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Kinds of Q Terms modified by Q Selected AbstractsPhysical foundations, models, and methods of diffusion magnetic resonance imaging of the brain: A reviewCONCEPTS IN MAGNETIC RESONANCE, Issue 5 2007Ludovico Minati Abstract The foundations and characteristics of models and methods used in diffusion magnetic resonance imaging, with particular reference to in vivo brain imaging, are reviewed. The first section introduces Fick's laws, propagators, and the relationship between tissue microstructure and the statistical properties of diffusion of water molecules. The second section introduces the diffusion-weighted signal in terms of diffusion of magnetization (Bloch,Torrey equation) and of spin-bearing particles (cumulant expansion). The third section is dedicated to the rank-2 tensor model, the bb -matrix, and the derivation of indexes of anisotropy and shape. The fourth section introduces diffusion in multiple compartments: Gaussian mixture models, relationship between fiber layout, displacement probability and diffusivity, and effect of the b -value. The fifth section is devoted to higher-order generalizations of the tensor model: singular value decompositions (SVD), representation of angular diffusivity patterns and derivation of generalized anisotropy (GA) and scaled entropy (SE), and modeling of non-Gaussian diffusion by means of series expansion of Fick's laws. The sixth section covers spherical harmonic decomposition (SHD) and determination of fiber orientation by means of spherical deconvolution. The seventh section presents the Fourier relationship between signal and displacement probability (Q -space imaging, QSI, or diffusion-spectrum imaging, DSI), and reconstruction of orientation-distribution functions (ODF) by means of the Funk,Radon transform (Q -ball imaging, QBI). © 2007 Wiley Periodicals, Inc. Concepts Magn Reson Part A 30A: 278,307, 2007. [source] A performance comparison between the Earth Simulator and other terascale systems on a characteristic ASCI workload,CONCURRENCY AND COMPUTATION: PRACTICE & EXPERIENCE, Issue 10 2005Darren J. Kerbyson Abstract This work gives a detailed analysis of the relative performance of the recently installed Earth Simulator and the next top four systems in the Top500 list using predictive performance models. The Earth Simulator uses vector processing nodes interconnected using a single-stage, cross-bar network, whereas the next top four systems are built using commodity based superscalar microprocessors and interconnection networks. The performance that can be achieved results from an interplay of system characteristics, application requirements and scalability behavior. Detailed performance models are used here to predict the performance of two codes representative of the ASCI workload, namely SAGE and Sweep3D. The performance models encapsulate fully the behavior of these codes and have been previously validated on many large-scale systems. One result of this analysis is to size systems, built from the same nodes and networks as those in the top five, that will have the same performance as the Earth Simulator. In particular, the largest ASCI machine, ASCI Q, is expected to achieve a similar performance to the Earth Simulator on the representative workload. Published in 2005 by John Wiley & Sons, Ltd. [source] Stabilization of Radiation-Condensation Instability by Light Impurity InjectionCONTRIBUTIONS TO PLASMA PHYSICS, Issue 3-5 2010A. A. Pshenov Abstract As it has been shown in [1,2], Radiation-Condensation Instability (RCI) may initiate Microfaceted Asymmetric Radiation from the Edge (MARFE) in tokamaks (see also review papers [3-5]). Nevertheless, experiments demonstrate the stable regimes with strongly radiated edge plasmas after Ne injection [6-8] or in siliconized discharges. Two effects destabilize radiative plasmas, the decrease of radiation losses Q with the electron temperature Te increase, and the increase of Q with electron and impurity densities rise. The finite relaxation time of impurity distribution over ionization states [6] as well as the thermal force acting on the growth rate doesn't shift the instability margin. Hence, one can examine the stability margin using the approximation of the coronal equilibrium. Radiation losses of intrinsic impurities like beryllium, carbon and nitrogen usually decrease with the temperature increase at the temperature range typical for the edge (see Fig. 1, curve 1). The situation may be significantly different for impurity mixtures. Radiation losses L , Q /(nenI)normalized by electron and impurity densities ne and nI for the mixture of carbon and neon are shown in Fig. 1, curves 2-5. One can see that ,Q/,T > 0 for practically any temperature at the edge if the concentration ratio nNe/nC , 5. Hence, one can expect the stabilization of RCI by injection of additional impurity and achievement of stable regime with the strongly radiated edge plasmas. The stability of plasmas with few impurity mixtures is examined in the present paper numerically (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Does female board representation influence firm performance?CORPORATE GOVERNANCE, Issue 2 2007The Danish evidence Board diversity has become a major issue within corporate governance where a number of studies seek to explore the impact of diversity on firm performance. The debate focuses on questions such as whether a corporation's board should reflect the firm's stakeholders or be more in line with society in general. This article uses a sample of listed Danish firms during the period of 1998,2001 in a cross sectional analysis. Despite that fact that Denmark has gone very far in the liberalisation of women, Danish board rooms are still to a large extent dominated by men. Contrary to a number of other studies, this article does not find any significant link between firm performance as measured by Tobin's Q and female board representation. This is also the case for board members' educational background as well as the proportion of foreigners. It is argued that board members with an unconventional background are socialised unconsciously adopting the ideas of the majority of conventional board members, which entails that a potential performance effect does not materialise. [source] Media Reviews Available OnlineACADEMIC EMERGENCY MEDICINE, Issue 12 2006Article first published online: 28 JUN 200 Book reviewed in this article: Pediatric Resuscitation: A Practical Approach. Edited by Mark G. Roback, Stephen J. Teach. Anyone, Anything, Anytime (A History of Emergency Medicine) By Brian J. Zink. Emergency Medicine Decision Making: Critical Choices in Chaotic Environments By Scott Weingart, Peter Wyer. Cardiology Clinics: Chest Pain Units issue Edited by Ezra A. Amsterdam, J. Douglas Kirk MD. Pediatric Emergency Medicine Quick Glance Edited by Ghazala Q. Sharieff, Madeline Matar Joseph, Todd W. Wylie. Emergency Medicine Written Board Review. By Scott H. Plantz, Dwight Collman. Emergency Medicine Oral Board Review. By William Gossman, Scott H. Plantz. Emergency Medicine Q & A. By Joseph Lex, Lance W. Kreplick, Scott H. Plantz, Daniel Girazadas Jr. [source] Crystal structure of 4'-O-methylalpinumisoflavone at 90KCRYSTAL RESEARCH AND TECHNOLOGY, Issue 7 2006R. Kingsford-Adaboh Abstract 4,-O-Methylalpinumisoflavone crystals which hitherto had been difficult to crystallize for X-ray diffraction analyses have been obtained from a demethylated product of O, O-dimethylalpinumisoflavone. The structural and conformational features of the crystal measured at 90 K are reported and compared with previously reported work of O,O-dimethylalpinumisoflavone and 5-O-methyl-4,-O-(3-methyl-but-2-en-1-yl) alpinumisoflavone. Each of these compounds is characterized by a six membered ring that is further fused to a benzopyrone isoflavone moiety resulting in a tricyclic ring system. This six membered ring shows a half-chair conformation in all the molecules studied, with the ring in the title compound showing the least Cremer-Pople puckering amplitude Q and shorter inter and intramolecular contacts. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Dynamic compartmentalization of protein tyrosine phosphatase receptor Q at the proximal end of stereocilia: Implication of myosin VI-based transportCYTOSKELETON, Issue 7 2008Hirofumi Sakaguchi Abstract Hair cell stereocilia are apical membrane protrusions filled with uniformly polarized actin filament bundles. Protein tyrosine phosphatase receptor Q (PTPRQ), a membrane protein with extracellular fibronectin repeats has been shown to localize at the stereocilia base and the apical hair cell surface, and to be essential for stereocilia integrity. We analyzed the distribution of PTPRQ and a possible mechanism for its compartmentalization. Using immunofluorescence we demonstrate that PTPRQ is compartmentalized at the stereocilia base with a decaying gradient from base to apex. This distribution can be explained by a model of transport directed toward the stereocilia base, which counteracts diffusion of the molecules. By mathematical analysis, we show that this counter transport is consistent with the minus end-directed movement of myosin VI along the stereocilia actin filaments. Myosin VI is localized at the stereocilia base, and exogenously expressed myosin VI and PTPRQ colocalize in the perinuclear endosomes in COS-7 cells. In myosin VI-deficient mice, PTPRQ is distributed along the entire stereocilia. PTPRQ-deficient mice show a pattern of stereocilia disruption that is similar to that reported in myosin VI-deficient mice, where the predominant features are loss of tapered base, and fusion of adjacent stereocilia. Thin section and freeze-etching electron microscopy showed that localization of PTPRQ coincides with the presence of a dense cell surface coat. Our results suggest that PTPRQ and myosin VI form a complex that dynamically maintains the organization of the cell surface coat at the stereocilia base and helps maintain the structure of the overall stereocilia bundle. Cell Motil. Cytoskeleton 2008. Published 2008 Wiley-Liss, Inc. [source] The effects of lipid-lowering drug therapy on cardiovascular responsiveness in type 2 diabetic patientsDIABETES OBESITY & METABOLISM, Issue 1 2006Laurence Guy HowesArticle first published online: 18 MAR 200 Type 2 diabetes is associated with a high prevalence of dyslipidaemia and a high incidence of cardiovascular disease. Lipid lowering therapy with HMG Co-A reductase inhibitors (statins) reduce the risk of cardiovascular events in type 2 diabetic and non-diabetic patients, effects which are believed to be partly due to improvements in vascular function. The aetiology of abnormal vascular function in type 2 diabetics is likely to be multifactorial and the pattern of vascular dysfunction in type 2 diabetes may differ from that which occurs in non-diabetic patients with dyslipidaemia. Abnormalities in endothelium derived hyperpolarising factor (EDHF) mediated vasodilation in resistance vessels may be more prominent in both type 1 and type 2 diabetes than in non-diabetic patients with endothelial dysfunction. The effects of lipid lowering therapy on vascular responsiveness may differ in type 2 diabetic patients from those found in non-diabetic patients. Statin therapy does not appear to improve responses to endothelial dependent vasodilators in type 2 diabetics, but may alter the ratio between nitric oxide (NO) and EDHF mediated responses. Fibrate therapy improves flow mediated dilation of brachial arteries in type 2 diabetic patients, but only appears to improve endothelium dependant vasodilator responses in resistance vessels when given in conjunction with co-enzyme Q. [source] A systematic review of the effectiveness of brief interventions with substance using adolescents by type of drugDRUG AND ALCOHOL REVIEW, Issue 3 2003Dr ROBERT J. TAIT Abstract The aim of this paper is to evaluate the effectiveness of brief interventions (BI) with adolescents (mean age < 20) in reducing alcohol, tobacco or other drug (ATOD) use by means of a systematic review of BI for adolescent substance use in the English language literature up to 2002. We identified 11 studies involving 3734 adolescents. Follow-up ranged from 6 weeks to 24 months. Motivational interviewing was the predominant approach, underpinning eight studies: the remaining three provided personalized health information. Seven papers reported outcomes for alcohol interventions and four involved other substances (including one with separate alcohol outcomes). The overall effect size was d= 0.126 with borderline homogeneity (Q = 14.9, df = 9, p = 0.09). The effect size from the eight alcohol interventions (n = 1075) was classified as significant but "small" (d = 0.275). The remaining non-alcohol studies were considered separately as interventions involving tobacco or multiple substance use. The two interventions with tobacco involved a substantial sample (n = 2626) but had a very small effect (d = 0.037), while the two interventions addressing multiple substances involved few participants (n = 110) but had a medium , large effect (d = 0.78). Across a diverse range of settings (dental clinic, schools, universities, substance treatment centres) and, therefore, probably diverse clients, BI conferred benefits to adolescent substance users. BI had a small effect on alcohol consumption and related measures. The data for tobacco interventions suggested a very small reduction, particularly with general community interventions. The effect of BI with multiple substances appears substantial but the small sample cautions against expansive generalization. [source] An attenuation model for distant earthquakesEARTHQUAKE ENGINEERING AND STRUCTURAL DYNAMICS, Issue 2 2004Adrian Chandler Abstract Large magnitude earthquakes generated at source,site distances exceeding 100km are typified by low-frequency (long-period) seismic waves. Such induced ground shaking can be disproportionately destructive due to its high displacement, and possibly high velocity, shaking characteristics. Distant earthquakes represent a potentially significant safety hazard in certain low and moderate seismic regions where seismic activity is governed by major distant sources as opposed to nearby (regional) background sources. Examples are parts of the Indian sub-continent, Eastern China and Indo-China. The majority of ground motion attenuation relationships currently available for applications in active seismic regions may not be suitable for handling long-distance attenuation, since the significance of distant earthquakes is mainly confined to certain low to moderate seismicity regions. Thus, the effects of distant earthquakes are often not accurately represented by conventional empirical models which were typically developed from curve-fitting earthquake strong-motion data from active seismic regions. Numerous well-known existing attenuation relationships are evaluated in this paper, to highlight their limitations in long-distance applications. In contrast, basic seismological parameters such as the Quality factor (Q -factor) could provide a far more accurate representation for the distant attenuation behaviour of a region, but such information is seldom used by engineers in any direct manner. The aim of this paper is to develop a set of relationships that provide a convenient link between the seismological Q -factor (amongst other factors) and response spectrum attenuation. The use of Q as an input parameter to the proposed model enables valuable local seismological information to be incorporated directly into response spectrum predictions. The application of this new modelling approach is demonstrated by examples based on the Chi-Chi earthquake (Taiwan and South China), Gujarat earthquake (Northwest India), Nisqually earthquake (region surrounding Seattle) and Sumatran-fault earthquake (recorded in Singapore). Field recordings have been obtained from these events for comparison with the proposed model. The accuracy of the stochastic simulations and the regression analysis have been confirmed by comparisons between the model calculations and the actual field observations. It is emphasized that obtaining representative estimates for Q for input into the model is equally important.Thus, this paper forms part of the long-term objective of the authors to develop more effective communications across the engineering and seismological disciplines. Copyright © 2003 John Wiley & Sons, Ltd. [source] Estimation and Confidence Regions for Parameter Sets in Econometric Models,ECONOMETRICA, Issue 5 2007Victor Chernozhukov This paper develops a framework for performing estimation and inference in econometric models with partial identification, focusing particularly on models characterized by moment inequalities and equalities. Applications of this framework include the analysis of game-theoretic models, revealed preference restrictions, regressions with missing and corrupted data, auction models, structural quantile regressions, and asset pricing models. Specifically, we provide estimators and confidence regions for the set of minimizers ,I of an econometric criterion function Q(,). In applications, the criterion function embodies testable restrictions on economic models. A parameter value ,that describes an economic model satisfies these restrictions if Q(,) attains its minimum at this value. Interest therefore focuses on the set of minimizers, called the identified set. We use the inversion of the sample analog, Qn(,), of the population criterion, Q(,), to construct estimators and confidence regions for the identified set, and develop consistency, rates of convergence, and inference results for these estimators and regions. To derive these results, we develop methods for analyzing the asymptotic properties of sample criterion functions under set identification. [source] R-learning with multiple state-action value tablesELECTRICAL ENGINEERING IN JAPAN, Issue 3 2007Koichiro Ishikawa Abstract We propose a method to improve the performance of R-learning, a reinforcement learning algorithm, by using multiple state-action value tables. Unlike Q- or Sarsa learning, R-learning learns a policy to maximize undiscounted rewards. Multiple state-action value tables cause substantial explorations as needed and make R-learning work well. Efficiency of the proposed method is verified through experiments in a simulated environment. © 2007 Wiley Periodicals, Inc. Electr Eng Jpn, 159(3): 34, 47, 2007; Published online in Wiley InterScience (www.interscience. wiley.com). DOI 10.1002/eej.20473 [source] EOF using the Ritz method: Application to superelliptic microchannelsELECTROPHORESIS, Issue 18 2007Chang Yi Wang Abstract An efficient Ritz method is developed from the variational principle to solve the Poisson,Boltzmann equation under the Debye,Hückel approximation for studying the EOF in microchannels. The method is applied to the family of superelliptic cross sections which includes the elliptic channel and the rectangular channel as limiting cases. Several accurate tables presented are useful for design of electroosmotic channels, especially rectangular channels with rounded corners. It is shown how the flow rate Q is a sophisticated consequence of the nondimensional electrokinetic width K, the aspect ratio b as well as the superelliptic exponent n. [source] Distribution patterns of the Q and B biotypes of Bemisia tabaci in the Mediterranean Basin based on microsatellite variationENTOMOLOGIA EXPERIMENTALIS ET APPLICATA, Issue 3 2007B. Simón Abstract At least five of the biotypes described in the Bemisia tabaci (Gennadius) (Homoptera: Aleyrodidae) complex are known to be present in the Mediterranean Basin area. Only two of them, however, are economically relevant, that is, biotypes B and Q. Biological and genetic differences between the two biotypes have been well studied, but less is known about their patterns of genetic variation and population structure. To address these issues, a study was undertaken based on variation at six microsatellite loci among a subset of nine B. tabaci populations (five belonging to the Q and four to the B biotype). The data obtained show that (i) these loci showed considerable polymorphism in the Q and B biotypes populations although the presence of null alleles can obscure the picture; (ii) the Iberian-Q, Canarian-Q, and Egyptian-B populations exhibit heterozygosity excess as a result of bottleneck events; (iii) the low genetic differentiation between the Israeli, Iberian Peninsula, and Italian populations suggest that these populations share a common gene pool; (iv) the genetic distances between the Canarian-Q population and the geographically close population from Morocco indicates spatial isolation and a limited gene flow; and finally (v) the microsatellite data for the B populations indicate that the whiteflies from Egypt and Israel have a close phylogenetic relationship, but the source of these biotype B invasions into the Mediterranean area remains unknown. [source] Abundance of six tetracycline resistance genes in wastewater lagoons at cattle feedlots with different antibiotic use strategiesENVIRONMENTAL MICROBIOLOGY, Issue 1 2007Nicholas Peak Summary The abundance of six tetracycline resistance genes tet(O), tet(Q), tet(W), tet(M), tet(B) and tet(L), were quantified over time in wastewater lagoons at concentrated animal feeding operations (CAFO) to assess how feedlot operation affects resistance genes in downstream surface waters. Eight lagoons at five cattle feedlots in the Midwestern United States were monitored for 6 months. Resistance and 16S-rRNA gene abundances were quantified using real-time PCR, and physicochemical lagoon conditions, tetracycline levels, and other factors (e.g. feedlot size and weather conditions) were monitored over time. Lagoons were sorted according to antibiotic use practice at each site, and designated as ,no-use', ,mixed-use' or ,high-use' for comparison. High-use lagoons had significantly higher detected resistance gene levels (tetR; 2.8 × 106 copies ml,1) relative to no-use lagoons (5.1 × 103 copies ml,1; P < 0.01) and mixed-use lagoons (7.3 × 105 copies ml,1; P = 0.076). Bivariate correlation analysis on pooled data (n = 54) confirmed that tetR level strongly correlated with feedlot area (r = 0.67, P < 0.01) and ,total' bacterial 16S-rRNA gene level in each lagoon (r = 0.51, P < 0.01), which are both characteristic of large CAFOs. tet(M) was the most commonly detected gene, both in absolute number and normalized to 16S-rRNA gene level, although tet(O), tet(Q) and tet(W) levels were also high in the mixed and high-use lagoons. Finally, resistance gene levels were highly seasonal with abundances being 10,100 times greater in the autumn versus the summer. Results show that antibiotic use strategy strongly affects both the abundance and seasonal distribution of resistance genes in associated lagoons, which has implications on water quality and feedlot management practices. [source] Active immunization with IL-1 displayed on virus-like particles protects from autoimmune arthritisEUROPEAN JOURNAL OF IMMUNOLOGY, Issue 3 2008Gunther Spohn Abstract IL-1 is an important mediator of inflammation and a major cause of tissue damage in rheumatoid arthritis (RA). Therapeutic administration of recombinant IL-1 receptor antagonist (IL-1Ra) is efficacious in reducing clinical symptoms of disease, but suffers from several drawbacks, including the need for frequent administrations of large amounts. Here, we show that immunization of mice with either IL-1, or IL-1, chemically cross-linked to virus-like particles (VLP) of the bacteriophage Q, elicited a rapid and long-lasting autoantibody response. The induced Ab efficiently neutralized the binding of the respective IL-1 molecules to their receptors in vitro and their pro-inflammatory activities in vivo. In the collagen-induced arthritis model, both vaccines strongly protected mice from inflammation and degradation of bone and cartilage. Moreover, immunization with either vaccine showed superior efficacy than daily administrations of high amounts of IL-1Ra. In the T and B cell-independent collagen Ab transfer model, immunization with the IL-1, vaccine strongly protected from arthritis, whereas immunization with the IL-1, vaccine had no effect. Our results suggest that active immunization with IL-1,, and especially IL-1, conjugated to Q, VLP, might become an efficacious and cost-effective new treatment option for RA and other systemic IL-1-dependent inflammatory disorders. [source] Ruthenium ,6 -Hexamethylbenzene Complexes Containing Dichalcogenoimidodiphosphinate LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2009Wai-Man Cheung Abstract Treatment of [Ru(,6 -C6Me6)Cl2]2 with AgOTf (OTf, = triflato) followed by K[N(R2PQ)2] gave the 16-electron complexes [Ru(,6 -C6Me6){,2 -N(R2PQ)2}][OTf] [Q = S, R = Ph (1) or iPr (2); Q = Se, R = Ph (3) or iPr (4)] which were isolated as air-stable blue or dark green crystals. For complex 1, when the crude product was recrystallised from CH2Cl2/hexane in air, orange crystals of [Ru(,6 -C6Me6){,3 -N(Ph2PS)2}][OTf] (1a) were isolated as a minor product. The reaction of compound 1 with ammonia, hydrazine hydrate and 4,4,-bipyridyl(4,4,-bpy) gave the 18-electron adducts [Ru(,6 -C6Me6){,2 -N(Ph2PS)2}L][OTf] [L = NH3 (5), N2H4 (6)] and dinuclear[{Ru(,6 -C6Me6)[,2 -N(Ph2PS)2]}2(,-4,4,-bpy)][OTf]2 (7), respectively. Treatment of compound 2 with Li[BEt3H] and NaBH4 afforded the ethyl [Ru(,6 -C6Me6){N(iPr2PS)2}Et] (8) andhydride [Ru(,6 -C6Me6){,2 -N(iPr2PS)2}H] (9) compounds, respectively. Formal potentials for Ru[N(R2PQ)2] complexes have been determined. The structures for complexes 1, 1a, 5, 6, 8 and 9 have been established by X-ray crystallography. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Electronic Structure of Linearly Coordinated EQ Complexes of the Type [(N3N)W(EQ)] [N3N = N(CH2CH2NSiMe3)3; E = P, As, Sb, Bi; Q = O, S, Se, Te]: A DFT StudyEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2007Gábor Balázs Abstract Density functional theory (DFT) calculations were carried out on the terminal EQ complexes [(N3N)W(EQ)] {N3N = N(CH2CH2NSiMe3)3; E = P, As, Sb, Bi; Q = O, S, Se Te} to clarify the bonding situation within the linear Nax,W,E,Q core. This unusual structural motif gives rise to a bonding arrangement in which the ,-electron density is delocalised over the three atoms of the W,E,Q unit. Fragment calculations and natural bond order (NBO) data indicated that the ,-bonding component of the Nax,W,E,Q unit comprises two occupied , orbitals, while the , component of bonding comprises two sets of degenerate , orbitals. In general, the , orbitals of the Nax,W,E,Q core are higher in energy compared to the , orbitals. The phosphorus monoxide (EQ = PO) complexes provide an exception to this rule, with the 1, orbitals of the W,P,O core lower in energy than the , orbitals. Generally, as the atomic number of either the pnicogen (E) or chalcogen (Q) atom increases the extent of ,-orbital delocalisation decreases, whereas the ,-orbital delocalisation increases. Fractional bond orders and Wiberg bond indices were used to establish whether localisation of the ,-electron density gives rise to a W,E or an E,Q double or triple bond. Both methods indicate a W,E as well as an E,Q double bond. The ionic nature of the complexes were analysed by inspection of the Hirschfeld charge distribution which shows only a moderate ionic character. Exceptions are the pnicogen monoxide complexes, which are more ionic. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] [Re6Q7O(3,5-Me2PzH)6]Br2·3,5-Me2PzH (Q = S, Se) , New Octahedral Rhenium Cluster Complexes with Organic Ligands: Original Synthetic Approach and Unexpected Ligand Exchange in the Cluster CoreEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2005Yuri V. Mironov Abstract Two new octahedral rhenium cluster complexes, [Re6S7O(3,5-Me2PzH)6]Br2·3,5-Me2PzH (1) and [Re6Se7O(3,5-Me2PzH)6]Br2·3,5-Me2PzH (2), with the organic ligand 3,5-dimethylpyrazole (3,5-Me2PzH), have been synthesised by reaction of rhenium chalcobromides Cs3[Re6(µ3 -Q7Br)Br6] (Q = S, Se) with molten dimethylpyrazole. During the reaction, all six apical bromine ligands of the cluster complexes are substituted by the organic ligand, which is coordinated through the aromatic nitrogen atom N2. Additionally, the inner ligand µ3 -Br in the cluster core [Re6(µ3 -Q7Br)]3+ is substituted by oxygen, giving cluster cores [Re6(µ3 -Q7O)]2+ with mixed chalcogen/oxygen ligands. Compounds 1 and 2 have been characterised by single-crystal X-ray diffraction analysis. They are isostructural and crystallise with four formula units in the unit cell. Absorption spectra and luminescence characteristics of these two cluster compounds have been investigated in methanol. Absorption starts below 400 nm. For both compounds, broad emissions were found. The fluorescence decays of the two compounds follow a diexponential decay behaviour. The main fluorescence intensity decays have longer fluorescence lifetimes of 3.07 ± 0.03 (1) and 3.96 ± 0.02 µs (2). Studying the thermal stability of both compounds in vacuo showed that the release of 3,5-dimethylpyrazole ligands begins near 200 °C, and decomposition, with the removal of 7 molecules of 3,5-Me2PzH, is complete at 330 °C. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] (4-Acyl-5-pyrazolonato)titanium Derivatives: Oligomerization, Hydrolysis, Voltammetry, and DFT StudyEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2003Francesco Caruso Abstract Twenty 4-acyl-5-pyrazolonato (Q) titanium derivatives of varied nuclearity have been synthesized from Ti(OR)4 or TiCl4 and characterized with spectroscopic methods (IR, NMR, ESI-MS). While Ti,(,-diketonato) cleavage is not seen in isolated solids, Ti,O(alkoxy) (or Ti,Cl) bonds cleave upon hydrolysis, leading to several structural forms, including oligomers. Ionic Q species with no Ti, i.e., obtained after Ti,Q cleavage, are seen for some Ti,Q derivatives by ESI-MS, which also indicates a varied nuclearity for a given species, e.g., the isolated polynuclear [Q2Ti-,-O]n has several "n" values. Mononuclear Ti complexes are obtained under rigorous anhydrous conditions. The cis structures of the mononuclear species (QT)2Ti(OCH3)2, QT = 3-methyl-4-(neopentylcarbonyl)-1-phenylpyrazol-5-onato have been analyzed with DFT methods. A trans influence is a major driving force that accounts for several sets of Ti,O bonds. One of the cis stereoisomers is 56 kcal/mol higher in energy than the other two. In contrast, all (QT)2TiCl2cis isomers show similar energies. Voltammetry of the mononuclear species (QT)2Ti(OnPr)2 and the antitumor tetranuclear compound [(QB)2Ti-,-O]4, (QB = 4-benzoyl-3-methyl-1-phenylpyrazol-5-onato) indicate that the TiIV is less prone to reduction to TiIII in the latter (Epc for the TiIV/TiIII couple is ,1.71 V and ,1.46 V versus Fc+/Fc, respectively). Potential antitumor compounds having a Ti/Q ratio of 1:1 do not disproportionate, unlike the equivalent acetylacetonato derivatives, and are water-soluble. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Dominance of the lurcher mutation in heteromeric kainate and AMPA receptor channelsEUROPEAN JOURNAL OF NEUROSCIENCE, Issue 5 2001Martin K. Schwarz Abstract Homomeric glutamate receptor (GluR) channels become spontaneously active when the last alanine residue within the invariant SYTANLAAF-motif in the third membrane segment is substituted by threonine. The same mutation in the orphan GluR,2 channel is responsible for neurodegeneration in ,Lurcher' (Lc) mice. Since most native GluRs are composed of different subunits, we investigated the effect of an Lc-mutated subunit in heteromeric kainate and AMPA receptors expressed in HEK293 cells. Kainate receptor KA2 subunits, either wild type or carrying the Lc mutation (KA2Lc), are retained inside the cell but are surface-expressed when assembled with GluR6 sununits. Importantly, KA2Lc dominates the gating of KA2Lc/GluR6WT channels, as revealed by spontaneous activation and by slowed desensitization and deactivation kinetics of ligand-activated whole-cell currents. Moreover, the AMPA receptor subunit GluR-BLc(Q) which forms spontaneously active homomeric channels with rectifying current-voltage relationships, dominates the gating of heteromeric GluR-BLc(Q)/GluR-A(R) channels. The spontaneous currents of these heteromeric AMPAR channels show linear current,voltage relationships, and the ligand-activated whole-cell currents display slower deactivation and desensitization kinetics than the respective wild-type channels. For heteromeric Lc-mutated kainate and AMPA receptors, the effects on kinetics were reduced relative to the homomeric Lc-mutated forms. Thus, an Lc-mutated subunit can potentially influence heteromeric channel function in vivo, and the severity of the phenotype will critically depend on the levels of homomeric GluRLc and heteromeric GluRLc/GluRWT channels. [source] Dentin surface treatment using a non-thermal argon plasma brush for interfacial bonding improvement in composite restorationEUROPEAN JOURNAL OF ORAL SCIENCES, Issue 5 2010Andy C. Ritts Ritts AC, Li H, Yu Q, Xu C, Yao X, Hong L, Wang Y. Dentin surface treatment using a non-thermal argon plasma brush for interfacial bonding improvement in composite restoration. Eur J Oral Sci 2010; 118: 510,516. © 2010 Eur J Oral Sci The objective of this study was to investigate the treatment effects of non-thermal atmospheric gas plasmas on dentin surfaces used for composite restoration. Extracted unerupted human third molars were prepared by removing the crowns and etching the exposed dentin surfaces with 35% phosphoric acid gel. The dentin surfaces were treated using a non-thermal atmospheric argon plasma brush for various periods of time. The molecular changes of the dentin surfaces were analyzed using Fourier transform infrared spectrophotometry/attenuated total reflectance (FTIR/ATR), and an increase in the amount of carbonyl groups was detected on plasma-treated dentin surfaces. Adper Single Bond Plus adhesive and Filtek Z250 dental composite were applied as directed. To evaluate the dentin/composite interfacial bonding, the teeth thus prepared were sectioned into micro-bars and analyzed using tensile testing. Student,Newman,Keuls tests showed that the bonding strength of the composite restoration to peripheral dentin was significantly increased (by 64%) after 30 s of plasma treatment. However, the bonding strength to plasma-treated inner dentin did not show any improvement. It was found that plasma treatment of the peripheral dentin surface for up to 100 s resulted in an increase in the interfacial bonding strength, while prolonged plasma treatment of dentin surfaces (e.g. 5 min) resulted in a decrease in the interfacial bonding strength. [source] Approximal caries development in surfaces in contact with fluoride-releasing and non-fluoride-releasing restorative materials: an in situ studyEUROPEAN JOURNAL OF ORAL SCIENCES, Issue 6 2007Áine M. Lennon This study investigated the effect of compomer on initial interproximal caries development. One-hundred and sixty cylindrical, and 40 semispherical, bovine enamel samples (control) were prepared, polished, and sterilized. Sixty semicircular samples were prepared from each of the compomer Dyract eXtra and the fluoride-free composite Spectrum TPH. Samples were stored in water and fluoridated twice daily for 28 d. A baseline quantitative light fluorescence (QLF) image was made of each cylindrical sample. Twenty volunteers received intra-oral appliances with eight sample chambers. Each wing contained 1 control sample and either 3 Dyract eXtra or 3 Spectrum TPH samples in contact with the enamel surface of a cylindrical enamel sample. Appliances were worn for 24 h a day for 28 d except during toothbrushing (twice daily) and placement in 10% sucrose solution (five times daily). A final QLF image was made after 28 d. Caries development was analyzed as the lesion area × mean fluorescence loss (,Q % mm2) between these and the baseline images using QLF subtract software. The median ,Q was significantly lower in the Dyract eXtra group (,6.1% mm2) than in the Spectrum TPH (,13.9% mm2, P , 0.001) or control (,11.4% mm2, P = 0.03) groups. Teeth in contact with the compomer developed less caries compared with controls. [source] Synthesis of Doubly Strapped meso,meso -Linked Porphyrin Arrays and Triply Linked Conjugated Porphyrin TapesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2006Toshiaki Ikeda Abstract 1,10-Dioxydecamethylene doubly strapped ZnII -porphyrin S1 was prepared and treated with AgPF6 to give meso,meso -linked porphyrin oligomers Sn (n = 2, 3, 4, 6, 8, and 12), which were converted to triply linked porphyrin tapes TSn by meso,meso, -dibromo meso,meso -linked porphyrin arrays BSn and meso,meso, -diphenyl meso,meso -linked porphyrin arrays PSn. The structures of S1 and S2 have been determined by single-crystal X-ray diffraction analysis. Characteristically, Sn exhibit sharp Q(0,0) absorption and fluorescence bands. Low energy Q-band-like absorption bands of TSn are progressively red-shifted with an increase in the number of porphyrins without saturation behavior of conjugation. The double straps suppress ,,, stacking to some extent as seen from partial preservation of vibration structures in the Q-band-like bands of TS4 and TS6 and improve the chemical stabilities of longer tapes such as TS8 and TS12. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] XNA, (xylo Nucleic Acid): A Summary and New DerivativesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 11 2005B. Ravindra Babu Abstract Fully modified homopyrimidine 2'-deoxy- xylo nucleic acid (dXNA) form triple helixes with complementary DNA/RNA with thermal stabilities comparable to those of the corresponding DNA:DNA and DNA:RNA duplexes. However, a single or few insertions of dXNA monomers in a DNA strand significantly lower duplex stabilities. The dXNA monomers are known to adopt predominantly an N -type furanose conformation in solution. With a desire to increase the binding affinity, seven sugar-modified XNA monomers (H, F, N, M, K, P and Q) have been synthesised and their effect on hybridization towards DNA and RNA complements studied. The introduction of 2'-fluoro and 2'-hydroxy substituents was expected to induce conformational restriction towards C3'- endo -type furanose conformation of monomer F derived from 1-(2'-deoxy-2'-fluoro-,- D -xylofuranosyl)thymine and monomer H derived from 1-(,- D -xylofuranosyl)thymine. The presence of functionalites facing the minor groove as in 1-(2'-amino-2'-deoxy-2'- N,4'- C -methylene-,- D -xylofuranosyl)thymine (monomer N), 1-[4- C -(N -methylpiperazinyl)methyl-,- D -xylofuranosyl]thymine (monomer P), 1-(4- C -piperazinylmethyl-,- D -xylofuranosyl)thymine (monomer Q), 1-(4- C -hydroxymethyl-,- D -xylofuranosyl)thymine (monomer M) and 9-(4- C -hydroxymethyl-,- D -xylofuranosyl)adenine (monomer K) was studied, with monomer N being locked in an N -type furanose conformation. Besides, an efficient synthesis of known xylo -LNA phosphoramidite 19, required for the incorporation of 1-(2'- O,4'- C -methylene-,- D -xylofuranosyl)thymine (monomer L) is described. For comparison, hydridization data of various XNAs reported in the literature are included in the discussion section. The thermal denaturation studies show that XNAs containing conformationally locked monomers (N and L) display improved binding affinity, and that partially modified DNA/XNA chimera, or fully modified XNA display preferential hybridization towards RNA complements. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Sorption of phosphorus in field-moist and air-dried samples from four weakly developed cultivated soil profilesEUROPEAN JOURNAL OF SOIL SCIENCE, Issue 1 2007T. PeltovuoriArticle first published online: 9 FEB 200 Summary Sorption of phosphorus (P) in complete soil profiles in northern Europe is not adequately documented. I measured the sorption in genetic horizons of four cultivated soils (Inceptisols, Spodosol) in Finland using both field-moist and air-dried soil samples, fitted modified Freundlich equations (Q = a × Ib , q) to the data, and presented the results in quantity/intensity (Q/I) graphs. Least-squares-estimates for the parameters of the modified Freundlich equation (a, b, q) were found to be imprecise measures of sorption. Values derived from the fitted equations (the amount of P sorbed at the P concentration of 2 mg litre,1 and P buffering capacity at the same concentration) were more precise. Both were correlated with concentrations of oxalate-extractable iron and aluminium. In all soils, there was a distinct difference in sorption between the fertilized Ap horizons and the subsurface horizons, which retained P strongly. Most of the sorption capacity was located in the B horizons at depths between 0.3 and 0.7 m. The results demonstrate the effects of soil-forming processes and human impact on the sorption of P in the soils. Drying the samples prior to the sorption experiments altered the shape of the Q/I graphs. It increased dissolution of P at small P concentrations, sorption at large P concentrations, and the estimates for P buffering capacity. The effects of drying soil samples on the results and the imprecision of the parameters estimated with the modified Freundlich equation should be taken into account when interpreting results of Q/I experiments. [source] The baroreflex is counteracted by autoregulation, thereby preventing circulatory instabilityEXPERIMENTAL PHYSIOLOGY, Issue 4 2004Roberto Burattini The aims of this study were (a) to apply in the animal with intact baroreflex a two-point method for estimation of overall, effective open-loop gain, G0e, which results from the combined action of baroregulation and total systemic autoregulation on peripheral resistance; (b) to predict specific baroreflex gain by correcting the effective gain for the autoregulation gain; and (c) to discuss why the effective gain is usually as low as 1,2 units. G0e was estimated from two measurements of both cardiac output, Q, and mean systemic arterial pressure, P: one in the reference state (set-point) and the other in a steady-state reached 1,3 min after a small cardiac output perturbation. In anaesthetized cats and dogs a cardiac output perturbation was accomplished by partial occlusion of the inferior vena cava and by cardiac pacing, respectively. Average (±s.e.m.) estimates of G0e were 1.4 ± 0.2 (n= 8) in the cat and 1.5 ± 0.4 (n= 5) in the dog. The specific baroreflex open-loop gain, G0b, found after correction for total systemic autoregulation, was 3.3 ± 0.4 in the cat and 2.8 ± 0.8 in the dog. A model-based analysis showed that, with G0e as low as 1.4, the closed-loop response of P to a stepwise perturbation in Q results in damped oscillations that disappear in about 1 min. The amplitude and duration of these oscillations, which have a frequency of about 0.1 Hz, increase with increasing G0e and cause instability when G0e is about 3. We conclude that autoregulation reduces the effectiveness of baroreflex gain by about 55%, thereby preventing instability of blood pressure response. [source] Recent Insights into Carotid Baroreflex Function in Humans Using the Variable Pressure Neck ChamberEXPERIMENTAL PHYSIOLOGY, Issue 6 2003Paul J. Fadel The variable pressure neck chamber has provided an invaluable research tool for the non-invasive assessment of carotid baroreflex (CBR) function in human investigations. The ability to construct complete stimulus-response curves and define specific parameters of the reflex function curve permits statistical comparisons of baroreflex function between different experimental conditions, such as rest and exercise. Results have convincingly indicated that the CBR stimulus-response curve is reset during exercise in an intensity-dependent manner to functionally operate around the prevailing pressure elicited by the exercise workload. Furthermore, both at rest and during exercise, alterations in stroke volume do not contribute importantly to the maintenance of arterial blood pressure by the carotid baroreceptors, and therefore, any reflex-induced changes in cardiac output (Q) are the result of CBR-mediated changes in heart rate. However, more importantly, the CBR-induced changes in mean arterial pressure (MAP) are primarily mediated by alterations in vascular conductance with only minimal contributions from Q to the initial reflex MAP response. Thus, the capacity of the CBR to regulate blood pressure depends critically on its ability to alter vascular tone both at rest and during exercise. This review will emphasize the utility of the variable pressure neck chamber to assess CBR function in human experimental investigations and the mechanisms by which the CBR responds to alterations in arterial blood pressure both at rest and during exercise. [source] Similarities of stress concentrations in contact at round punches and fatigue at notches: implications to fretting fatigue crack initiationFATIGUE & FRACTURE OF ENGINEERING MATERIALS AND STRUCTURES, Issue 7 2000Giannakopoulos A linear elastic model of the stress concentration due to contact between a rounded flat punch and a homogeneous substrate is presented, with the aim of investigating fretting fatigue crack initiation in contacting parts of vibrating structures including turbine engines. The asymptotic forms for the stress fields in the vicinity of a rounded punch-on-flat substrate are derived for both normal and tangential loading, using both analytical and finite element methods. Under the action of the normal load, P, the ensuing contact is of width 2b which includes an initial flat part of width 2a. The asymptotic stress fields for the sharply rounded flat punch contact have certain similarities with the asymptotic stress fields around the tip of a blunt crack. The analysis showed that the maximum tensile stress, which occurs at the contact boundary due to tangential load Q, is proportional to a mode II stress intensity factor of a sharp punch divided by the square root of the additional contact length due to the roundness of the punch, Q/(,(b,,,a),,b). The fretting fatigue crack initiation can then be investigated by relating the maximum tensile stress with the fatigue endurance stress. The result is analogous to that of Barsom and McNicol where the notched fatigue endurance stress was correlated with the stress intensity factor and the square root of the notch-tip radius. The proposed methodology establishes a ,notch analogue' by making a connection between fretting fatigue at a rounded punch/flat contact and crack initiation at a notch tip and uses fracture mechanics concepts. Conditions of validity of the present model are established both to avoid yielding and to account for the finite thickness of the substrate. The predictions of the model are compared with fretting fatigue experiments on Ti,6Al,4V and shown to be in good agreement. [source] Acetylcholinesterase from the invertebrate Ciona intestinalis is capable of assembling into asymmetric forms when co-expressed with vertebrate collagenic tail peptideFEBS JOURNAL, Issue 6 2008Adam Frederick To learn more about the evolution of the cholinesterases (ChEs), acetylcholinesterase (AChE) and butyrylcholinesterase in the vertebrates, we investigated the AChE activity of a deuterostome invertebrate, the urochordate Ciona intestinalis, by expressing in vitro a synthetic recombinant cDNA for the enzyme in COS-7 cells. Evidence from kinetics, pharmacology, molecular biology, and molecular modeling confirms that the enzyme is AChE. Sequence analysis and molecular modeling also indicate that the cDNA codes for the AChET subunit, which should be able to produce all three globular forms of AChE: monomers (G1), dimers (G2), and tetramers (G4), and assemble into asymmetric forms in association with the collagenic subunit collagen Q. Using velocity sedimentation on sucrose gradients, we found that all three of the globular forms are either expressed in cells or secreted into the medium. In cell extracts, amphiphilic monomers (G1a) and non-amphiphilic tetramers (G4na) are found. Amphiphilic dimers (G2a) and non-amphiphilic tetramers (G4na) are secreted into the medium. Co-expression of the catalytic subunit with Rattus norvegicus collagen Q produces the asymmetric A12 form of the enzyme. Collagenase digestion of the A12 AChE produces a lytic G4 form. Notably, only globular forms are present in vivo. This is the first demonstration that an invertebrate AChE is capable of assembling into asymmetric forms. We also performed a phylogenetic analysis of the sequence. We discuss the relevance of our results with respect to the evolution of the ChEs in general, in deuterostome invertebrates, and in chordates including vertebrates. [source] | |||||||||||||||||||||||||||||||||||||||||||||||||||||||