59 resultados para METASTABILITY


Relevância:

20.00% 20.00%

Publicador:

Resumo:

The aims of this chapter are twofold. First, we show how experiments related to nonlinear dynamical systems theory can bring about insights on the interconnectedness of different information sources for action. These include the amount of information as emphasised in conventional models of cognition and action in sport and the nature of perceptual information typically emphasised in the ecological approach. The second aim was to show how, through examining the interconnectedness of these information sources, one can study the emergence of novel tactical solutions in sport; and design experiments where tactical/decisional creativity can be observed. Within this approach it is proposed that perceptual and affective information can be manipulated during practice so that the athlete's cognitive and action systems can be transposed to a meta-stable dynamical performance region where the creation of novel action information may reside.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Objectives: Adaptive patterning of human movement is context specific and dependent on interacting constraints of the performer–environment relationship. Flexibility of skilled behaviour is predicated on the capacity of performers to move between different states of movement organisation to satisfy dynamic task constraints, previously demonstrated in studies of visual perception, bimanual coordination, and an interceptive combat task. Metastability is a movement system property that helps performers to remain in a state of relative coordination with their performance environments, poised between multiple co-existing states (stable and distinct movement patterns or responses). The aim of this study was to examine whether metastability could be exploited in externally paced interceptive actions in fast ball sports, such as cricket. Design: Here we report data on metastability in performance of multi-articular hitting actions by skilled junior cricket batters (n = 5). Methods: Participants’ batting actions (key movement timings and performance outcomes) were analysed in four distinct performance regions varied by ball pitching (bounce) location. Results: Results demonstrated that, at a pre-determined distance to the ball, participants were forced into a meta-stable region of performance where rich and varied patterns of functional movement behaviours emerged. Participants adapted the organisation of responses, resulting in higher levels of variability in movement timing in this performance region, without detrimental effects on the quality of interceptive performance outcomes. Conclusions: Findings provide evidence for the emergence of metastability in a dynamic interceptive action in cricket batting. Flexibility and diversity of movement responses were optimised using experiential knowledge and careful manipulation of key task constraints of the specific sport context.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

We have developed an alternate description of dynamics of nucleation in terms of an extended set of order parameters. The order parameters consist of an ordered set of kth largest clusters, ordered such that k = 1 is the largest cluster in the system, k = 2 is the second largest cluster, and so on. We have derived an analytic expression for the free energy for the kth largest cluster, which is in excellent agreement with the simulated results. At large supersaturation, the free energy barrier for the growth of the kth largest cluster disappears and the nucleation becomes barrierless. The major success of this extended theoretical formalism is that it can clearly explain the observed change in mechanism at large metastability P. Bhimalapuram et al., Phys. Rev. Lett. 98, 206104 (2007)] and the associated dynamical crossover. The classical nucleation theory cannot explain this crossover. The crossover from activated to barrierless nucleation is found to occur at a supersaturation where multiple clusters cross the critical size. We attribute the crossover as the onset of the kinetic spinodal. We have derived an expression for the rate of nucleation in the barrierless regime by modeling growth as diffusion on the free energy surface of the largest cluster. The model reproduces the slower increase in the rate of growth as a function of supersaturation, as observed in experiments.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order to understand the large numerical discrepancy between simulation predictions and experimental results, we carried out a study of the dependence on the range of intermolecular interactions of both the surface tension of an equilibrium planar gas-liquid interface and the free energy barrier of nucleation. Both are found to depend significantly on the range of interaction for the Lennard-Jones potential, both in two and three dimensions. The value of surface tension and also the free energy difference between the gas and the liquid phase increase significantly and converge only when the range of interaction is extended beyond 6-7 molecular diameters. We find, with the full range of interaction potential, that the surface tension shows only a weak dependence on supersaturation, so the reason for the breakdown of CNT (with simulated values of surface tension and free energy gap) cannot be attributed to the supersaturation dependence of surface tension. This remains an unsettled issue at present because of the use of the value of surface tension obtained at coexistence.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

As the beneficial effects of curcumin have often been reported to be limited to its small concentrations, we have undertaken a study to find the aggregation properties of curcumin in water by varying the number of monomers. Our molecular dynamics simulation results show that the equilibrated structure is always an aggregated state with remarkable structural rearrangements as we vary the number of curcumin monomers from 4 to 16 monomers. We find that the curcumin monomers form clusters in a very definite pattern where they tend to aggregate both in parallel and anti-parallel orientation of the phenyl rings, often seen in the formation of beta-sheet in proteins. A considerable enhancement in the population of parallel alignments is observed with increasing the system size from 12 to 16 curcumin monomers. Due to the prevalence of such parallel alignment for large system size, a more closely packed cluster is formed with maximum number of hydrophobic contacts. We also follow the pathway of cluster growth, in particular the transition from the initial segregated to the final aggregated state. We find the existence of a metastable structural intermediate involving a number of intermediate-sized clusters dispersed in the solution. We have constructed a free energy landscape of aggregation where the metatsable state has been identified. The course of aggregation bears similarity to nucleation and growth in highly metastable state. The final aggregated form remains stable with the total exclusion of water from its sequestered hydrophobic core. We also investigate water structure near the cluster surface along with their orientation. We find that water molecules form a distorted tetrahedral geometry in the 1st solvation layer of the cluster, interacting rather strongly with the hydrophilic groups at the surface of the curcumin. The dynamics of such quasi-bound water molecules near the surface of curcumin cluster is considerably slower than the bulk signifying a restricted motion as often found in protein hydration layer. (C) 2014 AIP Publishing LLC.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

A new approach is presented to resolve bias-induced metastability mechanisms in hydrogenated amorphous silicon (a-Si:H) thin film transistors (TFTs). The post stress relaxation of threshold voltage (V(T)) was employed to quantitatively distinguish between the charge trapping process in gate dielectric and defect state creation in active layer of transistor. The kinetics of the charge de-trapping from the SiN traps is analytically modeled and a Gaussian distribution of gap states is extracted for the SiN. Indeed, the relaxation in V(T) is in good agreement with the theory underlying the kinetics of charge de-trapping from gate dielectric. For the TFTs used in this work, the charge trapping in the SiN gate dielectric is shown to be the dominant metastability mechanism even at bias stress levels as low as 10 V.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Recent infrared spectroscpic observations of local vibrational mode absorptions have revealed a number of photosensitive centers in semi-insulating GaAs. They include (OVAs) center which has three modes at 730 cm(-1) (A), 715 cm(-1) (B), and 714 cm(-1) (C), respectively, a suggested NH center related to a line at 983 cm(-1) (X(1)), and centers related to hydrogen, such as (H-O) or (H-N) bonds, corresponding to a group of peaks in the region of 2900-3500 cm(-1). The photosensitivity of various local vibration centers was observed to have similar time dependence under near-infrared illumination and was suggested to be due to their charge-state interconversion. Mainly described in this work is the effect of the 1.25-eV illumination. It is confirmed that this photoinduced kinetic process results from both electron capture and hole capture, which are closely related to the photoionization behavior and metastability of the EL2 center.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

The spectroscopy and metastability of the carbon dioxide doubly charged ion, the CO22+ dication, have been studied with photoionization experiments: time-of-flight photoelectron photoelectron coincidence (TOF-PEPECO), threshold photoelectrons coincidence (TPEsCO), and threshold photoelectrons and ion coincidence (TPEsCO ion coincidence) spectroscopies. Vibrational structure is observed in TOF-PEPECO and TPEsCO spectra of the ground and first two excited states. The vibrational structure is dominated by the symmetric stretch except in the TPEsCO spectrum of the ground state where an antisymmetric stretch progression is observed. All three vibrational frequencies are deduced for the ground state and symmetric stretch and bending frequencies are deduced for the first two excited states. Some vibrational structure of higher electronic states is also observed. The threshold for double ionization of carbon dioxide is reported as 37.340+/-0.010 eV. The fragmentation of energy selected CO22+ ions has been investigated with TPEsCO ion coincidence spectroscopy. A band of metastable states from similar to38.7 to similar to41 eV above the ground state of neutral CO2 has been observed in the experimental time window of similar to0.1-2.3 mus with a tendency towards shorter lifetimes at higher energies. It is proposed that the metastability is due to slow spin forbidden conversion from bound excited singlet states to unbound continuum states of the triplet ground state. Another result of this investigation is the observation of CO++O+ formation in indirect dissociative double photoionization below the threshold for formation of CO22+. The threshold for CO++O+ formation is found to be 35.56+/-0.10 eV or lower, which is more than 2 eV lower than previous measurements. (C) 2005 American Institute of Physics.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Type III galactosemia is an inherited disease caused by mutations which affect the activity of UDP-galactose 4'-epimerase (GALE). We evaluated the impact of four disease-associated variants (p.N34S, p.G90E, p.V94M and p.K161N) on the conformational stability and dynamics of GALE. Thermal denaturation studies showed that wild-type GALE denatures at temperatures close to physiological, and disease-associated mutations often reduce GALE's thermal stability. This denaturation is under kinetic control and results partly from dimer dissociation. The natural ligands, NAD(+) and UDP-glucose, stabilize GALE. Proteolysis studies showed that the natural ligands and disease-associated variations affect local dynamics in the N-terminal region of GALE. Proteolysis kinetics followed a two-step irreversible model in which the intact protein is cleaved at Ala38 forming a long-lived intermediate in the first step. NAD(+) reduces the rate of the first step, increasing the amount of undigested protein whereas UDP-glucose reduces the rate of the second step, increasing accumulation of the intermediate. Disease-associated variants affect these rates and the amounts of protein in each state. Our results also suggest communication between domains in GALE. We hypothesize that, in vivo, concentrations of natural ligands modulate GALE stability and that it should be possible to discover compounds which mimic the stabilising effects of the natural ligands overcoming mutation-induced destabilization.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Advances in metastability exchange optical pumping (MEOP) of 3He at high laser powers, with its various applications, but also at high gas pressures p3 and high magnetic field strengths B, have provided strong motivation for revisiting the understanding and for investigating the limitations of this powerful technique. For this purpose, we present systematic experimental and theoretical studies of efficiency and of relaxation mechanisms in B≤30 mT and p3=0.63−2.45 mbar. 3He nuclear polarisation is measured by light absorption in longitudinal configuration where weak light beams at 1083 nm parallel to magnetic field and cell axis with opposite circular polarisations are used to probe the distribution of populations in the metastable state. This method is systematically tested to evaluate potential systematic biases and is shown to be reliable for the study of OP dynamics despite the redistribution of populations by OP light. Nuclear polarisation loss associated to the emission of polarised light by the plasma discharge used for MEOP is found to decrease above 10 mT, as expected, due to hyperfine decoupling in highly excited states. However, this does not lead to improved MEOP efficiency at high laser power. We find clear evidence of additional laser-induced relaxation instead. The strong OP-enhanced polarisation losses, currently limiting MEOP performances, are quantitatively investigated using an angular momentum budget approach and a recently developed comprehensive model that describes the combined effects of OP, ME and relaxation, validated by comparison to experimental results.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

The spectroscopy and metastability of the carbon dioxide doubly charged ion, the CO 2 2+ dication, have been studied with photoionization experiments: time-of-flight photoelectron photoelectron coincidence (TOF-PEPECO), threshold photoelectrons coincidence (TPEsCO), and threshold photoelectrons and ion coincidence (TPEsCO ion coincidence) spectroscopies. Vibrational structure is observed in TOF-PEPECO and TPEsCO spectra of the ground and first two excited states. The vibrational structure is dominated by the symmetric stretch except in the TPEsCO spectrum of the ground state where an antisymmetric stretch progression is observed. All three vibrational frequencies are deduced for the ground state and symmetric stretch and bending frequencies are deduced for the first two excited states. Some vibrational structure of higher electronic states is also observed. The threshold for double ionization of carbon dioxide is reported as 37.340±0.010 eV. The fragmentation of energy selected CO 2 2+ ions has been investigated with TPEsCO ion coincidence spectroscopy. A band of metastable states from ∼38.7 to ∼41 eV above the ground state of neutral CO 2 has been observed in the experimental time window of ∼0.1-2.3 μs with a tendency towards shorter lifetimes at higher energies. It is proposed that the metastability is due to slow spin forbidden conversion from bound excited singlet states to unbound continuum states of the triplet ground state. Another result of this investigation is the observation of CO ++O + formation in indirect dissociative double photoionization below the threshold for formation of CO 2 2+. The threshold for CO ++O + formation is found to be 35.56±0.10 eV or lower, which is more than 2 eV lower than previous measurements.

Relevância:

20.00% 20.00%

Publicador:

Resumo:

Organismal development, homeostasis, and pathology are rooted in inherently probabilistic events. From gene expression to cellular differentiation, rates and likelihoods shape the form and function of biology. Processes ranging from growth to cancer homeostasis to reprogramming of stem cells all require transitions between distinct phenotypic states, and these occur at defined rates. Therefore, measuring the fidelity and dynamics with which such transitions occur is central to understanding natural biological phenomena and is critical for therapeutic interventions.

While these processes may produce robust population-level behaviors, decisions are made by individual cells. In certain circumstances, these minuscule computing units effectively roll dice to determine their fate. And while the 'omics' era has provided vast amounts of data on what these populations are doing en masse, the behaviors of the underlying units of these processes get washed out in averages.

Therefore, in order to understand the behavior of a sample of cells, it is critical to reveal how its underlying components, or mixture of cells in distinct states, each contribute to the overall phenotype. As such, we must first define what states exist in the population, determine what controls the stability of these states, and measure in high dimensionality the dynamics with which these cells transition between states.

To address a specific example of this general problem, we investigate the heterogeneity and dynamics of mouse embryonic stem cells (mESCs). While a number of reports have identified particular genes in ES cells that switch between 'high' and 'low' metastable expression states in culture, it remains unclear how levels of many of these regulators combine to form states in transcriptional space. Using a method called single molecule mRNA fluorescent in situ hybridization (smFISH), we quantitatively measure and fit distributions of core pluripotency regulators in single cells, identifying a wide range of variabilities between genes, but each explained by a simple model of bursty transcription. From this data, we also observed that strongly bimodal genes appear to be co-expressed, effectively limiting the occupancy of transcriptional space to two primary states across genes studied here. However, these states also appear punctuated by the conditional expression of the most highly variable genes, potentially defining smaller substates of pluripotency.

Having defined the transcriptional states, we next asked what might control their stability or persistence. Surprisingly, we found that DNA methylation, a mark normally associated with irreversible developmental progression, was itself differentially regulated between these two primary states. Furthermore, both acute or chronic inhibition of DNA methyltransferase activity led to reduced heterogeneity among the population, suggesting that metastability can be modulated by this strong epigenetic mark.

Finally, because understanding the dynamics of state transitions is fundamental to a variety of biological problems, we sought to develop a high-throughput method for the identification of cellular trajectories without the need for cell-line engineering. We achieved this by combining cell-lineage information gathered from time-lapse microscopy with endpoint smFISH for measurements of final expression states. Applying a simple mathematical framework to these lineage-tree associated expression states enables the inference of dynamic transitions. We apply our novel approach in order to infer temporal sequences of events, quantitative switching rates, and network topology among a set of ESC states.

Taken together, we identify distinct expression states in ES cells, gain fundamental insight into how a strong epigenetic modifier enforces the stability of these states, and develop and apply a new method for the identification of cellular trajectories using scalable in situ readouts of cellular state.

Relevância:

10.00% 10.00%

Publicador:

Resumo:

Research on expertise, talent identification and development has tended to be mono-disciplinary, typically adopting geno-centric or environmentalist positions, with an overriding focus on operational issues. In this thesis, the validity of dualist positions on sport expertise is evaluated. It is argued that, to advance understanding of expertise and talent development, a shift towards a multidisciplinary and integrative science focus is necessary, along with the development of a comprehensive multidisciplinary theoretical rationale. Dynamical systems theory is utilised as a multidisciplinary theoretical rationale for the succession of studies, capturing how multiple interacting constraints can shape the development of expert performers. Phase I of the research examines experiential knowledge of coaches and players on the development of fast bowling talent utilising qualitative research methodology. It provides insights into the developmental histories of expert fast bowlers, as well as coaching philosophies on the constraints of fast bowling expertise. Results suggest talent development programmes should eschew the notion of common optimal performance models and emphasize the individual nature of pathways to expertise. Coaching and talent development programmes should identify the range of interacting constraints that impinge on the performance potential of individual athletes, rather than evaluating current performance on physical tests referenced to group norms. Phase II of this research comprises three further studies that investigate several of the key components identified as important for fast bowling expertise, talent identification and development extrapolated from Phase I of this research. This multidisciplinary programme of work involves a comprehensive analysis of fast bowling performance in a cross-section of the Cricket Australia high performance pathways, from the junior, emerging and national elite fast bowling squads. Briefly, differences were found in trunk kinematics associated with the generation of ball speed across the three groups. These differences in release mechanics indicated the functional adaptations in movement patterns as bowlers’ physical and anatomical characteristics changed during maturation. Second to the generation of ball speed, the ability to produce a range of delivery types was highlighted as a key component of expertise in the qualitative phase. The ability of athletes to produce consistent results on different surfaces and in different environments has drawn attention to the challenge of measuring consistency and flexibility in skill assessments. Examination of fast bowlers in Phase II demonstrated that national bowlers can make adjustments to the accuracy of subsequent deliveries during performance of a cricket bowling skills test, and perform a range of delivery types with increased accuracy and consistency. Finally, variability in selected delivery stride ground reaction force components in fast bowling revealed the degenerate nature of this complex multi-articular skill where the same performance outcome can be achieved with unique movement strategies. Utilising qualitative and quantitative methodologies to examine fast bowling expertise, the importance of degeneracy and adaptability in fast bowling has been highlighted alongside learning design that promotes dynamic learning environments.

Relevância:

10.00% 10.00%

Publicador:

Resumo:

It is well-known that the properties of semiconductor materials including gallium arsenide are controlled by defects and impurities. The characterization of these defects is important not only for better understanding of the solid state phenomena but also for improved reliability and performance of electronic devices. We have been investigating the defects in gallium arsenide for several years using deep level transient spectroscopy, photoconductivity, transient photoconductivity, photoluminescence etc. Results drawn from our recent studies are presented here to illustrate some of the problems concerning transition metal impurities, process-induced defects, occurrence of intracentre transitions and metastability of deep levels in gallium arsenide.