15 resultados para Dalton

em Aston University Research Archive


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Background Emotional-processing inhibition has been suggested as a mechanism underlying some of the clinical features of depersonalization and/or derealization. In this study, we tested the prediction that autonomic response to emotional stimuli would be reduced in patients with depersonalization disorder. Methods The skin conductance responses of 15 patients with chronic depersonalization disorder according to DSM-IV, 15 controls, and 11 individuals with anxiety disorders according to DSM-IV, were recorded in response to nonspecific elicitors (an unexpected clap and taking a sigh) and in response to 15 randomized pictures with different emotional valences: 5 unpleasant, 5 pleasant, and 5 neutral. Results The skin conductance response to unpleasant pictures was significantly reduced in patients with depersonalization disorder (magnitude of 0.017 µsiemens in controls and 0.103 µsiemens in patients with anxiety disorders; P = .01). Also, the latency of response to these stimuli was significantly prolonged in the group with depersonalization disorder (3.01 seconds compared with 2.5 and 2.1 seconds in the control and anxiety groups, respectively; P = .02). In contrast, latency to nonspecific stimuli (clap and sigh) was significantly shorter in the depersonalization and anxiety groups (1.6 seconds) than in controls (2.3 seconds) (P = .03). Conclusions In depersonalization disorder, autonomic response to unpleasant stimuli is reduced. The fact that patients with depersonalization disorder respond earlier to a startling noise suggests that they are in a heightened state of alertness and that the reduced response to unpleasant stimuli is caused by a selective inhibitory mechanism on emotional processing.

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Four novel mononuclear coordination compounds namely: [Fe(Hthpy)2](SO4)1/2·3.5H2O 1, [Fe(Hthpy)2]NO3·3H2O 2, [Fe(H2mthpy)2](CH3C6H4SO3)3·CH3CH2OH 3 and [Fe(Hethpy)(ethpy)]·8H2O 4, (H2thpy = pyridoxalthiosemicarbazone, H2mthpy = pyridoxal-4-methylthiosemicarbazone, H2ethpy = pyridoxal-4-ethylthiosemicarbazone), were synthesized in the absence or presence of organic base, Et3N and NH3. Compounds 1 and 2 are monocationic, and were prepared using the singly deprotonated form of pyridoxalthiosemicarbazone. Both compounds crystallise in the monoclinic system, C2/c and P21/c space group for 1 and 2, respectively. Complex 3 is tricationic, it is formed with neutral bis(ligand) complex and possesses an interesting 3D channel architecture, the unit cell is triclinic, P1 space group. For complex 4, the pH value plays an important role during its synthesis; 4 is neutral and crystallises with two inequivalent forms of the ligand: the singly and the doubly deprotonated chelate of H2ethpy, the unit cell is monoclinic, C2/c space group. Notably, in 1 and 4, there is an attractive infinite three dimensional hydrogen bonding network in the crystal lattice. Magnetic measurements of 1 and 4 revealed that a rather steep spin transition from the low spin to high spin Fe(III) states occurs above 300 K in the first heating step. This transition is accompanied by the elimination of solvate molecules and thus, stabilizes the high spin form due to the breaking of hydrogen bonding networks; compared to 2 and 3, which keep their low spin state up to 400 K.

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The reaction of [Re6Q8(OH)6]4- (Q = S, Se) with p-tertbutylpyridine (TBP) in water leads to neutral trans-[Re6Q8(TBP)4(OH)2] whose hydroxyl reactivity with carboxylic acid and TBP exchange reaction with functional pyridine have been investigated.

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Golfers, coaches and researchers alike, have all keyed in on golf putting as an important aspect of overall golf performance. Of the three principle putting tasks (green reading, alignment and the putting action phase), the putting action phase has attracted the most attention from coaches, players and researchers alike. This phase includes the alignment of the club with the ball, the swing, and ball contact. A significant amount of research in this area has focused on measuring golfer’s vision strategies with eye tracking equipment. Unfortunately this research suffers from a number of shortcomings, which limit its usefulness. The purpose of this thesis was to address some of these shortcomings. The primary objective of this thesis was to re-evaluate golfer’s putting vision strategies using binocular eye tracking equipment and to define a new, optimal putting vision strategy which was associated with both higher skill and success. In order to facilitate this research, bespoke computer software was developed and validated, and new gaze behaviour criteria were defined. Additionally, the effects of training (habitual) and competition conditions on the putting vision strategy were examined, as was the effect of ocular dominance. Finally, methods for improving golfer’s binocular vision strategies are discussed, and a clinical plan for the optometric management of the golfer’s vision is presented. The clinical management plan includes the correction of fundamental aspects of golfers’ vision, including monocular refractive errors and binocular vision defects, as well as enhancement of their putting vision strategy, with the overall aim of improving performance on the golf course. This research has been undertaken in order to gain a better understanding of the human visual system and how it relates to the sport performance of golfers specifically. Ultimately, the analysis techniques and methods developed are applicable to the assessment of visual performance in all sports.

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SQUID magnetometry, normally used to characterise the properties of solids, was used to follow a clock reaction in solution, namely the auto-catalytic oxidation of [Co(ii)EDTA] by HO, in real time and it was shown that, in combination with other methods (e.g., magnetic resonance proton relaxation studies and UV-vis absorption analysis), SQUID magnetometry can be a powerful method in elucidating and interpreting the time-profile of chemical reactions so as long as reactants, intermediates and products have suitably large differences in their respective magnetic susceptibilities. © 2009 The Royal Society of Chemistry.

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A series of novel polymeric compounds of formula [M(btzb)3][ClO4]2 (Mll = Fe, Ni or Cu) with btzb = 1,4-bis-(tetrazol-1-yl)butane have been prepared and their physical properties investigated. The btzb ligand has been prepared and its crystal structure determined, together with a tentative crystal structure of the 3-D compound [Fe(btzb)3][ClO4]2. The model of the latter shows two symmetry-related, interpenetrating Fe-btzb networks in which the iron(II) ions approach each other as close as 8.3 and 9.1 Å. This supramolecular catenane undergoes a sharp thermal spin transition around 160 K with hysteresis (20 K) along with a pronounced thermochromic effect. The spin crossover behaviour has been followed by magnetic, DSC, optical spectroscopy and 57Fe Mössbauer spectroscopy measurements. Irradiation with green light at low temperature leads to population of the metastable high-spin state for the thermally active iron(ll) ions. The nature of the spin crossover behaviour has been discussed in detail.

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The reaction of btzmp (1,2-bis(tetrazol-1-yl)-2-methylpropane) with Fe(ClO4)2 generates a 1D polymeric species, [Fe(μ-btzmp)2(btzmp)2](ClO4)2, showing a steep spin transition (T½↑ = 136 K and T ½↓ = 133 K) with a 3 K thermal hysteresis. The crystal structure at 100 and 200 K reveals that, in contrast to other bistetrazole based spin-transition systems such as [Fe(endi)3](BF4)2 and [Fe(btzp)3](ClO4)2, the present compound has only two ligands bridging the metallic centres, while the other two coordination positions are occupied by two mono-coordinated (non-bridging) btzmp ligands. This peculiarity confers an unprecedented crystal packing in the series of 1D bistetrazole based polymers. The change in spin state is accompanied by an order/disorder transition of the ClO4- counterion. A careful examination of the structural changes occurring upon the spin transition indicates that this order/disorder is most likely affected by the modification of the [tetrazole-centroid]-ND-Fe angle (which is typical of bistetrazole spin-transition materials). Apart from X-ray analysis, also magnetic susceptibility, Mössbauer and UV-vis spectroscopies have been used to characterise the HS and the LS states of [Fe(µ-btzmp)2(btzmp)2](ClO4)2. © The Royal Society of Chemistry.

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The synthesis and characterisation of a new, highly luminescent inorganic cluster complex, (Bu4N)2[Mo6I 8(NO3)6], are described. The complex possesses labile nitrato ligands and is therefore a useful precursor for the design of new luminescent materials. To exemplify this, functionalised polystyrene beads have been utilised as "polymeric ligands" to immobilise the molybdenum cluster complex. This journal is © the Partner Organisations 2014.

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Size-controlled, catalytically active PVP-stabilised Pd nanoparticles have been studied by operando liquid phase XAS during the Suzuki cross-coupling of iodonanisole and phenylboronic acid in MeOH-toluene using KOMe base. XAS reveals nanoparticles are stable to metal leaching throughout the reaction, with surface density Pd defect sites directly implicated in the catalytic cycle. The efficacy of popular selective chemical and structural poisons for distinguishing heterogeneous and homogeneous contributions in Pd catalysed cross-couplings is also explored. © 2010 The Royal Society of Chemistry.

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The objective of the study was to define common reasons for non-adherence (NA) to highly active antiretroviral therapy (HAART) and the number of reasons reported by non-adherent individuals. A confidential questionnaire was administered to HIV-seropositive patients taking proteinase inhibitor based HAART. Median self-reported adherence was 95% (n = 178, range = 60-100%). The most frequent reasons for at least 'sometimes' missing a dose were eating a meal at the wrong time (38.2%), oversleeping (36.3%), forgetting (35.0%) and being in a social situation (30.5%). The mean number of reasons occurring at least 'sometimes' was 3.2; 20% of patients gave six or more reasons; those reporting the lowest adherence reported a significantly greater numbers of reasons (ρ = - 0.59; p < 0.001). Three factors were derived from the data by principal component analysis reflecting 'negative experiences of HAART', 'having a low priority for taking medication' and 'unintentionally missing doses', accounting for 53.8% of the variance. On multivariate analysis only the latter two factors were significantly related to NA (odds ratios 0.845 and 0.849, respectively). There was a wide spectrum of reasons for NA in our population. The number of reasons in an individual increased as adherence became less. A variety of modalities individualized for each patient are required to support patients with the lowest adherence.

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Hybrid nanocomposites based on N-doped SrTiO3 nanoparticles wrapped in g-C3N4 nanosheets were successfully prepared by a facile and reproducible polymeric citrate and thermal exfoliation method. The results clearly indicated that the N-doped SrTiO3 nanoparticles are successfully wrapped in layers of the g-C3N4 nanosheets. The g-C3N4/N-doped SrTiO3 nanocomposites showed absorption edges at longer wavelengths compared with the pure g-C3N4 as well as N-doped SrTiO3. The hybrid nanocomposites exhibit an improved photocurrent response and photocatalytic activity under visible light irradiation. Interestingly, the hybrid nanocomposite possesses high photostability and reusability. Based on experimental results, the possible mechanism for prolonged lifetime of the photoinduced charge carrier was also discussed. The high performance of the g-C3N4/N-doped SrTiO3 photocatalysts is due to the synergic effect at the interface of g-C3N4 and N-doped SrTiO3 hetero/nanojunction including the high separation efficiency of the charge carrier, band energy matching and the suppressed recombination rate. Therefore, the hybrid photocatalyst could be of potential interest for water splitting and environmental remediation under natural sunlight.

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Purpose: In golf, the impact of eye-hand dominance on putting performance has long been debated. Eye-hand dominance is thought to impact how golfers judge the alignment of the ball with the target and the club with the ball, as well as how golfers visualize the line of the putt when making decisions about the force needed to hit the ball. Previous studies have all measured ocular dominance in primary gaze only, despite golfers spending a significant amount of their time in a putting stance (bent at the hips, head tilted down). Thus, the purpose of this study was to assess ocular dominance in both primary gaze (aligning the ball with the target) and putting gaze (addressing the ball and aligning the club). Methods: This study investigatedmeasuring pointing oculardominance in both primary and putting gaze positions on 31 golfers (14 amateur, 7 club professionals, and 10 top professionals). All playerswere right-handed golfers, although one reported having no hand dominance and one reported being strongly left hand dominant. Results: The results showed that (1) primary and putting gaze ocular dominances are not equal, nor are they predictive of each other; (2) themagnitude of putting ocular dominance is significantly less than themagnitude of primary gaze ocular dominance; (3) ocular dominance is not correlated with handedness in either primary or putting gaze; and (4) eye-hand dominance is not associated with increased putting skill, although ocular dominance may be associated with increased putting success. Conclusions: It is important that coaches assess golfers' ocular dominance in both primary and putting gaze positions to ensure they have the most accurate information upon which to base their vision strategy decisions.

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Keratoconus is a bilateral degenerative disease characterized by a non-inflammatory, progressive central corneal ectasia (typically asymmetric) and decreased vision. In its early stages it may be managed with spectacles and soft contact lenses but more commonly it is managed with rigid contact lenses. In advanced stages, when contact lenses can no longer be fit, have become intolerable, or corneal damage is severe, a penetrating keratoplasty is commonly performed. Alternative surgical techniques, such as the use of intra-stromal corneal ring segments (INTACS) have been developed to try and improve the fit of rigid contact lenses in keratoconic patients and avoid penetrating keratoplasties. This case report follows through the fitting of rigid contact lenses in an advanced keratoconic cornea after an INTACS procedure and discusses clinical findings, treatment options, and the use of mini-scleral and scleral lens designs as they relate to the challenges encountered in managing such a patient. Mini-scleral and scleral lenses are relatively easy to fit, and can be of benefit to many patients, including advanced keratoconic patients, post-INTAC patients and post-penetrating keratoplasty patients. © 2011 British Contact Lens Association.

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The penalty kick in football is a seemingly simplistic play; however, it has increased in complexity since 1997 when the rules changed allowing goalkeepers to move laterally along their goal line before the ball was kicked. Prior to 1997 goalkeepers were required to remain still until the ball was struck. The objective of this study was to determine the importance of the penalty kick in the modern game of football. A retrospective study of the 2002, 2006 and 2010 World Cup and the 2000, 2004 and 2008 European Championship tournaments was carried out, assessing the importance of the penalty kick in match play and shootouts and the effect of the time of the game on the shooter's success rate. This study demonstrated the conversion rate of penalties was 73% in shootouts and 68% in match play. Significantly more penalties were awarded late in the game: twice as many penalties in the second half than the first and close to four times as many in the fourth quarter vs. the first. Teams awarded penalty kicks during match play won 52%, drew 30% and lost 18% of the time; chances of winning increased to 61% if the penalty was scored, but decreased to 29% if missed. Teams participating in either the World Cup or European Championship final match had roughly a 50% chance of being involved in a penalty shootout during the tournament. Penalty shots and their outcome significantly impact match results in post 1997 football.

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This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] (where X- is Cl-, Br- or I-; OTs- is p-toluenesulfonate and PhSO3 - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>0.6) and narrowest emission bands were found for complexes with a {Mo6I8}4+ cluster core. Moreover, cyclic voltammetric studies revealed that (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes (nBu4N)2[{Mo6X8}X6].