1,093 research outputs found

    Structural investigations of phosphorus-nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6-n)(NHBut)(n) derivatives

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    A series of compounds of the N3P3Cl(6-n)(NHBut)n family (where n = 0, 1, 2, 4 and 6) are presented and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N3P3Cl5(NHBut) and N3P3Cl2(NHBut)4 have been determined at 120K and those of N3P3Cl6 and N3P3Cl4(NHBut)2 have been re-determined at 120K. These are compared with the known structure of N3P3(NHBut)6 studied at 150K. Trends in molecular parameters (phosphazene ring, P-Cl & P-N(HBut) distances, PCl2 angles and endo- and exo-cyclic phosphazene ring parameters) across the series are observed. Hydrogen-bonding motifs are identified, characterised and compared. Both the molecular and hydrogen bonding parameters are related to the electron distribution in bonds and the derived basicities of the cyclophosphazene series of compounds. These findings provide evidence for a proposed mechanism for nucleophilic substitution at a phosphorus site bearing a PCl(NHBut) moiety

    Dynamics of a Quantum Reference Frame

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    We analyze a quantum mechanical gyroscope which is modeled as a large spin and used as a reference against which to measure the angular momenta of spin-1/2 particles. These measurements induce a back-action on the reference which is the central focus of our study. We begin by deriving explicit expressions for the quantum channel representing the back-action. Then, we analyze the dynamics incurred by the reference when it is used to sequentially measure particles drawn from a fixed ensemble. We prove that the reference thermalizes with the measured particles and find that generically, the thermal state is reached in time which scales linearly with the size of the reference. This contrasts a recent conclusion of Bartlett et al. that this takes a quadratic amount of time when the particles are completely unpolarized. We now understand their result in terms of a simple physical principle based on symmetries and conservation laws. Finally, we initiate the study of the non-equilibrium dynamics of the reference. Here we find that a reference in a coherent state will essentially remain in one when measuring polarized particles, while rotating itself to ultimately align with the polarization of the particles

    T-Lymphocyte Activation is Not Affected by the Mobilization of Senescent T-Cells into the Peripheral Blood Following an Acute Bout of Exercise

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    It is well recognized that individuals are at an increased risk of illness following an arduous exercise regime. Exercise may affect activation status of cells and play a pivotal role in defense against pathogenic invasion. CD69 is the earliest known expressed cell surface antigen of T-cell activation and is a reliable marker of cell activation status (Green et al. Med. Sci. Sports Exerc. 35, 582-588: 2003). Exercise is known to alter the frequency of senescent cells in the blood expressing the cell surface glycoprotein killer cell lectin-like receptor G1 (KLRG1), and are antigen-experienced and unable to clonally expand upon further antigenic stimulation (Simpson et al. J. Appl. Phys. 103, 396-401:2007), PURPOSE: To examine the contribution of senescent T-cells mobilized by exercise on the overall activation status of the peripheral blood T-cell pool following an acute bout of exercise. METHODS: Ten moderately trained males (age: 24.6 ± 4.8; height: 183.1 ± 6.7cm; mass: 72.8 ± 7.9kg; ; 61.3 ± 5.9 ml.kg-1.min-1) ran at speeds corresponding to 80% until volitional exhaustion (time: 36.1 ± 5.8 minutes). Blood lymphocytes isolated before (PRE), immediately after (POST) and 1 hour after (1HrPOST) exercise were stimulated for 4 hours in culture with and without the mitogen PMA and assessed for KLRG1 and CD69 expression and co-expression on CD3+, CD3+/CD4+ (CD4+) and CD3+/CD8+ (CD8+) lymphocyte subsets using 4-colour flow cytometry. RESULTS: No changes in CD69 GMFI were observed on total CD3+, CD4+ and CD8+ T-cells POST or 1HrPOST exercise. The proportions of KLRG1+ cells among the total CD3+, CD4+ and CD8+ T-cell populations increased by 172%, 107% and 169% respectively POST exercise and fell below baseline values 1h later (p\u3c0.05). At all sample time points, CD69 GMFI was greater on stimulated KLRG1+ T-cells compared to KLRG1- cells (p\u3c0.05). CONCLUSION: We conclude that exercise does not affect the activation status of the total T-cell pool. Instead, the number of senescent cells expressing CD69 is greater than those that are not senescent at all times. This suggests that upon pathogenic invasion post-exercise

    Behavior change interventions: the potential of ontologies for advancing science and practice

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    A central goal of behavioral medicine is the creation of evidence-based interventions for promoting behavior change. Scientific knowledge about behavior change could be more effectively accumulated using "ontologies." In information science, an ontology is a systematic method for articulating a "controlled vocabulary" of agreed-upon terms and their inter-relationships. It involves three core elements: (1) a controlled vocabulary specifying and defining existing classes; (2) specification of the inter-relationships between classes; and (3) codification in a computer-readable format to enable knowledge generation, organization, reuse, integration, and analysis. This paper introduces ontologies, provides a review of current efforts to create ontologies related to behavior change interventions and suggests future work. This paper was written by behavioral medicine and information science experts and was developed in partnership between the Society of Behavioral Medicine's Technology Special Interest Group (SIG) and the Theories and Techniques of Behavior Change Interventions SIG. In recent years significant progress has been made in the foundational work needed to develop ontologies of behavior change. Ontologies of behavior change could facilitate a transformation of behavioral science from a field in which data from different experiments are siloed into one in which data across experiments could be compared and/or integrated. This could facilitate new approaches to hypothesis generation and knowledge discovery in behavioral science

    The structure of human 15-lipoxygenase-2 with a substrate mimic

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    Atherosclerosis is associated with chronic inflammation occurring over decades. The enzyme 15-lipoxygenase-2 (15-LOX-2) is highly expressed in large atherosclerotic plaques, and its activity has been linked to the progression of macrophages to the lipid-laden foam cells present in atherosclerotic plaques.We report here the crystal structure of human 15-LOX-2 in complex with an inhibitor that appears to bind as a substrate mimic. 15-LOX-2 contains a long loop, composed of hydrophobic amino acids, which projects from the amino-terminal membrane-binding domain. The loop is flanked by two Ca2+-binding sites that confer Ca2+-dependent membrane binding. A comparison of the human 15-LOX-2 and 5-LOX structures reveals similarities at the active sites, as well striking differences that can be exploited for design of isoform-selective inhibitors. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc

    In vitro influence of stem surface finish and mantle conformity on pressure generation in cemented hip arthroplasty

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    Background and purpose Under physiological loads, debonded cemented femoral stems have been shown to move within their cement mantle and generate a fluid pump that may facilitate peri-prosthetic osteolysis by pressurizing fluid and circulating wear debris. The long-term physiological loading of rough and polished tapered stems in vitro has shown differences in performance, with greater interface pressures generated by the rough stems. In this study we investigated the individual effects of stem surface finish, degree of mantle wear, and mode of loading on the stem pump mechanism
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