A simple computational model for predicting .pi.-facial selectivity in reductions of sterically unbiased ketones. Relative importance of electrostatic and orbital interactions

Various factore controlling the preferred facial selectivity in the reductions of a number of sterically unbiased ketones have been evaluated using a semiempirical MO procedure. MNDO optimized geometries do not reveal any significant ground-state distortions which can be correlated with the observed face selectivities. Electrostatic effecta due to an approaching reagent were modeled by placing a test negative charge at a fixed distance from the carbonyl carbon on each of the two faces. A second series of calculations was carried out using the hydride ion as a test nucleophile. The latter calculations effectively include orbital interactions involving the u and u* orbitals of the newly formed bond in the reaction. The computed energy differences with the charge model are generally much larger compared to those with the hydride ion. However, both models lead to predictions which are qualitatively consistent with the experimentally determined facial preferences for most of the systems. Thus, electrostatic interactions between the nucleophile and the substrate seem to effectively determine the face selectivities in these molecules. However, there are a few exceptions in which orbital interactions are found to contribute significantly and occasionally reverse the preference dictated by electrostatic effecta. The remarkable succew of the hydride model calculations, in spite of retaining the unperturbed geometries of the substrates, points to the unimportance of torsional effeds and orbital distortions associated with the pyramidalized carbonyl unit in the transition state in most of the substrates considered. Additional experimental results are reported which provide useful calibration for the present computational approach.

Improved modeling of groundwater recharge in agricultural watersheds using a combination of crop model and remote sensing

For improved water management and efficiency of use in agriculture, studies dealing with coupled crop-surface water-groundwater models are needed. Such integrated models of crop and hydrology can provide accurate quantification of spatio-temporal variations of water balance parameters such as soil moisture store, evapotranspiration and recharge in a catchment. Performance of a coupled crop-hydrology model would depend on the availability of a calibrated crop model for various irrigated/rainfed crops and also on an accurate knowledge of soil hydraulic parameters in the catchment at relevant scale. Moreover, such a coupled model should be designed so as to enable the use/assimilation of recent satellite remote sensing products (optical and microwave) in order to model the processes at catchment scales. In this study we present a framework to couple a crop model with a groundwater model for applications to irrigated groundwater agricultural systems. We discuss the calibration of the STICS crop model and present a methodology to estimate the soil hydraulic parameters by inversion of crop model using both ground and satellite based data. Using this methodology we demonstrate the feasibility of estimation of potential recharge due to spatially varying soil/crop matrix.

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.

Statistical inference about the relative efficiency of a new survey protocol, based on paired-tow survey calibration data

Paired-tow calibration studies provide information on changes in survey catchability that may occur because of some necessary change in protocols (e.g., change in vessel or vessel gear) in a fish stock survey. This information is important to ensure the continuity of annual time-series of survey indices of stock size that provide the basis for fish stock assessments. There are several statistical models used to analyze the paired-catch data from calibration studies. Our main contributions are results from simulation experiments designed to measure the accuracy of statistical inferences derived from some of these models. Our results show that a model commonly used to analyze calibration data can provide unreliable statistical results when there is between-tow spatial variation in the stock densities at each paired-tow site. However, a generalized linear mixed-effects model gave very reliable results over a wide range of spatial variations in densities and we recommend it for the analysis of paired-tow survey calibration data. This conclusion also applies if there is between-tow variation in catchability.

Model structure and uncertainty for stochastic non-point source modelling applications

The uncertainty associated with a rainfall-runoff and non-point source loading (NPS) model can be attributed to both the parameterization and model structure. An interesting implication of the areal nature of NPS models is the direct relationship between model structure (i.e. sub-watershed size) and sample size for the parameterization of spatial data. The approach of this research is to find structural limitations in scale for the use of the conceptual NPS model, then examine the scales at which suitable stochastic depictions of key parameter sets can be generated. The overlapping regions are optimal (and possibly the only suitable regions) for conducting meaningful stochastic analysis with a given NPS model. Previous work has sought to find optimal scales for deterministic analysis (where, in fact, calibration can be adjusted to compensate for sub-optimal scale selection); however, analysis of stochastic suitability and uncertainty associated with both the conceptual model and the parameter set, as presented here, is novel; as is the strategy of delineating a watershed based on the uncertainty distribution. The results of this paper demonstrate a narrow range of acceptable model structure for stochastic analysis in the chosen NPS model. In the case examined, the uncertainties associated with parameterization and parameter sensitivity are shown to be outweighed in significance by those resulting from structural and conceptual decisions. © 2011 Copyright IAHS Press.

Biomimetic calcium carbonate-gelatin composites as a model system for eggshell mineralization

The composite nature of mineralized natural materials is achieved through both the microstructural inclusion of an organic component and an overall microstructure that is controlled by templating onto organic macromolecules. A modification of an existing laboratory technique is developed for the codeposition of a CaCO3-gelatin composite with a controllable organic content. First, calibration curves are developed to determine the organic content of a CaCO3-gelatin composite from infrared spectra. Second, a CaCO3-gelatin composite is deposited on either glass coverslips or demineralized eggshell membranes using an automated alternating soaking process. Electron microscopy images and use of the infrared spectra calibration curves show that by altering the amount of gelatin in the ionic growth solutions, the final organic component of the mineral can be regulated over the range of 1-10%, similar to that of natural eggshell. © 2012 Materials Research Societ.

A Stochastic Model for Electron Multiplication Charge-Coupled Devices - From Theory to Practice

Electron multiplication charge-coupled devices (EMCCD) are widely used for photon counting experiments and measurements of low intensity light sources, and are extensively employed in biological fluorescence imaging applications. These devices have a complex statistical behaviour that is often not fully considered in the analysis of EMCCD data. Robust and optimal analysis of EMCCD images requires an understanding of their noise properties, in particular to exploit fully the advantages of Bayesian and maximum-likelihood analysis techniques, whose value is increasingly recognised in biological imaging for obtaining robust quantitative measurements from challenging data. To improve our own EMCCD analysis and as an effort to aid that of the wider bioimaging community, we present, explain and discuss a detailed physical model for EMCCD noise properties, giving a likelihood function for image counts in each pixel for a given incident intensity, and we explain how to measure the parameters for this model from various calibration images. © 2013 Hirsch et al.

Assessing boost-assist options for turbocharged engines using 1-D engine simulation and model predictive control

Delivering acceptable low end torque and good transient response is a significant challenge for all turbocharged engines. As downsized gasoline engines and Diesel engines make up a larger and larger proportion of the light-duty engines entering the market, the issue takes on greater significance. Several schemes have been proposed to improve torque response in highly boosted engines, including the use of electrical assist turbochargers and compressed air assist. In this paper we examine these methods with respect to their effectiveness in improving transient response and their relative performance along with some of the practical considerations for real world application. Results shown in this paper are from 1-D simulations using the Ricardo WAVE software package. The simulation model is based on a production light-duty Diesel engine modified to allow the introduction of compressed air at various points in the air-path as well as direct torque application to the turbocharger shaft (such as might be available from an electrical assist turbocharger). Whilst the 1-D simulation software provides a suitable environment for investigating the various boost assistance options, the overall air path performance also depends upon the control system. The introduction of boost assistance complicates the control in two significant ways: the system may run into constraints (such as compressor surge) that are not encountered in normal operation and the assistance introduces an additional control input. Production engine controllers are usually based on gain-scheduled PID control and extensive calibration. For this study, the non-linear nature of the engine together with the multiple configurations considered and the slower than real-time execution of 1-D models makes such an approach time consuming. Moreover, an ad-hoc approach would leave some doubt as to the fairness of comparisons between the different boost-assist options. Model Predictive Control has been shown to offer a convenient approach to controlling the 1-D simulations in a close to optimal manner for a typical Diesel VGT-EGR air path configuration. We show that the same technique can be applied to all the considered assistance methods with only modest calibration effort required. Copyright © 2012 SAE International.

Coupling model uncertainty for coupled rainfall/runoff and surface water quality models in river problems

Coupled hydrology and water quality models are an important tool today, used in the understanding and management of surface water and watershed areas. Such problems are generally subject to substantial uncertainty in parameters, process understanding, and data. Component models, drawing on different data, concepts, and structures, are affected differently by each of these uncertain elements. This paper proposes a framework wherein the response of component models to their respective uncertain elements can be quantified and assessed, using a hydrological model and water quality model as two exemplars. The resulting assessments can be used to identify model coupling strategies that permit more appropriate use and calibration of individual models, and a better overall coupled model response. One key finding was that an approximate balance of water quality and hydrological model responses can be obtained using both the QUAL2E and Mike11 water quality models. The balance point, however, does not support a particularly narrow surface response (or stringent calibration criteria) with respect to the water quality calibration data, at least in the case examined here. Additionally, it is clear from the results presented that the structural source of uncertainty is at least as significant as parameter-based uncertainties in areal models. © 2012 John Wiley & Sons, Ltd.

Measurement of a reciprocal four-port transmission line structure using the 16-term error model

A new method to measure reciprocal four-port structures, using a 16-term error model, is presented. The measurement is based on 5 two-port calibration standards connected to two of the ports, while the network analyzer is connected to the two remaining ports. Least-squares-fit data reduction techniques are used to lower error sensitivity. The effect of connectors is deembedded using closed-form equations. (C) 2007 Wiley Periodicals, Inc.

A 16-term error model based on linear equations of voltage and current variables

Formulation of a 16-term error model, based on the four-port ABCD-matrix and voltage and current variables, is outlined. Matrices A, B, C, and D are each 2 x 2 submatrices of the complete 4 x 4 error matrix. The corresponding equations are linear in terms of the error parameters, which simplifies the calibration process. The parallelism with the network analyzer calibration procedures and the requirement of five two-port calibration measurements are stressed. Principles for robust choice of equations are presented. While the formulation is suitable for any network analyzer measurement, it is expected to be a useful alternative for the nonlinear y-parameter approach used in intrinsic semiconductor electrical and noise parameter measurements and parasitics' deembedding.

Large depth-of-view portable three-dimensional laser scanner and its segmental calibration for robot vision

A portable 3D laser scanning system has been designed and built for robot vision. By tilting the charge coupled device (CCD) plane of portable 3D scanning system according to the Scheimpflug condition, the depth-of-view is successfully extended from less than 40 to 100 mm. Based on the tilted camera model, the traditional two-step camera calibration method is modified by introducing the angle factor. Meanwhile, a novel segmental calibration approach, i.e., dividing the whole work range into two parts and calibrating, respectively, with corresponding system parameters, is proposed to effectively improve the measurement accuracy of the large depth-of-view 3D laser scanner. In the process of 3D reconstruction, different calibration parameters are used to transform the 2D coordinates into 3D coordinates according to the different positions of the image in the CCD plane, and the measurement accuracy of 60 mu m is obtained experimentally. Finally, the experiment of scanning a lamina by the large depth-of-view portable 3D laser scanner used by an industrial robot IRB 4400 is also employed to demonstrate the effectiveness and high measurement accuracy of our scanning system. (C) 2007 Elsevier Ltd. All rights reserved.

A study of the Hobson and Rogers volatility model

We firstly examine the model of Hobson and Rogers for the volatility of a financial asset such as a stock or share. The main feature of this model is the specification of volatility in terms of past price returns. The volatility process and the underlying price process share the same source of randomness and so the model is said to be complete. Complete models are advantageous as they allow a unique, preference independent price for options on the underlying price process. One of the main objectives of the model is to reproduce the `smiles' and `skews' seen in the market implied volatilities and this model produces the desired effect. In the first main piece of work we numerically calibrate the model of Hobson and Rogers for comparison with existing literature. We also develop parameter estimation methods based on the calibration of a GARCH model. We examine alternative specifications of the volatility and show an improvement of model fit to market data based on these specifications. We also show how to process market data in order to take account of inter-day movements in the volatility surface. In the second piece of work, we extend the Hobson and Rogers model in a way that better reflects market structure. We extend the model to take into account both first and second order effects. We derive and numerically solve the pde which describes the price of options under this extended model. We show that this extension allows for a better fit to the market data. Finally, we analyse the parameters of this extended model in order to understand intuitively the role of these parameters in the volatility surface.

A model to predict the life of pneumatic conveyor bends

A new approach to the prediction of bend lifetime in pneumatic conveyors, subject to erosive wear is described. Mathematical modelling is exploited. Commercial Computational Fluid Dynamics (CFD) software is used for the prediction of air flow and particle tracks, and custom code for the modelling of bend erosion and lifetime prediction. The custom code uses a toroidal geometry, and employs a range of empirical data rather than trying to fit classical erosion models to a particular circumstance. The data used was obtained relatively quickly and easily from a gas-blast erosion tester. A full-scale pneumatic conveying rig was used to validate a sample of the bend lifetime predictions, and the results suggest accuracy of within ±65%, using calibration methods. Finally, the work is distilled into user-friendly interactive software that will make erosion lifetime predictions for a wide range of bends under varying conveying conditions. This could be a valuable tool for the pneumatic conveyor design or maintenance engineer.

The Development of a Two-Dimensional Transient Catalyst Model for Direct Injection Two-Stroke Applications.

This paper describes the development of a two-dimensional transient catalyst model. Although designed primarily for two-stroke direct injection engines, the model is also applicable to four-stroke lean burn and diesel applications. The first section describes the geometries, properties and chemical processes simulated by the model and discusses the limitations and assumptions applied. A review of the modeling techniques adopted by other researchers is also included. The mathematical relationships which are used to represent the system are then described, together with the finite volume method used in the computer program. The need for a two-dimensional approach is explained and the methods used to model effects such as flow and temperature distribution are presented. The problems associated with developing surface reaction rates are discussed in detail and compared with published research. Validation and calibration of the model is achieved by comparing predictions with measurements from a flow reactor. While an extensive validation process, involving detailed measurements of gas composition and thermal gradients, has been completed, the analysis is too detailed for publication here and is the subject of a separate technical paper.