Photochemical electron transfer at fixed distance : a synthetic model of the photosynthetic primary process

A series of meso-phenyloctamethylporphyrins covalently bonded at the 4'phenyl position to quinones via rigid bicyclo[2.2.2]octane spacers were synthesized for the study of the dependence of electron transfer reaction rate on solvent, distance, temperature, and energy gap. A general and convergent synthesis was developed based on the condensation of ac-biladienes with masked quinonespacer-benzaldehydes. From picosecond fluorescence spectroscopy emission lifetimes were measured in seven solvents of varying polarity. Rate constants were determined to vary from 5.0x10⁹sec^-1 in N,N-dimethylformamide to 1.15x10¹⁰ Sec^-1 in benzene, and were observed to rise at most by about a factor of three with decreasing solvent polarity. Experiments at low temperature in 2-MTHF glass (77K) revealed fast, nearly temperature-independent electron transfer characterized by non-exponential fluorescence decays, in contrast to monophasic behavior in fluid solution at 298K. This example evidently represents the first photosynthetic model system not based on proteins to display nearly temperature-independent electron transfer at high temperatures (nuclear tunneling). Low temperatures appear to freeze out the rotational motion of the chromophores, and the observed nonexponential fluorescence decays may be explained as a result of electron transfer from an ensemble of rotational conformations. The nonexponentiality demonstrates the sensitivity of the electron transfer rate to the precise magnitude of the electronic matrix element, which supports the expectation that electron transfer is nonadiabatic in this system. The addition of a second bicyclooctane moiety (15 Å vs. 18 Å edge-to-edge between porphyrin and quinone) reduces the transfer rate by at least a factor of 500-1500. Porphyrinquinones with variously substituted quinones allowed an examination of the dependence of the electron transfer rate constant κ_ET on reaction driving force. The classical trend of increasing rate versus increasing exothermicity occurs from 0.7 eV≤ |ΔG^0'(R)| ≤ 1.0 eV until a maximum is reached (κ_ET = 3 x 10⁸ sec^-1 rising to 1.15 x 10¹⁰ sec^-1 in acetonitrile). The rate remains insensitive to ΔG⁰ for ~ 300 mV from 1.0 eV≤ |ΔG^0’(R)| ≤ 1.3 eV, and then slightly decreases in the most exothermic case studied (cyanoquinone, κ_ET = 5 x 10⁹ sec^-1).

The far-field spatial coherence of Gaussian Schell-model beam in turbulence in terms of position vectors

Spatial coherence properties of beam produced by Gaussian Schell-model source when the beam is propagating through atmosphere have been analyzed in terms of position vectors. New expressions for cross-spectral density of optical field and spectral degree of coherence as well as radiant intensity have been developed. Numerical results illustrated in this paper indicate the coherence degradation suffered from atmospheric turbulence and their directional dependence. (C) 2007 Elsevier GmbH. All rights reserved.

Active reservoir management: a model solution

Steady-state procedures, of their very nature, cannot deal with dynamic situations. Statistical models require extensive calibration, and predictions often have to be made for environmental conditions which are often outside the original calibration conditions. In addition, the calibration requirement makes them difficult to transfer to other lakes. To date, no computer programs have been developed which will successfully predict changes in species of algae. The obvious solution to these limitations is to apply our limnological knowledge to the problem and develop functional models, so reducing the requirement for such rigorous calibration. Reynolds has proposed a model, based on fundamental principles of algal response to environmental events, which has successfully recreated the maximum observed biomass, the timing of events and a fair simulation of the species succession in several lakes. A forerunner of this model was developed jointly with Welsh Water under contract to Messrs. Wallace Evans and Partners, for use in the Cardiff Bay Barrage study. In this paper the authors test a much developed form of this original model against a more complex data-set and, using a simple example, show how it can be applied as an aid in the choice of management strategy for the reduction of problems caused by eutrophication. Some further developments of the model are indicated.

Tsunamis - a model of their generation and propagation

A general solution is presented for water waves generated by an arbitrary movement of the bed (in space and time) in a two-dimensional fluid domain with a uniform depth. The integral solution which is developed is based on a linearized approximation to the complete (nonlinear) set of governing equations. The general solution is evaluated for the specific case of a uniform upthrust or downthrow of a block section of the bed; two time-displacement histories of the bed movement are considered.

An integral solution (based on a linear theory) is also developed for a three-dimensional fluid domain of uniform depth for a class of bed movements which are axially symmetric. The integral solution is evaluated for the specific case of a block upthrust or downthrow of a section of the bed, circular in planform, with a time-displacement history identical to one of the motions used in the two-dimensional model.

Since the linear solutions are developed from a linearized approximation of the complete nonlinear description of wave behavior, the applicability of these solutions is investigated. Two types of non-linear effects are found which limit the applicability of the linear theory: (1) large nonlinear effects which occur in the region of generation during the bed movement, and (2) the gradual growth of nonlinear effects during wave propagation.

A model of wave behavior, which includes, in an approximate manner, both linear and nonlinear effects is presented for computing wave profiles after the linear theory has become invalid due to the growth of nonlinearities during wave propagation.

An experimental program has been conducted to confirm both the linear model for the two-dimensional fluid domain and the strategy suggested for determining wave profiles during propagation after the linear theory becomes invalid. The effect of a more general time-displacement history of the moving bed than those employed in the theoretical models is also investigated experimentally.

The linear theory is found to accurately approximate the wave behavior in the region of generation whenever the total displacement of the bed is much less than the water depth. Curves are developed and confirmed by the experiments which predict gross features of the lead wave propagating from the region of generation once the values of certain nondimensional parameters (which characterize the generation process) are known. For example, the maximum amplitude of the lead wave propagating from the region of generation has been found to never exceed approximately one-half of the total bed displacement. The gross features of the tsunami resulting from the Alaskan earthquake of 27 March 1964 can be estimated from the results of this study.

A model of the pelagic ecossystem in the eastern tropical Pacific Ocean

English: Recent calls for a more holistic approach to fisheries management have motivated development of trophic mass-balance models of ecosystems that underlie fisheries production. We developed a model hypothesis of the pelagic ecosystem in the eastern tropical Pacific Ocean (ETP) to gain insight into the relationships among the various species in the system and to explore the ecological implications of alternative methods of harvesting tunas. We represented the biomasses of and fluxes between the principal elements in the ecosystem with Ecopath, and examined the ecosystem's dynamic, time-series behavior with Ecosim. We parameterized the model for 38 species or groups of species, and described the sources, justifications, assumptions, and revisions of our estimates of the various parameters, diet relations, fisheries landings, and fisheries discards in the model. We conducted sensitivity analyses with an intermediate version of the model, for both the Ecopath mass-balance and the dynamic trajectories predicted by Ecosim. The analysis showed that changes in the basic parameters for two components at middle trophic levels, Cephalopods and Auxis spp., exert the greatest influence on the system. When the Cephalopod Q/B and Auxis spp. P/B were altered from their initial values and the model was rebalanced, the trends of the biomass trajectories predicted by Ecosim were not sensitive, but the scaling was sensitive for several components. We described the review process the model was subjected to, which included reviews by the IATTC Purse-seine Bycatch Working Group and by a working group supported by the National Center for Ecological Analysis and Synthesis. We fitted the model to historical time series of catches per unit of effort and mortality rates for yellowfin and bigeye tunas in simulations that incorporated historical fishing effort and a climate driver to represent the effect of El Niño-Southern Oscillation-scale variation on the system. The model was designed to evaluate the possible ecological implications of fishing for tunas in various ways. We recognize that a model cannot possibly represent all the complexity of a pelagic ocean ecosystem, but we believe that the ETP model provides insight into the structure and function of the pelagic ETP. Spanish: Llamamientos recientes hacia un enfoque más holístico al ordenamiento de la pesca han motivado el desarrollo de modelos tróficos de balance de masas de los ecosistemas que sostienen la producción pesquera. Desarrollamos una hipótesis modelo del ecosistema pelágico en el Océano Pacífico oriental tropical (POT) con miras a mejorar los conocimientos de las relaciones entre las distintas especies en el sistema y explorar las implicaciones ecológicas de métodos alternativos de capturar atunes. Con Ecopath representamos las biomasas de los elementos principales en el ecosistema, y los flujos entre los mismos, y con Ecosim examinamos el comportamiento dinámico del ecosistema con el tiempo. Parametrizamos el modelo para 38 especies o grupos de especies (denominados “componentes” del modelo), y describimos las fuentes, justificaciones, supuestos, y revisiones de nuestras estimaciones de los distintos parámetros, relaciones basadas en dieta, capturas retenidas de las pesquerías, y descartes de las mismas en el modelo. Realizamos análisis de sensibilidad con una versión intermedia del modelo, para el balance de masas de Ecopath y las trayectorias dinámicas predichas por Ecosim también. El análisis demostró que cambios en los parámetros básicos para dos componentes en niveles tróficos medianos, Cefalópodos y Auxis spp., ejercieron la mayor influencia sobre el sistema. Cuando se alteraron el Q/B de los Cefalópodos y el P/B de los Auxis spp. de sus valores iniciales y se balanceó el modelo de nuevo, las tendencias de las trayectorias de la biomasa predichas por Ecosim no fueron sensibles, pero la escala fue sensible para varios componentes. Describimos el proceso de revisión al que fue sujeto el modelo, inclusive revisiones por el Grupo de Trabajo sobre Captura Incidental de la CIAT y un grupo de trabajo apoyado por el Centro Nacional para Síntesis y Análisis Ecológicos. Ajustamos el modelo a series de tiempo históricas de capturas por unidad de esfuerzo y tasas de mortalidad de atunes aleta amarilla y patudo en simulaciones que incorporaron esfuerzo de pesca histórico e impulsos climáticos para representar el efecto de variaciones a escala de El Niño-Oscilación del Sur sobre el sistema. El modelo fue diseñado para evaluar las posibles implicaciones ecológicas de la pesca atunera de varias formas. Reconocemos la imposibilidad de que el modelo represente toda la complejidad de un ecosistema oceánico pelágico, pero creemos que el modelo del POT mejora los conocimientos de la estructura y función del POT pelágico.

Observational constraints on the unified dark matter and dark energy model based on the quark bag model

In this work we investigate if a small fraction of quarks and gluons, which escaped hadronization and survived as a uniformly spread perfect fluid, can play the role of both dark matter and dark energy. This fluid, as developed in [1], is characterized by two main parameters: beta, related to the amount of quarks and gluons which act as dark matter; and gamma, acting as the cosmological constant. We explore the feasibility of this model at cosmological scales using data from type Ia Supernovae (SNeIa), Long Gamma-Ray Bursts (LGRB) and direct observational Hubble data. We find that: (i) in general, beta cannot be constrained by SNeIa data nor by LGRB or H(z) data; (ii) gamma can be constrained quite well by all three data sets, contributing with approximate to 78% to the energy matter content; (iii) when a strong prior on (only) baryonic matter is assumed, the two parameters of the model are constrained successfully. (C) 2014 The Authors. Published by Elsevier B.V.

A behavior model for blood donors and marketing strategies to retain and attract them

Objective: analyze and propose a theoretical model that describes blood donor decisions to help staff working in blood banks (nurses and others) in their efforts to capture and retain donors. Methods: analysis of several studies on the motivations to give blood in Spain over the last six years, as well as past literature on the topic, the authors' experiences in the last 25 years in over 15 Non Governmental Organizations with different levels of responsibilities, their experiences as blood donors and the informal interviews developed during those 25 years. Results: a model is proposed with different internal and external factors that influence blood donation, as well as the different stages of the decision-making process. Conclusion: the knowledge of the donation process permits the development of marketing strategies that help to increase donors and donations.

Using experiments and expert judgment to model catchability of Pacific rockfishes in trawl surveys, with application to bocaccio (Sebastes paucispinis) off British Columbia

The time series of abundance indices for many groundfish populations, as determined from trawl surveys, are often imprecise and short, causing stock assessment estimates of abundance to be imprecise. To improve precision, prior probability distributions (priors) have been developed for parameters in stock assessment models by using meta-analysis, expert judgment on catchability, and empirically based modeling. This article presents a synthetic approach for formulating priors for rockfish trawl survey catchability (qgross). A multivariate prior for qgross for different surveys is formulated by using 1) a correction factor for bias in estimating fish density between trawlable and untrawlable areas, 2) expert judgment on trawl net catchability, 3) observations from trawl survey experiments, and 4) data on the fraction of population biomass in each of the areas surveyed. The method is illustrated by using bocaccio (Sebastes paucipinis) in British Columbia. Results indicate that expert judgment can be updated markedly by observing the catch-rate ratio from different trawl gears in the same areas. The marginal priors for qgross are consistent with empirical estimates obtained by fitting a stock assessment model to the survey data under a noninformative prior for qgross. Despite high prior uncertainty (prior coefficients of variation ≥0.8) and high prior correlation between qgross, the prior for qgross still enhances the precision of key stock assessment quantities.

Defining plausible migration rates based on historical tagging data: a Bayesian mark-recapture model applied to English sole (Parophrys vetulus)

A generalized Bayesian population dynamics model was developed for analysis of historical mark-recapture studies. The Bayesian approach builds upon existing maximum likelihood methods and is useful when substantial uncertainties exist in the data or little information is available about auxiliary parameters such as tag loss and reporting rates. Movement rates are obtained through Markov-chain Monte-Carlo (MCMC) simulation, which are suitable for use as input in subsequent stock assessment analysis. The mark-recapture model was applied to English sole (Parophrys vetulus) off the west coast of the United States and Canada and migration rates were estimated to be 2% per month to the north and 4% per month to the south. These posterior parameter distributions and the Bayesian framework for comparing hypotheses can guide fishery scientists in structuring the spatial and temporal complexity of future analyses of this kind. This approach could be easily generalized for application to other species and more data-rich fishery analyses.

A catch-free stock assessment model with application to goliath grouper (Epinephelus itajara) off southern Florida

Many modern stock assessment methods provide the machinery for determining the status of a stock in relation to certain reference points and for estimating how quickly a stock can be rebuilt. However, these methods typically require catch data, which are not always available. We introduce a model-based framework for estimating reference points, stock status, and recovery times in situations where catch data and other measures of absolute abundance are unavailable. The specif ic estimator developed is essentially an age-structured production model recast in terms relative to pre-exploitation levels. A Bayesian estimation scheme is adopted to allow the incorporation of pertinent auxiliary information such as might be obtained from meta-analyses of similar stocks or anecdotal observations. The approach is applied to the population of goliath grouper (Epinephelus itajara) off southern Florida, for which there are three indices of relative abundance but no reliable catch data. The results confirm anecdotal accounts of a marked decline in abundance during the 1980s followed by a substantial increase after the harvest of goliath grouper was banned in 1990. The ban appears to have reduced fishing pressure to between 10% and 50% of the levels observed during the 1980s. Nevertheless, the predicted fishing mortality rate under the ban appears to remain substantial, perhaps owing to illegal harvest and depth-related release mortality. As a result, the base model predicts that there is less than a 40% chance that the spawning biomass will recover to a level that would produce a 50% spawning potential ratio.

Low Effort L-i Nuclear Fusion Plasma Control Using Model Predictive Control Laws

One of the main problems of fusion energy is to achieve longer pulse duration by avoiding the premature reaction decay due to plasma instabilities. The control of the plasma inductance arises as an essential tool for the successful operation of tokamak fusion reactors in order to overcome stability issues as well as the new challenges specific to advanced scenarios operation. In this sense, given that advanced tokamaks will suffer from limited power available from noninductive current drive actuators, the transformer primary coil could assist in reducing the power requirements of the noninductive current drive sources needed for current profile control. Therefore, tokamak operation may benefit from advanced control laws beyond the traditionally used PID schemes by reducing instabilities while guaranteeing the tokamak integrity. In this paper, a novel model predictive control (MPC) scheme has been developed and successfully employed to optimize both current and internal inductance of the plasma, which influences the L-H transition timing, the density peaking, and pedestal pressure. Results show that the internal inductance and current profiles can be adequately controlled while maintaining the minimal control action required in tokamak operation.

Toward a Model for Fisheries Social Impact Assessment

This paper presents a model for Fisheries Social Impact Assessment (SIA) that lays the groundwork for development of fisheries-focused, quantitative social assessments with a clear conceptual model. The usefulness of current fisheries SIA’s has been called into question by some as incompatible with approaches taken by fisheries biologists and economists when assessing potential effects of management actions. Our model’s approach is closer to the economists’ and biologists’ assessments and is therefore more useful for Fishery Management Council members. The paper was developed by anthropologists initially brought together in 2004 for an SIA Modeling Workshop by the National Marine Fisheries Service, NOAA. Opinions and conclusions expressed or implied are solely those of the authors and do not necessarily reflect the views or policy of the National Marine Fisheries Service, NOAA.

Development and experimental validation of a mathematical model for friction between fabrics and a volar forearm phantom.

An analytical mathematical model for friction between a fabric strip and the volar forearm has been developed and validated experimentally. The model generalizes the common assumption of a cylindrical arm to any convex prism, and makes predictions for pressure and tension based on Amontons' law. This includes a relationship between the coefficient of static friction (mu) and forces on either end of a fabric strip in contact with part of the surface of the arm and perpendicular to its axis. Coefficients of friction were determined from experiments between arm phantoms of circular and elliptical cross-section (made from Plaster of Paris covered in Neoprene) and a nonwoven fabric. As predicted by the model, all values of mu calculated from experimental results agreed within +/- 8 per cent, and showed very little systematic variation with the deadweight, geometry, or arc of contact used. With an appropriate choice of coordinates the relationship predicted by this model for forces on either end of a fabric strip reduces to the prediction from the common model for circular arms. This helps to explain the surprisingly accurate values of mu obtained by applying the cylindrical model to experimental data on real arms.

An extended computational model of the circulatory system for designing ventricular assist devices.

An extended computational model of the circulatory system has been developed to predict blood flow in the presence of ventricular assist devices (VADs). A novel VAD, placed in the descending aorta, intended to offload the left ventricle (LV) and augment renal perfusion is being studied. For this application, a better understanding of the global hemodynamic response of the VAD, in essence an electrically driven pump, and the cardiovascular system is necessary. To meet this need, a model has been established as a nonlinear, lumped-parameter electrical analog, and simulated results under different states [healthy, congestive heart failure (CHF), and postinsertion of VAD] are presented. The systemic circulation is separated into five compartments and the descending aorta is composed of three components to accurately yield the system response of each section before and after the insertion of the VAD. Delays in valve closing time and blood inertia in the aorta were introduced to deliver a more realistic model. Pump governing equations and optimization are based on fundamental theories of turbomachines and can serve as a practical initial design point for rotary blood pumps. The model's results closely mimic established parameters for the circulatory system and confirm the feasibility of the intra-aortic VAD concept. This computational model can be linked with models of the pump motor to provide a valuable tool for innovative VAD design.

A habitat-use model to determine essential fish habitat for juvenile brown shrimp (Farfantepenaeus aztecus) in Galveston Bay, Texas

A density prediction model for juvenile brown shrimp (Farfantepenaeus aztecus) was developed by using three bottom types, five salinity zones, and four seasons to quantify patterns of habitat use in Galveston Bay, Texas. Sixteen years of quantitative density data were used. Bottom types were vegetated marsh edge, submerged aquatic vegetation, and shallow nonvegetated bottom. Multiple regression was used to develop density estimates, and the resultant formula was then coupled with a geographical information system (GIS) to provide a spatial mosaic (map) of predicted habitat use. Results indicated that juvenile brown shrimp (<100 mm) selected vegetated habitats in salinities of 15−25 ppt and that seagrasses were selected over marsh edge where they co-occurred. Our results provide a spatially resolved estimate of high-density areas that will help designate essential fish habitat (EFH) in Galveston Bay. In addition, using this modeling technique, we were able to provide an estimate of the overall population of juvenile brown shrimp (<100 mm) in shallow water habitats within the bay of approximately 1.3 billion. Furthermore, the geographic range of the model was assessed by plotting observed (actual) versus expected (model) brown shrimp densities in three other Texas bays. Similar habitat-use patterns were observed in all three bays—each having a coefficient of determination >0.50. These results indicate that this model may have a broader geographic application and is a plausible approach in refining current EFH designations for all Gulf of Mexico estuaries with similar geomorphological and hydrological characteristics.