Relative basicities of free base porphyrins : understanding the role of macrocyclic distortion

Porphyrins have been the center of numerous investigations in different areas of chemistry, geochemistry, and the life sciences. In nature the conformation of the porphyrin macrocycle varies, depending on the function of its apoenzyme. It is believed that the conformation of the porphyrin ring is necessary for the enzyme to achieve its function and modify its reactivity. It is important to understand how the conformation of the porphyrin ring will influence its properties. In synthetic porphyrins particular conformations and ring deformations can be achieved by peripheral substitution, metallation, core substitution, and core protonation among other alterations of the macrocycle. The macrocyclic distortions will affect the ring current, the ability of pyrroles to intramolecularly hydrogen bond and the relative basicity of each of the porphyrins. To understand these effects different theoretical models are used. The ground state structure of each of 19 free base porphyrins is determined using molecular mechanics (MM+) and semiempirical methods (PM3). The energetics of deformation of the macrocyclic core is calculated by carrying out single point energy calculations for the conformation achieved by each synthetic compound. Enthalpies of solution and enthalpies of protonation of 10 porphyrins with varying degrees of macrocyclic deformation and varying electron withdrawing groups in the periphery are determined using solution calorimetry. Using Hess's Law, the relative basicity of each of the different free base porphyrins is calculated. NMR results are described, including the determination of free energies of activation of ring tautomerization and hydrogen bonding for several compounds. It was found that in the absence of electronic effects, the greater macrocyclic deformation, the greater the basicity of the porphyrins. This basicity is attenuated by the presence of electron withdrawing groups and ability to of the macrocycle to intramolecularly hydrogen bond.

Suppression of nonlinear distortion in few-mode fibres using strong mode coupling

In this paper, we investigate the impact of linear mode coupling on the efficiency of intermodal four-wave mixing and on the group delay statistics in few-mode fibres. The investigation will include not only the weak or strong linear coupling regimes, but also the transition region between them, the intermediate coupling regime. This analysis will allow to assess the level of coupling strength require to suppress the nonlinear distortion in a few-mode fibre below the level of distortion for single-mode propagation without mode coupling.

Nonlinear distortion in mode delay compensated few-mode fibre spans with intermediate coupling

Nonlinear distortion in delay-compensated spans for intermediate coupling is studied for the first time. Coupling strengths under -30dB/100m allow distortion reduction using shorter compensation lengths and higher delays. For higher coupling strengths no significant penalty results from shorter compensation lengths.

A Decade-Bandwidth Low-Noise Mixer RFIC with a Distortion-Canceling Output Amplifier

This paper presents a 1-10 GHz low-noise downconvert mixer RFIC suitable for wideband receivers. A switched transconductor mixing core is adopted to reduce noise at high frequencies. By adding a series inductor to the RF transconductor, a flat 4-5 dB noise figure (NF) and a high gain of 26.5 dB can be achieved over a broad bandwidth out to 10 GHz. A CMOS output amplifier is also integrated on-chip, employing derivative superposition (DS) for high linearity and an OIP3 of 16.5 dBm. The circuit consumes less than 20 mW of dc power and occupies an active chip area of less than 0.2 mm2.

Nonlinear distortion generation mechanisms in Doherty amplifiers

Nowadays, wireless communications systems demand for greater mobility and higher data rates. Moreover, the need for spectral efficiency requires the use of non-constant envelope modulation schemes. Hence, power amplifier designers have to build highly efficient, broadband and linear amplifiers. In order to fulfil these strict requirements, the practical Doherty amplifier seems to be the most promising technique. However, due to its complex operation, its nonlinear distortion generation mechanisms are not yet fully understood. Currently, only heuristic interpretations are being used to justify the observed phenomena. Therefore, the main objective of this work is to provide a model capable of describing the Doherty power amplifier nonlinear distortion generation mechanisms, allowing the optimization of its design according to linearity and efficiency criteria. Besides that, this approach will allow a bridge between two different worlds: power amplifier design and digital pre-distortion since the knowledge gathered from the Doherty operation will serve to select the most suitable pre-distortion models.

Investigating the use of LiDAR scanning as a method for the measurement of timber distortion features

Measuring the extent to which a piece of structural timber has distorted at a macroscopic scale is fundamental to assessing its viability as a structural component. From the sawmill to the construction site, as structural timber dries, distortion can render it unsuitable for its intended purposes. This rejection of unusable timber is a considerable source of waste to the timber industry and the wider construction sector. As such, ensuring accurate measurement of distortion is a key step in addressing ineffciencies within timber processing. Currently, the FRITS frame method is the established approach used to gain an understanding of timber surface profile. The method, while reliable, is dependent upon relatively few measurements taken across a limited area of the overall surface, with a great deal of interpolation required. Further, the process is unavoidably slow and cumbersome, the immobile scanning equipment limiting where and when measurements can be taken and constricting the process as a whole. This thesis seeks to introduce LiDAR scanning as a new, alternative approach to distortion feature measurement. In its infancy as a measurement technique within timber research, the practicalities of using LiDAR scanning as a measurement method are herein demonstrated, exploiting many of the advantages the technology has over current approaches. LiDAR scanning creates a much more comprehensive image of a timber surface, generating input data multiple magnitudes larger than that of the FRITS frame. Set-up and scanning time for LiDAR is also much quicker and more flexible than existing methods. With LiDAR scanning the measurement process is freed from many of the constraints of the FRITS frame and can be done in almost any environment. For this thesis, surface scans were carried out on seven Sitka spruce samples of dimensions 48.5x102x3000mm using both the FRITS frame and LiDAR scanner. The samples used presented marked levels of distortion and were relatively free from knots. A computational measurement model was created to extract feature measurements from the raw LiDAR data, enabling an assessment of each piece of timber to be carried out in accordance with existing standards. Assessment of distortion features focused primarily on the measurement of twist due to its strong prevalence in spruce and the considerable concern it generates within the construction industry. Additional measurements of surface inclination and bow were also made with each method to further establish LiDAR's credentials as a viable alternative. Overall, feature measurements as generated by the new LiDAR method compared well with those of the established FRITS method. From these investigations recommendations were made to address inadequacies within existing measurement standards, namely their reliance on generalised and interpretative descriptions of distortion. The potential for further uses of LiDAR scanning within timber researches was also discussed.

An identification procedure of multi-input Wiener models for the distortion analysis of nonlinear circuits

In this contribution, a system identification procedure of a two-input Wiener model suitable for the analysis of the disturbance behavior of integrated nonlinear circuits is presented. The identified block model is comprised of two linear dynamic and one static nonlinear block, which are determined using an parameterized approach. In order to characterize the linear blocks, an correlation analysis using a white noise input in combination with a model reduction scheme is adopted. After having characterized the linear blocks, from the output spectrum under single tone excitation at each input a linear set of equations will be set up, whose solution gives the coefficients of the nonlinear block. By this data based black box approach, the distortion behavior of a nonlinear circuit under the influence of an interfering signal at an arbitrary input port can be determined. Such an interfering signal can be, for example, an electromagnetic interference signal which conductively couples into the port of consideration. © 2011 Author(s).

Direct Observation of Tetragonal Distortion in Epitaxial Structures through Secondary Peak Split in a Synchrotron Radiation Renninger Scan

This paper reports a direct observation of an interesting split of the (022)(022) four-beam secondary peak into two (022) and (022) three-beam peaks, in a synchrotron radiation Renninger scan (phi-scan), as an evidence of the layer tetragonal distortion in two InGaP/GaAs (001) epitaxial structures with different thicknesses. The thickness, composition, (a perpendicular to) perpendicular lattice parameter, and (01) in-plane lattice parameter of the two epitaxial ternary layers were obtained from rocking curves (omega-scan) as well as from the simulation of the (022)(022) split, and then, it allowed for the determination of the perpendicular and parallel (in-plane) strains. Furthermore, (022)(022) omega:phi mappings were measured in order to exhibit the multiple diffraction condition of this four-beam case with their split measurement.

IMPACT OF PLUG-IN ELECTRIC VEHICLES AND WIND GENERATORS ON HARMONIC DISTORTION OF ELECTRIC DISTRIBUTION SYSTEMS

Harmonic distortion on voltages and currents increases with the increased penetration of Plug-in Electric Vehicle (PEV) loads in distribution systems. Wind Generators (WGs), which are source of harmonic currents, have some common harmonic profiles with PEVs. Thus, WGs can be utilized in careful ways to subside the effect of PEVs on harmonic distortion. This work studies the impact of PEVs on harmonic distortions and integration of WGs to reduce it. A decoupled harmonic three-phase unbalanced distribution system model is developed in OpenDSS, where PEVs and WGs are represented by harmonic current loads and sources respectively. The developed model is first used to solve harmonic power flow on IEEE 34-bus distribution system with low, moderate, and high penetration of PEVs, and its impact on current/voltage Total Harmonic Distortions (THDs) is studied. This study shows that the voltage and current THDs could be increased upto 9.5% and 50% respectively, in case of distribution systems with high PEV penetration and these THD values are significantly larger than the limits prescribed by the IEEE standards. Next, carefully sized WGs are selected at different locations in the 34-bus distribution system to demonstrate reduction in the current/voltage THDs. In this work, a framework is also developed to find optimal size of WGs to reduce THDs below prescribed operational limits in distribution circuits with PEV loads. The optimization framework is implemented in MATLAB using Genetic Algorithm, which is interfaced with the harmonic power flow model developed in OpenDSS. The developed framework is used to find optimal size of WGs on the 34-bus distribution system with low, moderate, and high penetration of PEVs, with an objective to reduce voltage/current THD deviations throughout the distribution circuits. With the optimal size of WGs in distribution systems with PEV loads, the current and voltage THDs are reduced below 5% and 7% respectively, which are within the limits prescribed by IEEE.

CCTV scene perspective distortion estimation from low-level motion features

Our aim is to estimate the perspective-effected geometric distortion of a scene from a video feed. In contrast to most related previous work, in this task we are constrained to use low-level spatiotemporally local motion features only. This particular challenge arises in many semiautomatic surveillance systems that alert a human operator to potential abnormalities in the scene. Low-level spatiotemporally local motion features are sparse (and thus require comparatively little storage space) and sufficiently powerful in the context of video abnormality detection to reduce the need for human intervention by more than 100-fold. This paper introduces three significant contributions. First, we describe a dense algorithm for perspective estimation, which uses motion features to estimate the perspective distortion at each image locus and then polls all such local estimates to arrive at the globally best estimate. Second, we also present an alternative coarse algorithm that subdivides the image frame into blocks and uses motion features to derive block-specific motion characteristics and constrain the relationships between these characteristics, with the perspective estimate emerging as a result of a global optimization scheme. Third, we report the results of an evaluation using nine large sets acquired using existing closed-circuit television cameras, not installed specifically for the purposes of this paper. Our findings demonstrate that both proposed methods are successful, their accuracy matching that of human labeling using complete visual data (by the constraints of the setup unavailable to our algorithms).

The effect of alternate supply of shielding gases in austenite stainless steel GTA welding

Welding system has now been concentrated on the development of new process to achieve cost savings, higher productivity and better quality in manufacturing industry. Discrete alternate supply of shielding gas is a new technology that alternately supplies the different kinds of shielding gases in weld zone. As the newdevelopedmethods compared to the previous generalwelding with a mixing supply of shielding gas, it cannot only increase thewelding quality, but also reduce the energy by 20% and the emission rate of fume. As a result, under thesamewelding conditions,comparedwith thewelding by supplying pure argon, argon + 67% helium mixture by conventional method and thewelding by supplying alternately pure argon and pure helium by alternate method showed the increased welding speed. Also, the alternate method showed the same welding speed with argon + 67% helium mixture without largely deteriorating of weld penetration. The alternate method with argon and helium compared with the conventional methods of pure argon and argon + 67% helium mixture produced the lowest degree of welding distortion.

A numerical method to quantify the axial shortening of vertical elements in concrete buildings

Differential axial shortening, distortion and deformation in high rise buildings is a serious concern. They are caused by three time dependent modes of volume change; “shrinkage”, “creep” and “elastic shortening” that takes place in every concrete element during and after construction. Vertical concrete components in a high rise building are sized and designed based on their strength demand to carry gravity and lateral loads. Therefore, columns and walls are sized, shaped and reinforced differently with varying concrete grades and volume to surface area ratios. These structural components may be subjected to the detrimental effects of differential axial shortening that escalates with increasing the height of buildings. This can have an adverse impact on other structural and non-structural elements. Limited procedures are available to quantify axial shortening, and the results obtained from them differ because each procedure is based on various assumptions and limited to few parameters. All these prompt to a need to develop an accurate numerical procedure to quantify the axial shortening of concrete buildings taking into account the important time varying functions of (i) construction sequence (ii) Young’s Modulus and (iii) creep and shrinkage models associated with reinforced concrete. General assumptions are refined to minimize variability of creep and shrinkage parameters to improve accuracy of the results. Finite element techniques are used in the procedure that employs time history analysis along with compression only elements to simulate staged construction behaviour. This paper presents such a procedure and illustrates it through an example. Keywords: Differential Axial Shortening, Concrete Buildings, Creep and Shrinkage, Construction Sequence, Finite Element Method.

Introduction

The title of this book, Hard Lesson: Reflections on Crime control in Late Modernity, contains a number of clues about its general theoretical direction. It is a book concerned, fist and foremost, with the vagaries of crime control in western neo-liberal and English speaking countries. More specifically, Hard Lessons draws attention to a number of examples in which discrete populations – those who have in one way or another offended against the criminal law - have become the subjects of various forms of stare intervention, regulation and control. We are concerned most of all with the ways in which recent criminal justice policies and practices have resulted in what are variously described as unintended consequences, unforeseen outcomes, unanticipated results, counter-productive effects or negative side effects. At their simplest, such terms refer to the apparent gulf between intention and outcome; they often form the basis for considerable amount of policy reappraisal, soul searching and even nihilistic despair among the mamandirns of crime control. Unintended consequences can, of course, be both positive and negative. Occasionally, crime control measures may result in beneficial outcomes, such as the use of DNA to acquit wrongly convicted prisoners. Generally, however, unforeseen effects tend to be negative and even entirely counterproductive, and/or directly opposite to what were originally intended. All this, of course, presupposes some sort of rational, well meaning and transparent policy making process so beloved by liberal social policy theorists. Yet, as Judith Bessant points out in her chapter, this view of policy formulation tends to obscure the often covert, regulatory and downright malevolent intentions contained in many government policies and practices. Indeed, history is replete with examples of governments seeking to mask their real aims from a prying public eye. Denials and various sorts of ‘techniques of neutralisation’ serve to cloak the real or ‘underlying’ aims of the powerful (Cohen 2000). The latest crop of ‘spin doctors’ and ‘official spokespersons’ has ensured that the process of governmental obfuscation, distortion and concealment remains deeply embedded in neo-liberal forms of governance. There is little new or surprising in this; nor should we be shocked when things ‘go wrong’ in the domain of crime control since many unintended consequences are, more often than not, quite predictable. Prison riots, high rates of recidivism and breaches of supervision orders, expansion rather than contraction of control systems, laws that create the opposite of what was intended – all these are normative features of western crime control. Indeed, without the deep fault lines running between policy and outcome it would be hard to imagine what many policy makers, administrators and practitioners would do: their day to day work practices and (and incomes) are directly dependent upon emergent ‘service delivery’ problems. Despite recurrent howls of official anguish and occasional despondency it is apparent that those involved in the propping up the apparatus of crime control have a vested interest in ensuring that polices and practices remain in an enduring state of review and reform.