.4 and the action spectrum for the reaction in corn seedlings follows the absorption spectrum of protochlorophyllide. As the first step in our mechanistic investigation of this important reaction, we have determined the regiochemistry and the stereochemistry of the reduction catalyzed by the oats enzyme. On the basis of this information, we propose a model for the active site of the enzyme.

  18. 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.

  19. Collapsed bipolar glycolipids at the air/water interface: effect of the stereochemistry on the stretched/bent conformations.

    PubMed

    Jacquemet, Alicia; Terme, Nolwenn; Benvegnu, Thierry; Vié, Véronique; Lemiègre, Loïc

    2013-12-15

    This article describes a comparative study of several bipolar lipids derived from tetraether structures. The sole structural difference between the main two glycolipids is a unique stereochemical variation on a cyclopentyl ring placed in the middle of the lipids. We discuss the comparative results obtained at the air/water interface on the basis of tensiometry and ellipsometry. Langmuir-Blodgett depositions during lipid film compressions and decompressions were also analyzed by AFM. The lactosylated tetraether (bipolar) lipid structures involved the formation of highly stable multilayers, which are still present at 10 mN m(-1) during decompression. This study suggests also that the stereochemistry of a central cyclopentyl ring dramatically drives the conformation of the corresponding bipolar lipids. Both isomers (trans and cis) adopt a U-shaped (bent) conformation at the air/water interface but the trans cyclopentyl ring induces a much more frustration within this type of conformation. Consequently, this bipolar lipid (trans-tetraether) undergoes a flip of one polar head-group (lactosyl) leading to a stretched conformation during collapse.

  20. 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.

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

    PubMed

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

    1990-04-25

    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.

  2. Imposing function down a (cupin)-barrel: secondary structure and metal stereochemistry in the αKG-dependent oxygenases

    PubMed Central

    Hangasky, John A.; Taabazuing, Cornelius Y.; Valliere, Meaghan A.; Knapp, Michael J.

    2014-01-01

    The Fe(II)/αketoglutarate (αKG) dependent oxygenases catalyze a diverse range of reactions significant in biological processes such as antibiotic biosynthesis, lipid metabolism, oxygen sensing, and DNA and RNA repair. Although functionally diverse, the eight-stranded β-barrel (cupin) and HX(D/E)XnH facial triad motifs are conserved in this super-family of enzymes. Crystal structure analysis of 25 αKG oxygenases reveals two stereoisomers of the Fe cofactor, Anti and Clock, which differ in the relative position of the exchangeable ligand position and the primary substrate. Herein, we discuss the relationship between the chemical mechanism and the secondary coordination sphere of the αKG oxygenases, within the constraints of the stereochemistry of the Fe cofactor. Sequence analysis of the cupin barrel indicates that a small subset of positions constitute the second coordination sphere, which has significant ramifications for the structure of the ferryl intermediate. The competence of both Anti and Clock stereoisomers of Fe points to a ferryl intermediate that is 5 coordinate. The small number of conserved close contacts within the active sites of αKG oxygenases can be extended to chemically related enzymes, such as the αKG-dependent halogenases SyrB2 and CytC3, and the non-αKG dependent dioxygenases isopenicillin N synthase (IPNS) and cysteine dioxygenase (CDO). PMID:23446356

  3. 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

  4. Cell-penetrating compounds preferentially bind glycosaminoglycans over plasma membrane lipids in a charge density- and stereochemistry-dependent manner.

    PubMed

    Prevette, Lisa E; Benish, Nicolas C; Schoenecker, Amber R; Braden, Kristin J

    2015-12-01

    Cell-penetrating compounds (CPCs) are often conjugated to drugs and genes to facilitate cellular uptake. We hypothesize that the electrostatic interaction between the positively charged amines of the cell-penetrating compounds and the negatively charged glycosaminoglycans (GAGs) extending from cell surfaces is the initiating step in the internalization process. The interactions of generation 5 PAMAM dendrimer, Tat peptide and 25 kDa linear PEI with four different GAGs have been studied using isothermal titration calorimetry to elucidate structure-function relationships that could lead to improved drug and gene delivery methods to a wide variety of cell types. Detailed thermodynamic analysis has determined that CPC-GAG binding constants range from 8.7×10(3) to 2.4×10(6)M(-1) and that affinity is dependent upon GAG charge density and stereochemistry and CPC molecular weight. The effect of GAG composition on affinity is likely due to hydrogen bonding between CPC amines and amides and GAG hydroxyl and amine groups. These results were compared to the association of CPCs with lipid vesicles of varying composition as model plasma membranes to finally clarify the relative importance of each cell surface component in initial cell recognition. CPC-lipid affinity increases with anionic lipid content, but GAG affinity is higher for all cell-penetrating compounds, confirming the role these heterogeneous polysaccharides play in cellular association and clustering.

  5. Significance of stereochemistry of 3'-terminal phosphorothioate-modified primer in DNA polymerase-mediated chain extension.

    PubMed

    Nawrot, Barbara; Paul, Natasha; Rebowska, Beata; Stec, Wojciech J

    2008-10-01

    Influence of stereochemistry of the 3'-terminal phosphorothioate (PS)-modified primers was studied in a single base extension (SBE) assay to evaluate any improvements in specificity. SBE reactions were catalyzed by members of the high fidelity Pfu family of DNA polymerases with (exo+) or without (exo-) 3' --> 5' exonucleolytic activity. The diastereomerically pure PS-labeled primers used in these studies were obtained either by the stereospecific chemical synthesis invented in our laboratory or by the more conventional ion-exchange chromatographic method for separation of a mixture of diastereomers (R(P) and S(P)). When the SBE reaction was performed in the presence of mispaired 2'-deoxyribonucleoside triphosphates (dNTPs), the "racemic" 3'-phosphorothioate primer mixture resulted in a lower level of 3' --> 5' exonuclease-mediated cleavage products in comparison to the SBE reactions carried out with the corresponding unmodified primer. When the diastereomerically pure RP 3'-phosphorothioate primer was examined, the results were largely the same as for the racemic 3'-phosphorothioate primer mixture. In contrast, a 3'-PS primer of S(P) configuration displayed significantly improved performance in the SBE reaction. This included the lack of 3' --> 5' proofreading products, less mispriming, and improved yield of incorporation of the correct nucleotide.

  6. Stereochemistry of Furfural Reduction by a Saccharomyces cerevisiae Aldehyde Reductase That Contributes to In Situ Furfural Detoxification▿

    PubMed Central

    Bowman, Michael J.; Jordan, Douglas B.; Vermillion, Karl E.; Braker, Jay D.; Moon, Jaewoong; Liu, Z. Lewis

    2010-01-01

    Ari1p from Saccharomyces cerevisiae, recently identified as an intermediate-subclass short-chain dehydrogenase/reductase, contributes in situ to the detoxification of furfural. Furfural inhibits efficient ethanol production by yeast, particularly when the carbon source is acid-treated lignocellulose, which contains furfural at a relatively high concentration. NADPH is Ari1p's best known hydride donor. Here we report the stereochemistry of the hydride transfer step, determined by using (4R)-[4-2H]NADPD and (4S)-[4-2H]NADPD and unlabeled furfural in Ari1p-catalyzed reactions and following the deuterium atom into products 2-furanmethanol or NADP+. Analysis of the products demonstrates unambiguously that Ari1p directs hydride transfer from the si face of NADPH to the re face of furfural. The singular orientation of substrates enables construction of a model of the Michaelis complex in the Ari1p active site. The model reveals hydrophobic residues near the furfural binding site that, upon mutation, may increase specificity for furfural and enhance enzyme performance. Using (4S)-[4-2H]NADPD and NADPH as substrates, primary deuterium kinetic isotope effects of 2.2 and 2.5 were determined for the steady-state parameters kcatNADPH and kcat/KmNADPH, respectively, indicating that hydride transfer is partially rate limiting to catalysis. PMID:20525870

  7. Mechanism of estrogen biosynthesis. Stereochemistry of C-1 hydrogen elimination in the aromatization of 2 beta-hydroxy-19-oxoandrostenedione.

    PubMed

    Fishman, J; Raju, M S

    1981-05-10

    19-Hydroxy[1 alpha-3H]androstenedione was synthesized and its specific activity was accurately determined. Upon aromatization of the above material by placental microsomal aromatase preparation, a process involving 1 beta hydrogen elimination, only 7.4% of the isotope was lost establishing the alpha orientation of the 3H at C-1 in the substrate. The 19-hydroxy[1 alpha]3H]androstenedione was used as the starting material in the synthesis of 2 beta-hydroxy-19-oxo[1 alpha-3H]androstenedione which therefore had the same specific activity and isotope orientation as its precursor. The nonenzymatic collapse of 2 beta-hydroxy-19-oxo[1 alpha-3H]androstenedione in pH 7.1 buffer to estrone was associated with the elimination of only 2.6% of the isotope indicating that this process proceeds also with stereospecific 1 beta hydrogen elimination. The stereochemistry of hydrogen loss in the nonenzymatic aromatization of the 2 beta-hydroxy-19-oxo derivative is therefore beta and identical with that of estrogen biosynthesis. This provides further evidence in support of the hypothesis that the final enzymatic hydroxylation of the aromatization sequence takes place at position 2 beta of the androgen substrate and that its product, the 2 beta-hydroxy-19-aldehyde, is the proximate precursor of estrogen with the final conversion occurring nonenzymatically.

  8. 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

  9. Theoretical study of the potential energy surface governing the stereochemistry in ClC sub 2 H sub 4 reactions

    SciTech Connect

    Engels, B.; Peyerimhoff, S.D. ); Skell, P.S. )

    1990-02-22

    Large-scale multireference configuration interaction calculations in a double-{xi}-type AO basis including polarization functions are carried out for the potential surface of the ClC{sub 2}H{sub 4} system. The charge distribution for various extreme points of the surface is discussed. The absolute minimum is found for an asymmetric ClC{sub 2}H{sub 4} structure. The symmetrical bridged nuclear conformation is also found to be stable with respect to dissociation into Cl + C{sub 2}H{sub 4}. The activation energy for rotation about the C-C axis is calculated to be around 18 kJ/mol, which is comparable to that for the 1,2 migration (around 26 kJ mol). The stereochemistry is governed by the fact that addition of Cl to C{sub 2}H{sub 4} (or dissociation) is a two-step reaction proceeding through a symmetrical intermediate. The direct addition pathway possesses a small barrier of about 8 kJ/mol.

  10. 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

  11. Reactions to safer-sex public service announcement message features: attention, perceptions of realism, and cognitive responses.

    PubMed

    Van Stee, Stephanie K; Noar, Seth M; Allard, Suzanne; Zimmerman, Rick; Palmgreen, Philip; McClanahan, Kitty

    2012-11-01

    For this article, we conducted a qualitative investigation of participants' reactions to five televised public service announcements (PSAs) that were aired as part of a large safer-sex mass media campaign to increase condom use among young adults. We conducted qualitative interviews (N = 139) to determine which features of PSAs participants thought were most effective in terms of attention and recall, perceived realism of characters and situations, and cognitive responses. Our analysis of the results highlights the importance of high-sensation-value messages for gaining attention as well as the critical role of personal relevance for enhancing perceptions of realism. Cognitive responses to PSAs were mostly positive, but there was evidence of third-person effects. That is, many participants indicated that the safer-sex messages were important for other people but not for themselves. We discuss the implications of our results for designing PSAs that are attention-catching, realistic, and persuasive.

  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

    2015-06-25

    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.

  13. Overcoming the barrier of narrative adherence in conflicts through awareness of the psychological bias of naïve realism.

    PubMed

    Nasie, Meytal; Bar-Tal, Daniel; Pliskin, Ruthie; Nahhas, Eman; Halperin, Eran

    2014-11-01

    One significant socio-psychological barrier for peaceful resolution of conflicts is each party's adherence to its own collective narrative. We hypothesized that raising awareness to the psychological bias of naïve realism and its identification in oneself would provide a path to overcoming this barrier, thus increasing openness to the adversary's narrative. We conducted three experimental studies in the context of the Israeli-Palestinian conflict. Studies 1 and 2, conducted among Jewish Israelis and Palestinian Israelis, respectively, revealed that participants with hawkish political ideology reported greater openness to the adversary's narrative when they were made aware of naïve realism bias. Study 3 revealed that hawkish participants at the baseline adhered to the ingroup narrative and resisted the adversary's narrative more than dovish participants. They were also more able to identify the bias in themselves upon learning about it. This identification may explain why the manipulation led to bias correction only among hawkish participants.

  14. The Spin-S Einstein - Podolsky - Rosen Experiment and the Recovery of Local Realism in the Classical Limit.

    NASA Astrophysics Data System (ADS)

    Garg, Anupam Kumar

    This thesis consists of a study of the general spin Einstein-Podolsky-Rosen experiment, with a view to seeing how classical behavior is recovered in the infinite -spin limit. In Bohm's version of the experiment, two spin -s particles fly apart in the singlet state. Quantum theory predicts that if the spin of one particle is measured to be m along a direction a, the other will necessarily have a sping of -m along a. Since the spins of the two far apart particles can be measured in an infinitesimal time interval, the requirement of locality suggests that the particles' spins are predetermined along all directions, in defiance of quantum theoretic precepts. It was shown by Bell and by Clauser and Horne that an alternative point of view called local realism which attempts to explain the spin correlations by introducing hidden variables mut be incompatible with the quantitative predictions of quantum theory for spin- 1/2. Chapters II and III of this thesis contain extensions of their arguments to arbitrary spin. It is found that no matter how large the spin gets, quantum mechanics and local realism do not become more compatible, and classical mechanics does not emerge as a smooth infinite-spin limit. Chapter IV gives a general procedure (with several examples) for deciding whether or not a given set of joint distributions for the spins of the two particles is compatible with local realism. In Chapter V it is argued that local realism can emerge in the infinite-spin limit only if limitations in detector resolution (quite unrelated to those imposed by the uncertainty principle) are explicitly included. Some questions stemming from this point of view are answered for spin- 1/2, and a specific model for including detector error is studied for higher spin.

  15. Display signaling in augmented reality: effects of cue reliability and image realism on attention allocation and trust calibration.

    PubMed

    Yeh, M; Wickens, C D

    2001-01-01

    This experiment seeks to examine the relationships among three advanced technology features (presentation of target cuing, reliability of target cuing, and level of image reality and the attention and trust given to that information). The participants were 16 military personnel who piloted an unmanned air vehicle and searched for targets camouflaged in terrain, which was presented at two levels of image realism. Cuing was available for some targets, and the reliability of this information was manipulated at two levels (100% and 75%). The results showed that the presence of cuing aided target detection for expected targets but drew attention away from the presence of unexpected targets. Cuing benefits and attentional tunneling were both reduced when cuing became less reliable. Increasing image realism was compelling but increased reliance on the cuing information when those data were reliable. Potential applications include a cost-benefit analysis of how trust modulates attention in the use of automated target recognition systems and the extent to which increased realism may influence this trust.

  16. THE CRYSTAL STRUCTURE OF ASPIRIN ACETYLATED HUMAN CYCLOOXYGENASE-2: INSIGHT INTO THE FORMATION OF PRODUCTS WITH REVERSED STEREOCHEMISTRY

    PubMed Central

    Lucido, Michael J.; Orlando, Benjamin J.; Vecchio, Alex J.; Malkowski, Michael G.

    2016-01-01

    Aspirin and other nonsterroidal anti-inflammatory drugs target the Cyclooxygenase enzymes (COX-1 and COX-2) to block the formation of prostaglandins. Aspirin is unique in that it covalently modifies each enzyme by acetylating Ser-530 within the cyclooxygenase active site. Acetylation of COX-1 leads to complete loss of activity, while acetylation of COX-2 results in the generation of the mono-oxygenated product 15(R)-hydroxyeicosatetraenoic acid (15R-HETE). Ser-530 has also been shown to influence the stereochemistry for oxygen addition into the prostaglandin product. We determined the crystal structures of S530T murine (mu) COX-2, aspirin-acetylated human (hu) COX-2, and huCOX-2 in complex with salicylate to 1.9Å, 2.0Å, and 2.4Å, respectively. The structures reveal that: 1) the acetylated Ser-530 completely blocks access to the hydrophobic groove; 2) the observed binding pose of salicylate is reflective of the enzyme-inhibitor complex prior to acetylation; and 3) the observed Thr-530 rotamer in the S530T muCOX-2 crystal structure does not impede access to the hydrophobic groove. Based on these structural observations, along with functional analysis of the S530T/G533V double mutant, we propose a working hypothesis for the generation of 15R-HETE by aspirin-acetylated COX-2. We also observe differential acetylation of COX-2 purified in various detergent systems and nanodiscs, indicating that detergent and lipid binding within the membrane-binding domain of the enzyme alters the rate of the acetylation reaction in vitro. PMID:26859324

  17. 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.

  18. Crystal Structure of Aspirin-Acetylated Human Cyclooxygenase-2: Insight into the Formation of Products with Reversed Stereochemistry.

    PubMed

    Lucido, Michael J; Orlando, Benjamin J; Vecchio, Alex J; Malkowski, Michael G

    2016-03-01

    Aspirin and other nonsteroidal anti-inflammatory drugs target the cyclooxygenase enzymes (COX-1 and COX-2) to block the formation of prostaglandins. Aspirin is unique in that it covalently modifies each enzyme by acetylating Ser-530 within the cyclooxygenase active site. Acetylation of COX-1 leads to complete loss of activity, while acetylation of COX-2 results in the generation of the monooxygenated product 15(R)-hydroxyeicosatetraenoic acid (15R-HETE). Ser-530 has also been shown to influence the stereochemistry for the addition of oxygen to the prostaglandin product. We determined the crystal structures of S530T murine (mu) COX-2, aspirin-acetylated human (hu) COX-2, and huCOX-2 in complex with salicylate to 1.9, 2.0, and 2.4 Å, respectively. The structures reveal that (1) the acetylated Ser-530 completely blocks access to the hydrophobic groove, (2) the observed binding pose of salicylate is reflective of the enzyme-inhibitor complex prior to acetylation, and (3) the observed Thr-530 rotamer in the S530T muCOX-2 crystal structure does not impede access to the hydrophobic groove. On the basis of these structural observations, along with functional analysis of the S530T/G533V double mutant, we propose a working hypothesis for the generation of 15R-HETE by aspirin-acetylated COX-2. We also observe differential acetylation of COX-2 purified in various detergent systems and nanodiscs, indicating that detergent and lipid binding within the membrane-binding domain of the enzyme alters the rate of the acetylation reaction in vitro.

  19. Stereochemistry and Mechanism of Undecylprodigiosin Oxidative Carbocyclization to Streptorubin B by the Rieske Oxygenase RedG.

    PubMed

    Withall, David M; Haynes, Stuart W; Challis, Gregory L

    2015-06-24

    The prodiginines are a group of specialized metabolites that share a 4-methoxypyrrolyldipyrromethene core structure. Streptorubin B is a structurally remarkable member of the prodiginine group produced by Streptomyces coelicolor A3(2) and other actinobacteria. It is biosynthesized from undecylprodigiosin by an oxidative carbocyclization catalyzed by the Rieske oxygenase-like enzyme RedG. Undecylprodigiosin derives from the RedH-catalyzed condensation of 2-undecylpyrrole and 4-methoxy-2, 2'-bipyrrole-5-carboxaldehyde (MBC). To probe the mechanism of the RedG-catalyzed reaction, we synthesized 2-(5-pentoxypentyl)-pyrrole, an analogue of 2-undecylpyrrole with an oxygen atom next to the site of C-C bond formation, and fed it, along with synthetic MBC, to Streptomyces albus expressing redH and redG. This resulted in the production of the 6'-oxa analogue of undecylprodigiosin. In addition, a small amount of a derivative of this analogue lacking the n-pentyl group was produced, consistent with a RedG catalytic mechanism involving hydrogen abstraction from the alkyl chain of undecylprodigiosin prior to pyrrole functionalization. To investigate the stereochemistry of the RedG-catalyzed oxidative carbocyclization, [7'-(2)H](7'R)-2-undecylpyrrole and [7'-(2)H](7'S)-2-undecylpyrrole were synthesized and fed separately, along with MBC, to S. albus expressing redH and redG. Analysis of the extent of deuterium incorporation into the streptorubin B produced in these experiments showed that the pro-R hydrogen atom is abstracted from C-7' of undecylprodigiosin and that the reaction proceeds with inversion of configuration at C-7'. This contrasts sharply with oxidative heterocyclization reactions catalyzed by other nonheme iron-dependent oxygenase-like enzymes, such as isopenicillin N synthase and clavaminate synthase, which proceed with retention of configuration at the carbon center undergoing functionalization.

  20. Determination of stereochemistry stability coefficients of amino acid side-chains in an amphipathic alpha-helix.

    PubMed

    Chen, Y; Mant, C T; Hodges, R S

    2002-01-01

    We describe here a systematic study to determine the effect on secondary structure of d-amino acid substitutions in the nonpolar face of an amphipathic alpha-helical peptide. The helix-destabilizing ability of 19 d-amino acid residues in an amphipathic alpha-helical model peptide was evaluated by reversed-phase HPLC and CD spectroscopy. l-Amino acid and d-amino acid residues show a wide range of helix-destabilizing effects relative to Gly, as evidenced in melting temperatures (DeltaTm) ranging from -8.5 degrees C to 30.5 degrees C for the l-amino acids and -9.5 degrees C to 9.0 degrees C for the d-amino acids. Helix stereochemistry stability coefficients defined as the difference in Tm values for the l- and d-amino acid substitutions [(DeltaTm' = TmL and TmD)] ranging from 1 degrees C to 34.5 degrees C. HPLC retention times [DeltatR(XL-XD)] also had values ranging from -0.52 to 7.31 min at pH 7.0. The helix-destabilizing ability of a specific d-amino acid is highly dependent on its side-chain, with no clear relationship to the helical propensity of its corresponding l-enantiomers. In both CD and reversed-phase HPLC studies, d-amino acids with beta-branched side-chains destabilize alpha-helical structure to the greatest extent. A series of helix stability coefficients was subsequently determined, which should prove valuable both for protein structure-activity studies and de novo design of novel biologically active peptides.

  1. 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

  2. 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

  3. 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.

  4. Single Stage Tandem Mass Spectrometry Assignment of the C-5 Uronic Acid Stereochemistry in Heparan Sulfate Tetrasaccharides using Electron Detachment Dissociation

    NASA Astrophysics Data System (ADS)

    Agyekum, Isaac; Zong, Chengli; Boons, Geert-Jan; Amster, I. Jonathan

    2017-09-01

    The analysis of heparan sulfate (HS) glycosaminoglycans presents many challenges, due to the high degree of structural heterogeneity arising from their non-template biosynthesis. Complete structural elucidation of glycosaminoglycans necessitates the unambiguous assignments of sulfo modifications and the C-5 uronic acid stereochemistry. Efforts to develop tandem mass spectrometric-based methods for the structural analysis of glycosaminoglycans have focused on the assignment of sulfo positions. The present work focuses on the assignment of the C-5 stereochemistry of the uronic acid that lies closest to the reducing end. Prior work with electron-based tandem mass spectrometry methods, specifically electron detachment dissociation (EDD), have shown great promise in providing stereo-specific product ions, such as the B3 ´ -CO2, which has been found to distinguish glucuronic acid (GlcA) from iduronic acid (IdoA) in some HS tetrasaccharides. The previously observed diagnostic ions are generally not observed with 2- O-sulfo uronic acids or for more highly sulfated heparan sulfate tetrasaccharides. A recent study using electron detachment dissociation and principal component analysis revealed a series of ions that correlate with GlcA versus IdoA for a set of 2- O-sulfo HS tetrasaccharide standards. The present work comprehensively investigates the efficacy of these ions for assigning the C-5 stereochemistry of the reducing end uronic acid in 33 HS tetrasaccharides. A diagnostic ratio can be computed from the sum of the ions that correlate to GlcA to those that correlate to IdoA. [Figure not available: see fulltext.

  5. Control of prostaglandin stereochemistry at the 15-carbon by cyclooxygenases-1 and -2. A critical role for serine 530 and valine 349.

    PubMed

    Schneider, Claus; Boeglin, William E; Prusakiewicz, Jeffery J; Rowlinson, Scott W; Marnett, Lawrence J; Samel, Nigulas; Brash, Alan R

    2002-01-04

    Prostaglandin synthesis by cyclooxygenases-1 and -2 (COX-1 and COX-2) involves an initial oxygenation of arachidonic acid at C-11, followed by endoperoxide and cyclopentane ring formation, and then a second reaction with molecular oxygen in the S configuration at C-15. The resulting 15S-hydroxyl group of prostaglandins is crucial for their bioactivity. Using human COX-1 and human and murine COX-2, we have identified two amino acids located in the oxygenase active site that control the stereochemistry at C-15. The most crucial determinant is Ser-530, the residue that is acetylated by aspirin. In COX-2, site-directed mutagenesis of Ser-530 to methionine, threonine, or valine produced highly active enzymes that formed 82-95% 15R-configuration prostaglandins; these have the opposite stereochemistry at C-15 to the natural products. In COX-1, the corresponding Ser-530 mutations inactivated the enzyme. The second residue, Val-349, exerts a more subtle influence. When Val-349 was replaced by isoleucine, the mutant COX-1 and COX-2 enzymes formed 41 and 65% 15R-prostaglandins, respectively. This change was highly specific for isoleucine, as mutations of Val-349 to alanine, leucine, asparagine, or threonine did not alter or only slightly altered (< or =13%) the S-configuration at C-15. These results establish a previously unrecognized role for Ser-530 and Val-349 in maintaining the correct S stereochemistry of the carbon-15 hydroxyl group during prostaglandin synthesis. The findings may also explain the absolute conservation of Ser-530, the target of aspirin, throughout the families of cyclooxygenase enzymes.

  6. Synthesis of precursors to and spectroscopic characterization of highly unsaturated carbenes and diradicals and development and implementation of a web-based stereochemistry tutorial

    NASA Astrophysics Data System (ADS)

    Burrmann, Nicola Jean

    A variety of substituted diynols, diynals, and diynones have been prepared en route to the synthesis of precursors to dialkynyl carbenes (R1--C≡C--C--C≡C--R 2). In light of the unique reactivity associated with these simple systems, several strategies were required to assemble the carbon backbones (Chapter I). Tosylhydrazone and trisylhydrazone precursors to 2-diazo-3-pentyne ( 1), 2-diazo-3-butyne (2), and Idiazo-2-butyne ( 3) were synthesized and then converted into their respective diazo compounds. Various attempts to study these diazo compounds using matrix isolation IR and EPR spectroscopy were made and proved to be unsuccessful. Computations were done to characterize the C5H6 potential energy surface, as well as to determine the IR vibrational frequencies of the isomers on this surface (Chapter 2). A web-based Stereochemistry Tutorial that details the core definitions and structural representations relevant to organic stereochemistry was designed and implemented into several introductory-level organic chemistry classes. This tutorial also allows for students to select their preferred structural representation and method for making stereochemical comparisons between molecules. The tutorial was evaluated, either qualitatively, quantitatively, or both, by students in three different introductory organic chemistry courses at the University of Wisconsin---Madison. The data show that students did use a variety of different methods for making stereochemical comparisons between molecules, and that prior exposure to lectures on stereochemistry by the course professor strongly influenced these choices. Furthermore, the level of improvement in stereochemical knowledge as a result of using only the tutorial was comparable to, or higher than, that achieved by students who were only exposed to lectures by the course professor, regardless of the method chosen for making stereochemical comparisons between molecules (Chapter 3)

  7. Single Stage Tandem Mass Spectrometry Assignment of the C-5 Uronic Acid Stereochemistry in Heparan Sulfate Tetrasaccharides using Electron Detachment Dissociation

    NASA Astrophysics Data System (ADS)

    Agyekum, Isaac; Zong, Chengli; Boons, Geert-Jan; Amster, I. Jonathan

    2017-04-01

    The analysis of heparan sulfate (HS) glycosaminoglycans presents many challenges, due to the high degree of structural heterogeneity arising from their non-template biosynthesis. Complete structural elucidation of glycosaminoglycans necessitates the unambiguous assignments of sulfo modifications and the C-5 uronic acid stereochemistry. Efforts to develop tandem mass spectrometric-based methods for the structural analysis of glycosaminoglycans have focused on the assignment of sulfo positions. The present work focuses on the assignment of the C-5 stereochemistry of the uronic acid that lies closest to the reducing end. Prior work with electron-based tandem mass spectrometry methods, specifically electron detachment dissociation (EDD), have shown great promise in providing stereo-specific product ions, such as the B3 ´ -CO2, which has been found to distinguish glucuronic acid (GlcA) from iduronic acid (IdoA) in some HS tetrasaccharides. The previously observed diagnostic ions are generally not observed with 2-O-sulfo uronic acids or for more highly sulfated heparan sulfate tetrasaccharides. A recent study using electron detachment dissociation and principal component analysis revealed a series of ions that correlate with GlcA versus IdoA for a set of 2-O-sulfo HS tetrasaccharide standards. The present work comprehensively investigates the efficacy of these ions for assigning the C-5 stereochemistry of the reducing end uronic acid in 33 HS tetrasaccharides. A diagnostic ratio can be computed from the sum of the ions that correlate to GlcA to those that correlate to IdoA.

  8. Synthesis, Properties and Stereochemistry of 2-Halo-1,2λ⁵-oxaphosphetanes.

    PubMed

    Kolodiazhna, Anastasy O; Kolodiazhnyi, Oleg I

    2016-10-17

    Results of research into four-membered 2-halo-1,2λ⁵-oxaphosphetane phosphorus(V)-heterocycles are presented. The preparation of 2-halo-1,2λ⁵-oxaphosphetanes by reaction of P-haloylides with carbonyl compounds is described. The mechanism of asynchronous [2+2]-сycloaddition of ylides to aldehydes was proposed on the base of low-temperature NMR investigations. 2-Halo-1,2λ⁵-oxaphosphetanes were isolated as individual compounds and their structures were confirmed by ¹Н-, (13)C-, (19)F- and (31)Р-NMR spectra. These compounds are convenient reagents for preparing of various organic and organophosphorus compounds hardly available by other methods. Chemical and physical properties of the 2-halo-1,2λ⁵-oxaphosphetanes are reviewed. The 2-chloro-1,2λ⁵-oxaphosphetanes, rearrange with formation of 2-chloroalkyl-phosphonates or convert into trans-phosphorylated alkenes depending on the substituents at the α-carbon atom. Prospective synthetic applications of 2-halo-1,2λ⁵-oxaphosphetanes are analyzed. The 2-halo-1,2λ⁵-oxaphosphetanes may be easily converted to various alkenylphosphonates: allyl- or vinylphosphonates, phosphorus ketenes, thioketenes, ketenimines.

  9. N-benzoyl-1,5-benzothiazepine and its S-oxide as vasopressin receptor ligands: insight into the active stereochemistry around the seven-membered ring.

    PubMed

    Yoneda, Tetsuya; Tabata, Hidetsugu; Tasaka, Tomohiko; Oshitari, Tetsuta; Takahashi, Hideyo; Natsugari, Hideaki

    2015-04-09

    The stereochemistry of N-benzoyl-1,5-benzothiazepine and its S-oxide derivatives as vasopressin receptor ligands was examined in detail by freezing the conformation with a methyl group at the C6 or C9 of 1,5-benzothiazepine. It was revealed that the active forms recognized by the receptors are (cis,aS) for 1,5-benzothiazepine (5-7)-II and (cis,1S,aS) (syn) for its S-oxide (8-10)-II. The C9-methyl derivative of 1,5-benzothiazepine S-oxide (10-II) was designed and synthesized, achieving the putative active syn-isomer.

  10. 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.

  11. 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.

  12. 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.

  13. Biomarkers: are realism and control mutually exclusive in integrated pollution assessment?

    PubMed

    Wilson, J G; McHugh, B; Giltrap, M

    2014-12-01

    The conventional view of pollution monitoring is that any choice is a trade-off between realism and precision, as the control over confounding variables decreases with the increasing degree of organization of the test system. Dublin Bay is subject to considerable anthropogenic pressures and there have been many attempts to quantify the status of the system at organizational levels from DNA strand breaks (Comet) to the system itself (Ecological Network analysis, ENA). Using Dublin Bay as an example, the data show there was considerable variability at all levels of organization. At intracellular level, Lysosome Membrane Stability (LMS, assessed by Neutral Red Retention, NRR) varied almost 4-fold with season and individual condition, while the community level AZTI Marine biotic Index (AMBI) had a similar range within a single, supposedly homogeneous, site. Overall, there was no evidence that biomarkers of the lower levels of organisation reduced the variability of the measure, despite the extra control over influencing variables, nor was there any evidence that variability was additive at higher levels of organisation. This poses problems for management, especially given the fixed limits of Ecological Quality Standards (EQSs). Clearly while the integrated approach to pollution monitoring does offer the potential to link effects across the organizational range, it should also be possible to improve their capability by widening the database for reference values, particularly at the higher level of organization, and by process models, including the confounding variables found in the field, for those at lower level.

  14. [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.

  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.

  16. Perceptions of risk in motorcyclists: unrealistic optimism, relative realism and predictions of behaviour.

    PubMed

    Rutter, D R; Quine, L; Albery, I P

    1998-11-01

    In the first phase of a prospective investigation, a national sample of motorcyclists completed a postal questionnaire about their perceptions of risk, their behaviour on the roads and their history of accidents and spills. In the second phase a year later, they reported on their accident history and behaviour over the preceding 12 months. A total of 723 respondents completed both questionnaires. Four sets of findings are reported. First, the group as a whole showed unrealistic optimism: on average, respondents believed themselves to be less at risk than other motorcyclists of an accident needing hospital treatment in the next year. Second, optimism was tempered by 'relative realism', in that respondents who were young and inexperienced saw themselves as more at risk than other motorcyclists, as did riders who reported risky behaviours on the road. Third, there was some evidence of debiasing by personal history, in that having a friend or a relative who had been killed or injured on the roads was associated with perceptions of absolute risk of injury or death--though there were no effects on comparative risk and no effects on any of the judgments of a history of accidents of one's own. Finally, there was good evidence that perceptions of risk predicted subsequent behaviour, though generally in the direction not of precaution adoption but of precaution abandonment: the greater the perceived risk at time 1, the more frequent the risky behaviour at time 2. The implications of the findings are discussed, and possible interpretations are suggested.

  17. A strict experimental test of macroscopic realism in a superconducting flux qubit

    PubMed Central

    Knee, George C.; Kakuyanagi, Kosuke; Yeh, Mao-Chuang; Matsuzaki, Yuichiro; Toida, Hiraku; Yamaguchi, Hiroshi; Saito, Shiro; Leggett, Anthony J.; Munro, William J.

    2016-01-01

    Macroscopic realism is the name for a class of modifications to quantum theory that allow macroscopic objects to be described in a measurement-independent manner, while largely preserving a fully quantum mechanical description of the microscopic world. Objective collapse theories are examples which aim to solve the quantum measurement problem through modified dynamical laws. Whether such theories describe nature, however, is not known. Here we describe and implement an experimental protocol capable of constraining theories of this class, that is more noise tolerant and conceptually transparent than the original Leggett–Garg test. We implement the protocol in a superconducting flux qubit, and rule out (by ∼84 s.d.) those theories which would deny coherent superpositions of 170 nA currents over a ∼10 ns timescale. Further, we address the ‘clumsiness loophole' by determining classical disturbance with control experiments. Our results constitute strong evidence for the superposition of states of nontrivial macroscopic distinctness. PMID:27811844

  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.

  19. An assessment of the realism of digital human manikins used for simulation in ergonomics.

    PubMed

    Nérot, Agathe; Skalli, Wafa; Wang, Xuguang

    2015-01-01

    In this study, the accuracy of the joint centres of the manikins generated by RAMSIS and Human Builder (HB), two digital human modelling (DHM) systems widely used in industry for virtual ergonomics simulation, was investigated. Eighteen variously sized females and males were generated from external anthropometric dimensions and six joint centres (knee, hip and four spine joints) were compared with their anatomic locations obtained from the three-dimensional reconstructed bones from a low-dose X-ray system. Both RAMSIS and HB could correctly reproduce external anthropometric dimensions, while the estimation of internal joint centres location presented an average error of 27.6 mm for HB and 38.3 mm for RAMSIS. Differences between both manikins showed that a more realistic kinematic linkage led to better accuracy in joint location. This study opens the way to further research on the relationship between the external body geometry and internal skeleton in order to improve the realism of the internal skeleton of DHMs, especially for a biomechanical analysis requiring information of joint load and muscle force estimation. This study assessed two digital human modelling (DHM) systems widely used in industry for virtual ergonomics. Results support the need of a more realistic human modelling, especially for a biomechanical analysis and a standardisation of DHMs.

  20. 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