The hard-soft acid-base principle in enzymatic catalysis: dual reactivity of phosphoenolpyruvate.

In this paper, the chemical reactivity of C3 of phosphoenolpyruvate (PEP) has been analyzed in terms of density functional theory quantified through quantum chemistry calculations. PEP is involved in a number of important enzymatic reactions, in which its C3 atom behaves like a base. In three different enzymatic reactions analyzed here, C3 sometimes behaves like a soft base and sometimes behaves like a hard base in terms of the hard-soft acid-base principle. This dual nature of C3 of PEP was found to be related to the conformational change of the molecule. This leads to a testable hypothesis: that PEP adopts particular conformations in the enzyme-substrate complexes of different PEP-using enzymes, and that the enzymes control the reactivity through controlling the dihedral angle between the carboxylate and the C==C double bond of PEP.

Interaction of liquid copper with sintered iron compacts

Interaction of liquid copper with sintered iron is important in brazing, liquid phase sintering and infiltration. In brazing, the penetration of liquid copper into the pores is to be `avoided', whereas in infiltration processes it is `encouraged', and in liquid phase sintering it should be `controlled' so that optimum mechanical properties are achieved. The main objective of the research is to model the interaction by studying the effect of the process variables on the mechanisms of copper interaction in Fe-Cu and Fe-Cu-C systems. This involves both theoretical and experimental considerations. Dilatometric investigations at 950, 1125 and 1200oC, together with metallographic analyses were carried out to clarify the copper growth phenomenon. It is shown that penetration of liquid copper into the iron grain boundaries is the major cause of dimensional changes. Infiltration profiles revealed that copper penetration between the iron interparticle contact points and along iron grain boundaries is a rapid process. The extent of copper penetration depends on the dihedral angle. Large dihedral angles hinder, and small angles promote copper penetration into the grain boundaries. Dihedral angle analysis shows that the addition of 0.6wt.% graphite reduces the number of zero dihedral angle from 27 to 3o and increases the mean dihedral angle from 9.8 to 41.5o. The dihedral angle was lowest at 1125oC and then increased to higher values as the system approached its equilibrium condition. Elementally mixed (E.M.) Fe-Cu compacts showed a rapid expansion at the copper melting point. However, graphite additions reduced compact growth by increasing the mean dihedral angle. In order to reduce the copper growth phenomenon, iron powder was coated with a thin layer of copper by an immersion coating (I.C.) technique. The dilatometric curves revealed an overall shrinkage in the I.C. compacts compared to their corresponding E.M. compacts. Multiple regression models showed that temperature had the most effect on dimensional changes and density had the most contributing effect upon the copper penetration area in the infiltrated powder metallurgy compacts.

Aerodynamic parametric analysis of an unconventional joined-wing aircraft configuration

In this paper, the experimental results of an unconventional joined-wing aircraft configuration are presented. The test model uses two different wings, forward and rear, both joined in tandem and forming diamond shapes both in plant and front views. The wings are joined in such a way that it is possible to change the rear wing dihedral angle values and the rear wing sweep angle values in 25 different positions that modify the relative distance and the relative height between the wings. To measure the system aerodynamic coefficients itis necessary to perform wind tunnel tests. The datapresented corresponds to the lift, drag and induced drag aerodynamic coefficients, as well as the aerodynamic efficiency and the parameter for minimum required power, from the calculated values of the lift and drag time series measured by a 6-axis force and torque sensor. The results show the influence on the aerodynamic coefficients of the rear wing sweep and dihedral angles parameters. As a main result, it can be concluded that, in general terms, the lift and induced drag aerodynamic coefficients values decrease as both the distance and height between the wings increase, on the other hand, the total drag aerodynamic coefficient decreases if the distance between the wings increases, but nevertheless shows a slight tendency to increase if the height of the rear wing increases, whereas the aerodynamic efficiency and the parameter for minimum required power increase if the distance between the wings increases

Liquid Mixtures Involving Hydrogenated and Fluorinated Alcohols: Thermodynamics, Spectroscopy, and Simulation

This article reports a combined thermodynamic, spectroscopic, and computational study on the interactions and structure of binary mixtures of hydrogenated and fluorinated substances that simultaneously interact through strong hydrogen bonding. Four binary mixtures of hydrogenated and fluorinated alcohols have been studied, namely, (ethanol + 2,2,2-trifluoroethanol (TFE)), (ethanol + 2,2,3,3,4,4,4-heptafluoro-1-butanol), (1-butanol (BuOH) + TFE), and (BuOH + 2,2,3,3,4,4,4-heptafluoro-1-butanol). Excess molar volumes and vibrational spectra of all four binary mixtures have been measured as a function of composition at 298 K, and molecular dynamics simulations have been performed. The systems display a complex behavior when compared with mixtures of hydrogenated alcohols and mixtures of alkanes and perfluoroalkanes. The combined analysis of the results from different approaches indicates that this results from a balance between preferential hydrogen bonding between the hydrogenated and fluorinated alcohols and the unfavorable dispersion forces between the hydrogenated and fluorinated chains. As the chain length increases, the contribution of dispersion increases and overcomes the contribution of H-bonds. In terms of the liquid structure, the simulations suggest the possibility of segregation between the hydrogenated and fluorinated segments, a hypothesis corroborated by the spectroscopic results. Furthermore, a quantitative analysis of the infrared spectra reveals that the presence of fluorinated groups induces conformational changes in the hydrogenated chains from the usually preferred all-trans to more globular arrangements involving gauche conformations. Conformational rearrangements at the CCOH dihedral angle upon mixing are also disclosed by the spectra.

Predictions of angle dependent tortuosity and elasticity effects on sound propagation in cancellous bone

The anisotropic pore structure and elasticity of cancellous bone cause wave speeds and attenuation in cancellous bone to vary with angle. Previously published predictions of the variation in wave speed with angle are reviewed. Predictions that allow tortuosity to be angle dependent but assume isotropic elasticity compare well with available data on wave speeds at large angles but less well for small angles near the normal to the trabeculae. Claims for predictions that only include angle-dependence in elasticity are found to be misleading. Audio-frequency data obtained at audio-frequencies in air-filled bone replicas are used to derive an empirical expression for the angle-and porosity-dependence of tortuosity. Predictions that allow for either angle dependent tortuosity or angle dependent elasticity or both are compared with existing data for all angles and porosities.

Wide-angle visual feature matching for outdoor localization

Wide-angle images exhibit significant distortion for which existing scale-space detectors such as the scale-invariant feature transform (SIFT) are inappropriate. The required scale-space images for feature detection are correctly obtained through the convolution of the image, mapped to the sphere, with the spherical Gaussian. A new visual key-point detector, based on this principle, is developed and several computational approaches to the convolution are investigated in both the spatial and frequency domain. In particular, a close approximation is developed that has comparable computation time to conventional SIFT but with improved matching performance. Results are presented for monocular wide-angle outdoor image sequences obtained using fisheye and equiangular catadioptric cameras. We evaluate the overall matching performance (recall versus 1-precision) of these methods compared to conventional SIFT. We also demonstrate the use of the technique for variable frame-rate visual odometry and its application to place recognition.

Wide-baseline keypoint detection and matching with wide-angle images for vision based localisation

This thesis addresses the problem of detecting and describing the same scene points in different wide-angle images taken by the same camera at different viewpoints. This is a core competency of many vision-based localisation tasks including visual odometry and visual place recognition. Wide-angle cameras have a large field of view that can exceed a full hemisphere, and the images they produce contain severe radial distortion. When compared to traditional narrow field of view perspective cameras, more accurate estimates of camera egomotion can be found using the images obtained with wide-angle cameras. The ability to accurately estimate camera egomotion is a fundamental primitive of visual odometry, and this is one of the reasons for the increased popularity in the use of wide-angle cameras for this task. Their large field of view also enables them to capture images of the same regions in a scene taken at very different viewpoints, and this makes them suited for visual place recognition. However, the ability to estimate the camera egomotion and recognise the same scene in two different images is dependent on the ability to reliably detect and describe the same scene points, or ‘keypoints’, in the images. Most algorithms used for this purpose are designed almost exclusively for perspective images. Applying algorithms designed for perspective images directly to wide-angle images is problematic as no account is made for the image distortion. The primary contribution of this thesis is the development of two novel keypoint detectors, and a method of keypoint description, designed for wide-angle images. Both reformulate the Scale- Invariant Feature Transform (SIFT) as an image processing operation on the sphere. As the image captured by any central projection wide-angle camera can be mapped to the sphere, applying these variants to an image on the sphere enables keypoints to be detected in a manner that is invariant to image distortion. Each of the variants is required to find the scale-space representation of an image on the sphere, and they differ in the approaches they used to do this. Extensive experiments using real and synthetically generated wide-angle images are used to validate the two new keypoint detectors and the method of keypoint description. The best of these two new keypoint detectors is applied to vision based localisation tasks including visual odometry and visual place recognition using outdoor wide-angle image sequences. As part of this work, the effect of keypoint coordinate selection on the accuracy of egomotion estimates using the Direct Linear Transform (DLT) is investigated, and a simple weighting scheme is proposed which attempts to account for the uncertainty of keypoint positions during detection. A word reliability metric is also developed for use within a visual ‘bag of words’ approach to place recognition.

Controller structure and design of firing angle controllers for (unit connected) HVDC systems

This paper investigates the control of a HVDC link, fed from an AC source through a controlled rectifier and feeding an AC line through a controlled inverter. The overall objective is to maintain maximum possible link voltage at the inverter while regulating the link current. In this paper the practical feedback design issues are investigated with a view of obtaining simple, robust designs that are easy to evaluate for safety and operability. The investigations are applicable to back-to-back links used for frequency decoupling and to long DC lines. The design issues discussed include: (i) a review of overall system dynamics to establish the time scale of different feedback loops and to highlight feedback design issues; (ii) the concept of using the inverter firing angle control to regulate link current when the rectifier firing angle controller saturates; and (iii) the design issues for the individual controllers including robust design for varying line conditions and the trade-off between controller complexity and the reduction of nonlinearity and disturbance effects

Operation and control of hybrid microgrid with angle droop controller

This paper compares the performance of two droop control schemes in a hybrid microgrid. With presence of both converter interfaced and inertial sources, the droop controller share power in a decentralized fashion. Both the droop controllers facilitate reactive power sharing based on voltage droop. However in frequency droop control, the real power sharing depends on the frequency, while in angle droop control, it depends on output voltage angle. For converter interfaced sources this reference voltage is tracked while for inertial DG, reference power for the prime mover is calculated from the reference angle with the proposed angle control scheme. This coordinated control scheme shows significant improvement in system performance. The comparison with the conventional frequency droop shows that the angle control scheme shares power with much lower frequency deviation. This is a significant improvement particularly in a frequent load changing scenario.