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PubMed2006

Effects of anharmonicity on nonadiabatic electron transfer: a model.

The effect of anharmonicity in the intramolecular modes of a model system for exothermic intramolecular nonadiabatic electron transfer is probed by examining the dependence of the transition probability on the exoergicity. The Franck-Condon factor for the Morse potential is written in terms of the Gauss hypergeometric function both for a ground initial state and for the general case, and comparisons are made between the first-order perturbation theory results for transition probability for harmonic and Morse oscillators. These results are verified with quantum dynamical simulations using wave-packet propagations on a numerical grid. The transition-probability expression incorporating a high-frequency quantum mode and low-frequency medium mode is compared for Morse and harmonic oscillators in different temperature ranges and with various coarse-graining treatments of the delta function from the Fermi golden rule expression. We find that significant deviations from the harmonic approximation are expected for even moderately anharmonic quantum modes at large values of exoergicity. The addition of a second quantum mode of opposite displacement negates the anharmonic effect at small energy change, but in the inverted regime a significantly flatter dependence on exoergicity is predicted for anharmonic modes.

Journal Article↗
PubMed1996

Stochastic comparison of processes generated by random interruptions of monotone functions and related results.

Many stochastic processes considered in applied probability models, and, in particular, in reliability theory, are processes of the following form: Shocks occur according to some point process, and each shock causes the process to have a random jump. Between shocks the process increases or decreases in some deterministic fashion. In this paper we study processes for which the rate of increase or decrease between shocks depends only on the height of the process. For such processes we find conditions under which the processes can be stochastically compared. We also study 'hybrid' processes in which periods of increase and periods of decrease alternate. A further result yields a stochastic comparison of processes that start with a random jump, rather than processes in which there is at the beginning some random delay time before the first jump.

Life Tables↗
PubMed1986

Flow-induced anisotropy in the susceptibility of a particle suspension.

The initial susceptibility, or low-field high-frequency permeability, of a rod-like particle suspension or polymer solution can become anisotropic when the particles or molecules interact with a magnetic field in a directional manner and are nonrandomly oriented by certain types of flow field. This is the alignment that leads to thixotropy and deviatoric stresses during rheological measurements on these fluids. A general expression for the particle order parameter and the fluid permeability in terms of Legendre polynomials is derived by calculating the ensemble average over all possible orientation angles. This is an integral containing the orientation angle-dependent orientation probability function. The example case of single-domain magnetic particles suspended in extensional flow of a newtonian fluid is examined by using the following well-known models: chain-of-spheres model for the magnetic properties of a particle and the Kirkwood-Auer theory for the orientation probability function. From this, the particle orientation in the flow direction downstream from a sharp circular convergence is predicted to dramatically increase with an increase in the ratio of the extension rate to the particle rotary diffusion coefficient. Consequently, the measured permeability of the fluid is predicted to decrease parallel to, and to increase perpendicular to, the flow direction.

Journal Article↗
PubMed2005

Probability densities of periodically driven noisy systems: an approximation scheme incorporating linear-response and adiabatic theory.

We consider periodically driven noisy systems in the limit of long times. To deduce their asymptotic time-periodic probability distributions, two approaches are commonly used: adiabatic theory, valid if driving is very slow, and linear-response theory, applicable when driving is weak. We introduce an approximation scheme that combines these two approaches to yield the driven probability distribution even when driving is strong and moderately fast, so that both linear-response and adiabatic approximations break down. The high accuracy of this scheme is demonstrated on a driven overdamped noisy oscillator in a bistable quartic potential.

Journal Article↗
PubMed1983

The current status of the psychoanalytic theory of instinctual drives. I: Drive concept, classification, and development.

The evolution of Freud's theory of instinctual drives, with the accompanying models of a mental apparatus, is remarkable for its tenacious adherence to addressing the fundamental problems of human psychology, here phrased as the problems of body-mind-environment relationships. The concept of instinctual drives continues to be one of the most pervasive concepts of psychoanalysis, weathering considerable attack over the last several decades, although losing some clarity in the process. I have cited and discussed as basic issues of the concept of instinctual drives: the relationship of observational data and theoretical constructs in psychology; whether our construct of drives is or should be or can be purely psychological; the problem of conceptualizing the ontogenetic origin of mind; the issues of the "force-meaning conjunction" and the problem of psychic energy in psychoanalytic constructs; and the relation of our concept of instinctual drives to the concept of instincts in general. It seems that progress with these fundamental issues might be made by utilizing models that are more homologous with present knowledge in related fields than is Freud's reflex arc model of the nervous system, in order to build a better drive construct within the framework of psychoanalysis. The classification of instinctual drives remains a problem. Clinically, aggression seems to be a factor in conflict, very much like sexuality. Despite widespread acceptance of the idea of aggression as simply parallel to sexuality in all respects, there are major discrepancies. Perhaps aggression cannot be viewed as a drive after all; perhaps our drive construct needs to be modified to accommodate aggression. Certainly, controversy in this area has interfered with the production of good clinical studies which could begin to increase our understanding of aggression and its place in the human personality. The psychoanalytic theory of drive development has probably undergone less change in the last forty years than other aspects of drive theory, although careful observational work has led to alterations of our views of the age of onset of genital awareness, of female sexual development and function, and of the latency period. This is the conclusion of the first of two papers examining the post-Freud development of the theory of instinctual drives in psychoanalysis. The companion paper follows on p. 402 of this issue of The Psychoanalytic Quarterly.

Aggression↗
PubMed1994

Effect of preheating on potato texture.

Preheating potatoes at 50 to 80 degrees C has a firming effect on the cooked potato tissue. This effect is particularly pronounced at a preheating temperature of 60 to 70 degrees C followed by cooling. Several theories have been presented in the literature to explain this firming effect: retrogradation of starch, leaching of amylose, stabilization of the middle lamellae and cell walls by the activation of the pectin methylesterase (PME) enzyme, and by the release of calcium from gelatinized starch and the formation of calcium bridges between pectin molecules. Most probably, none of these theories alone can explain the phenomenon and more than one mechanism seems to be involved. Some of these mechanisms seem to be interdependent. As an example, calcium could be considered as a link all the way through release after starch gelatinization to cross-linking pectin substances in the cell wall and the middle lamellae, which has been demethylated by the PME enzyme. More research and "clear cut" experiments are needed in order to elucidate the role of each mechanism, especially which of them is the main contributor to the process of firming. Most probably, the calcium-pectin-PME mechanism plays a secondary role, that is, it only retards the collapse of the tissue structure that would otherwise occur during the final heating without preheating, and it is not the main factor of firmness.

Carboxylic Ester Hydrolases↗
PubMedDate not supplied

Probability judgement in medicine: discounting unspecified possibilities.

Research in cognitive psychology has indicated that alternative descriptions of the same event can give rise to different probability judgments. This observation has led to the development of a descriptive account, called support theory, which assumes that the judged probability of an explicit description of an event (that lists specific possibilities) generally exceeds the judged probability of an implicit description of the same event (that does not mention specific possibilities). To investigate this assumption in medical judgment, the authors presented physicians with brief clinical scenarios describing individual patients and elicited diagnostic and prognostic probability judgments. The results showed that the physicians tended to discount unspecified possibilities, as predicted by support theory. The authors suggest that an awareness of the discrepancy between intuitive judgments and the laws of chance may provide opportunities for improving medical decision making.

Bias↗
PubMed2003

Prospect relativity: how choice options influence decision under risk.

In many theories of decision under risk (e.g., expected utility theory, rank-dependent utility theory, and prospect theory), the utility of a prospect is independent of other options in the choice set. The experiments presented here show a large effect of the available options, suggesting instead that prospects are valued relative to one another. The judged certainty equivalent for a prospect is strongly influenced by the options available. Similarly, the selection of a preferred prospect is strongly influenced by the prospects available. Alternative theories of decision under risk (e.g., the stochastic difference model, multialternative decision field theory, and range frequency theory), where prospects are valued relative to one another, can provide an account of these context effects.

Adolescent↗
PubMed1992

Stumpf's cognitive--evaluative theory of emotion.

As a historical contribution to the current cognition-emotion debate in psychology, this article seeks (a) to bring to the readers' attention the largely ignored tradition of cognitive emotion theory within introspective psychology by reviewing what is probably the most clearly formulated cognitive emotion theory of this period, that proposed by Carl Stumpf, and (b) to point out the relevance of Stumpf's contributions to the psychology of emotions for the contemporary cognition-emotion discussion. It is suggested that Stumpf's version of a cognitive-evaluative theory of emotion deserves the serious attention of contemporary investigators and that several of his objections to noncognitive theories of emotion retain their force against modern versions of these theories.

Cognition↗
PubMed2006

A Dirichlet process model for detecting positive selection in protein-coding DNA sequences.

Most methods for detecting Darwinian natural selection at the molecular level rely on estimating the rates or numbers of nonsynonymous and synonymous changes in an alignment of protein-coding DNA sequences. In some of these methods, the nonsynonymous rate of substitution is allowed to vary across the sequence, permitting the identification of single amino acid positions that are under positive natural selection. However, it is unclear which probability distribution should be used to describe how the nonsynonymous rate of substitution varies across the sequence. One widely used solution is to model variation in the nonsynonymous rate across the sequence as a mixture of several discrete or continuous probability distributions. Unfortunately, there is little population genetics theory to inform us of the appropriate probability distribution for among-site variation in the nonsynonymous rate of substitution. Here, we describe an approach to modeling variation in the nonsynonymous rate of substitution by using a Dirichlet process mixture model. The Dirichlet process allows there to be a countably infinite number of nonsynonymous rate classes and is very flexible in accommodating different potential distributions for the nonsynonymous rate of substitution. We implemented the model in a fully Bayesian approach, with all parameters of the model considered as random variables.

Animals↗
PubMedDate not supplied

Improved estimation of the ranking probabilities in partial orders using random linear extensions by approximation of the mutual ranking probability.

The application of partial order theory and Hasse diagram technique in environmental science is getting increasing attention. One of the latest developments in the field of Hasse diagram technique is the use of random linear extensions to estimate ranking probabilities. In the original algorithm for estimating the ranking probability it is assumed that the order between two incomparable pair of objects can be chosen randomly. However, if the total set of linear extensions is considered there is a specific probability that one object will be larger than another, which can be far from 50%. In this study it is investigated if an approximation of the mutual ranking probability can improve the algorithm. Applying an approximation of the mutual ranking probability the estimation of the ranking probabilities are significantly improved. Using a test set of 39 partial orders with randomly chosen values the relative mean root square difference (MRSD) decrease in average from 7.9% to 2.2% and a maximum relative improvement of 90% can be found. In the most successful case the relative MRSD goes as low as 0.77%.

Journal Article↗
PubMed2000

The biochemistry of aging.

Although philosophers and scientists have long been interested in the aging process, general interest in this fascinating and highly important topic was minimal before the 1960s. In recent decades, however, interest in aging has greatly accelerated, not only since the elderly form an ever-increasing percentage of the population, but because they utilize a significant proportion of the national expenditures. In addition, many people have come to the realization that one can now lead a very happy, active, and productive life well beyond the usual retirement age. Scientifically, aging is an extremely complex, multifactorial process, and numerous aging theories have been proposed; the most important of these are probably the genomic and free radical theories. Although it is abundantly clear that our genes influence aging and longevity, exactly how this takes place on a chemical level is only partially understood. For example, what kinds of genes are these, and what proteins do they control? Certainly they include, among others, those that regulate the processes of somatic maintenance and repair, such as the stress-response systems. The accelerated aging syndromes (i.e., Hutchinson-Gilford, Werner's, and Down's syndromes) are genetically controlled, and studies of them have decidedly increased our understanding of aging. In addition, C. elegans and D. melanogaster are important systems for studying aging. This is especially true for the former, in which the age-1 mutant has been shown to greatly increase the life span over the wild-type strain. This genetic mutation results in increased activities of the antioxidative enzymes, Cu-Zn superoxide dismutase and catalase. Thus, the genomic and free radical theories are closely linked. In addition, trisomy 21 (Down's syndrome) is characterized by a significantly shortened life span; it is also plagued by increased oxidative stress which results in various free radical-related disturbances. Exactly how this extra chromosome results in an increased production of reactive oxygen species is, however, only partially understood. There is considerable additional indirect evidence supporting the free radical theory of aging. Not only are several major age-associated diseases clearly affected by increased oxidative stress (atherosclerosis, cancer, etc.), but the fact that there are numerous natural protective mechanisms to prevent oxyradical-induced cellular damage speaks loudly that this theory has a key role in aging [the presence of superoxide dismutase, catalase, glutathione peroxidase, and glutathione reductase, among others; various important intrinsic (uric acid, bilirubin, -SH proteins, glutathione, etc.) and extrinsic (vitamins C, E, carotenoids, flavonoids, etc.) antioxidants; and metal chelating proteins to prevent Fenton and Haber-Weiss chemistry]. In addition, a major part of the free radical theory involves the damaging role of reactive oxygen species and various toxins on mitochondria. These lead to numerous mitochondrial DNA mutations which result in a progressive reduction in energy output, significantly below that needed in body tissues. This can result in various signs of aging, such as loss of memory, hearing, vision, and stamina. Oxidative stress also inactivates critical enzymes and other proteins. In addition to these factors, caloric restriction is the only known method that increases the life span of rodents; studies currently underway suggest that this also applies to primates, and presumably to humans. Certainly, oxidative stress plays an important role here, although other, as yet unknown, factors are also presumably involved. Exactly how the other major theories (i.e., immune, neuroendocrine, somatic mutation, error catastrophe) control aging is more difficult to define. The immune and neuroendocrine systems clearly deteriorate with age. (ABSTRACT TRUNCATED)

Aging↗
PubMed1997

A method to determine activation thresholds in fMRI paradigms.

Determining meaningful activation thresholds in functional magnetic resonance imaging (fMRI) paradigms is complicated by several factors. These include the time-series nature of the data, the influence of physiological rhythms (e.g. respiration) and vacillations introduced by the experimental design (e.g. cueing). We present an empirical threshold for each subject and each fMRI experiment that takes these factors into account. The method requires an additional fMRI data set as similar to the experimental paradigm as possible without dichotomously varying the experimental task of interest. A letter fluency task was used to illustrate this method. This technique differs from classical methods since the Pearson correlation probability values tabulated from statistical theory are not used. Rather each subject defines his or her own set of threshold probability values for correlations. It is against these empirical thresholds, not Pearson's, that an experimental fMRI correlation is assessed.

Adult↗
PubMed1984

Alpha-adrenergic blockade in the diagnosis of detrusor instability secondary to infravesical obstruction.

Detrusor instability secondary to infravesical obstruction is probably caused by overactive stretch receptors in the bladder wall. Since recent studies have shown that alpha-adrenergic blockade with phenoxybenzamine reduces the intravesical pressure under micturition, we undertook this investigation in order to see if phenoxybenzamine has an effect on detrusor instability caused by infravesical obstruction. We found that the detrusor instability was abolished by phenoxybenzamine, which supports the 'stretch receptor theory'. Further, phenoxybenzamine is probably a good test in the diagnosis of detrusor instability secondary to infravesical obstruction.

Aged↗
PubMed2005

Wall-fluid and liquid-gas interfaces of model colloid-polymer mixtures by simulation and theory.

We perform a study of the interfacial properties of a model suspension of hard sphere colloids with diameter sigma(c) and nonadsorbing ideal polymer coils with diameter sigma(p) . For the mixture in contact with a planar hard wall, we obtain from simulations the wall-fluid interfacial free energy, gamma(wf) , for size ratios q =sigma(p)/sigma(c) =0.6 and 1, using thermodynamic integration, and study the (excess) adsorption of colloids, Gamma(c) , and of polymers, Gamma(p) , at the hard wall. The interfacial tension of the free liquid-gas interface, gamma(lg) , is obtained following three different routes in simulations: (i) from studying the system size dependence of the interfacial width according to the predictions of capillary wave theory, (ii) from the probability distribution of the colloid density at coexistence in the grand canonical ensemble, and (iii) for state points where the colloidal liquid wets the wall completely, from Young's equation relating gamma(lg) to the difference of wall-liquid and wall-gas interfacial tensions, gamma(wl)-gamma(wg) . In addition, we calculate gamma(wf) ,Gamma(c) , and Gamma(p) using density functional theory and a scaled particle theory based on free volume theory. Good agreement is found between the simulation results and those from density functional theory, while the results from scaled particle theory quantitatively deviate but reproduce some essential features. Simulation results for gamma(lg) obtained from the three different routes are all in good agreement. Density functional theory predicts gamma(lg) with good accuracy for high polymer reservoir packing fractions, but yields deviations from the simulation results close to the critical point.

Journal Article↗
PubMed1991

Probabilistic secretion of quanta in the central nervous system: granule cell synaptic control of pattern separation and activity regulation.

The implications of probabilistic secretion of quanta for the functioning of neural networks in the central nervous system have been explored. A model of stochastic secretion at synapses in simple networks, consisting of large numbers of granule cells and a relatively small number of inhibitory interneurons, has been analysed. Such networks occur in the input to the cerebellum Purkinje cells as well as to hippocampal CA3 pyramidal cells and to pyramidal cells in the visual cortex. In this model the input axons terminate on granule cells as well as on an inhibitory interneuron that projects to the granule cells. Stochastic secretion at these synapses involves both temporal variability in secretion at single synapses in the network as well as spatial variability in the secretion at different synapses. The role of this stochastic variability in controlling the size of the granule cell output to a level independent of the size of the input and in separating overlapping inputs has been determined analytically as well as by simulation. The regulation of granule-cell output activity to a reasonably constant value for different size inputs does not occur in the absence of an inhibitory interneuron when both spatial and temporal stochastic variability occurs at the remaining synapses; it is still very poor in the presence of such an interneuron but in the absence of stochastic variability. However, quite good regulation is achieved when the inhibitory interneuron is present with spatial and temporal stochastic variability of secretion at synapses in the network. Excellent regulation is achieved if, in addition, allowance is made for the nonlinear behaviour of the input-output characteristics of inhibitory interneurons. The capacity of granule-cell networks to separate overlapping patterns of activity on their inputs is adequate, with spatial variability in the secretion at synapses, but is improved if there is also temporal variability in the stochastic secretion at individual synapses, although this is at the expense of reliability in the network. Other factors which improve pattern separation are control of the output to very low activity levels, and a restriction on the cumulative size of the excitatory input terminals of each granule cell. Application of the theory to the input neural networks of the cerebellum and the hippocampus shows the role of stochastic variability in quantal transmission in determining the capacity of these networks for pattern separation and activity regulation.

Animals↗
PubMed1989

Probability and sampling.

The concept of probability is introduced, and the role of probability distributions in statistical theory is discussed, with particular reference to the Normal distribution and its characteristics. Sampling and sampling variation are described, together with sampling error, the standard error of the mean, and confidence intervals for determining the likely magnitude of a population mean.

Child↗