Catalyst, additive and substrate effects in intramolecular aromatic additions of alpha-diazoketones

This thesis is focused on transition metal catalysed reaction of α-diazoketones leading to aromatic addition to form azulenones, with particular emphasis on enantiocontrol through use of chiral copper catalysts. The first chapter provides an overview of the influence of variation of the substituent at the diazo carbon on the outcome of subsequent reaction pathways, focusing in particular on C-H insertion, cyclopropanation, aromatic addition and ylide formation drawing together for the first time input from a range of primary reports. Chapter two describes the synthesis of a range of novel α-diazoketones. Rhodium and copper catalysed cyclisation of these to form a range of azulenones is described. Variation of the transition metal catalyst was undertaken using both copper and rhodium based systems and ligand variation, including the design and synthesis of a novel bisoxazoline ligand. The influence of additives, especially NaBARF, on the enantiocontrol was explored in detail and displayed an interesting impact which was sensitive to substituent effects. Further exploration demonstrated that it is the sodium cation which is critical in the additive effects. For the first time, enantiocontrol in the aromatic addition of terminal diazoketones was demonstrated indicating enantiofacial control in the aromatic addition is feasible in the absence of a bridgehead substituent. Determination of the enantiopurity in these compounds was particularly challenging due to the lability of the products. A substantial portion of the work was focused on determining the stereochemical outcome of the aromatic addition processes, both the absolute stereochemistry and extent of enantiopurity. Formation of PTAD adducts was beneficial in this regard. The third chapter contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project, while details of chiral stationary phase HPLC and 1H NMR analysis are included in the appendix.

Interaction of additive and quantization noises in digital PLLs

Phase-locked loops (PLLs) are a crucial component in modern communications systems. Comprising of a phase-detector, linear filter, and controllable oscillator, they are widely used in radio receivers to retrieve the information content from remote signals. As such, they are capable of signal demodulation, phase and carrier recovery, frequency synthesis, and clock synchronization. Continuous-time PLLs are a mature area of study, and have been covered in the literature since the early classical work by Viterbi [1] in the 1950s. With the rise of computing in recent decades, discrete-time digital PLLs (DPLLs) are a more recent discipline; most of the literature published dates from the 1990s onwards. Gardner [2] is a pioneer in this area. It is our aim in this work to address the difficulties encountered by Gardner [3] in his investigation of the DPLL output phase-jitter where additive noise to the input signal is combined with frequency quantization in the local oscillator. The model we use in our novel analysis of the system is also applicable to another of the cases looked at by Gardner, that is the DPLL with a delay element integrated in the loop. This gives us the opportunity to look at this system in more detail, our analysis providing some unique insights into the variance `dip' seen by Gardner in [3]. We initially provide background on the probability theory and stochastic processes. These branches of mathematics are the basis for the study of noisy analogue and digital PLLs. We give an overview of the classical analogue PLL theory as well as the background on both the digital PLL and circle map, referencing the model proposed by Teplinsky et al. [4, 5]. For our novel work, the case of the combined frequency quantization and noisy input from [3] is investigated first numerically, and then analytically as a Markov chain via its Chapman-Kolmogorov equation. The resulting delay equation for the steady-state jitter distribution is treated using two separate asymptotic analyses to obtain approximate solutions. It is shown how the variance obtained in each case matches well to the numerical results. Other properties of the output jitter, such as the mean, are also investigated. In this way, we arrive at a more complete understanding of the interaction between quantization and input noise in the first order DPLL than is possible using simulation alone. We also do an asymptotic analysis of a particular case of the noisy first-order DPLL with delay, previously investigated by Gardner [3]. We show a unique feature of the simulation results, namely the variance `dip' seen for certain levels of input noise, is explained by this analysis. Finally, we look at the second-order DPLL with additive noise, using numerical simulations to see the effects of low levels of noise on the limit cycles. We show how these effects are similar to those seen in the noise-free loop with non-zero initial conditions.

Survey of the anticoccidial feed additive nicarbazin (as dinitrocarbanilide residues) in poultry and eggs

A survey was carried out on the occurrence of dinitrocarbanilide (DNC), the marker residue for nicarbazin, in poultry produced in Ireland during 2002-2004. Liver (n = 736) and breast muscle samples (n = 342) were tested. DNC residues were found in 40 and 26% of liver and breast muscle samples at levels greater than 12.5 and 5 mu g kg(-1), respectively. DNC residues were found at >200 mu g kg(-1) in 12 and 0% of liver and muscle samples, respectively. Samples of breast muscle (n = 217) imported from 11 countries were also tested for DNC residues. A lower incidence of DNC residues (6%) was found in imported breast muscle. Egg samples (n = 546) were tested and DNC residues were found in nine samples, with levels ranging between 14 and 122 mu g kg(-1). Analysis of poultry, carried out as part of official food inspection in the period 2004-2006, indicated a reduction in the number of broiler liver samples containing DNC at >200 mu g kg(-1), to approximately 7%. Low levels of DNC residues continue to be found in

Investigation of the causes for the occurrence of residues of the anticoccidial feed additive nicarbazin in commercial poultry

Investigations were undertaken to identify causes for the occurrence of high levels of the zootechnical feed additive nicarbazin in broiler liver at slaughter. The first investigation on 32 commercial broiler flocks involved sampling and analysis for nicarbazin ( as dinitrocarbanilide, DNC) in liver from birds during a 3-10-day period after withdrawal of nicarbazin from their feed and before commercial slaughter. DNC residues in liver samples of broilers scheduled as being withdrawn from nicarbazin for >= 6 days ranged from 20 to > 1600 mu g kg(-1) ( the specified withdrawal period for nicarbazin is 5 days and the Joint Expert Committee on Food Additives (JECFA)maximum residue limit (MRL) is 200 mu g kg(-1) liver). Further on-farm investigations on 12 of these flocks, selected on the basis of the feeding system in use and the levels of DNC residues determined in liver, identified issues in feed management contributing to elevated residues in broiler liver. A significant correlation (0.81, p

Modeling continuous self-report measures of perceived emotion using generalized additive mixed models

Emotion research has long been dominated by the “standard method” of displaying posed or acted static images of facial expressions of emotion. While this method has been useful it is unable to investigate the dynamic nature of emotion expression. Although continuous self-report traces have enabled the measurement of dynamic expressions of emotion, a consensus has not been reached on the correct statistical techniques that permit inferences to be made with such measures. We propose Generalized Additive Models and Generalized Additive Mixed Models as techniques that can account for the dynamic nature of such continuous measures. These models allow us to hold constant shared components of responses that are due to perceived emotion across time, while enabling inference concerning linear differences between groups. The mixed model GAMM approach is preferred as it can account for autocorrelation in time series data and allows emotion decoding participants to be modelled as random effects. To increase confidence in linear differences we assess the methods that address interactions between categorical variables and dynamic changes over time. In addition we provide comments on the use of Generalized Additive Models to assess the effect size of shared perceived emotion and discuss sample sizes. Finally we address additional uses, the inference of feature detection, continuous variable interactions, and measurement of ambiguity.

An iterative longest matching segment approach to speech enhancement with additive noise and channel distortion

This paper presents a new approach to speech enhancement from single-channel measurements involving both noise and channel distortion (i.e., convolutional noise), and demonstrates its applications for robust speech recognition and for improving noisy speech quality. The approach is based on finding longest matching segments (LMS) from a corpus of clean, wideband speech. The approach adds three novel developments to our previous LMS research. First, we address the problem of channel distortion as well as additive noise. Second, we present an improved method for modeling noise for speech estimation. Third, we present an iterative algorithm which updates the noise and channel estimates of the corpus data model. In experiments using speech recognition as a test with the Aurora 4 database, the use of our enhancement approach as a preprocessor for feature extraction significantly improved the performance of a baseline recognition system. In another comparison against conventional enhancement algorithms, both the PESQ and the segmental SNR ratings of the LMS algorithm were superior to the other methods for noisy speech enhancement.

Speech Enhancement from Additive Noise and Channel Distortion - a Corpus-Based Approach

This paper presents a new approach to single-channel speech enhancement involving both noise and channel distortion (i.e., convolutional noise). The approach is based on finding longest matching segments (LMS) from a corpus of clean, wideband speech. The approach adds three novel developments to our previous LMS research. First, we address the problem of channel distortion as well as additive noise. Second, we present an improved method for modeling noise. Third, we present an iterative algorithm for improved speech estimates. In experiments using speech recognition as a test with the Aurora 4 database, the use of our enhancement approach as a preprocessor for feature extraction significantly improved the performance of a baseline recognition system. In another comparison against conventional enhancement algorithms, both the PESQ and the segmental SNR ratings of the LMS algorithm were superior to the other methods for noisy speech enhancement. Index Terms: corpus-based speech model, longest matching segment, speech enhancement, speech recognition

Integration der Klebflächenbehandlung in die Fertigung

In vielen Fällen muss vor dem Kleben eine Klebflächenbehandlung durchgeführt werden, da Klebverbindungen mit unvorbehandelten Teilen häufig zu geringe Klebfestigkeiten und/oder eine unzureichende Alterungsbeständigkeit aufweisen. Zur Klebflächenbehandlung stehen unterschiedliche Verfahren zur Verfügung. Wenn mit mehreren Behandlungen klebtechnisch einwandfreie Verbindungen hergestellt werden können, gilt es, das Verfahren zu ermitteln, welches am besten in den Fertigungsfluss integriert werden kann und die geringsten Kosten verursacht. Dabei muss auch die Arbeitssicherheit und der Umweltschutz mit beachtet werden. Zur Beurteilung der Verfahren werden Bewertungskriterien gegeben. Die Verfahren werden abschließend kurz charakterisiert.

Zur rechten Zeit : Fertigung planen und steuern mit Softwarebausteinen für die Logistik

Unternehmen, die schnell auf veränderte Marktsituationen reagieren müssen, benötigen eine funktionierende Logistik, die eine Klammerfunktion für alle betrieblichen Bereiche ausübt. Kernstück eines Logistikkonzepts ist das PPS-System, das sich mit Hilfe zeitgemäßer Software immer mehr zur maßgeschneiderten Lösung entwickelt. Ein Weg, um Logistikmodule anforderungsgerecht einzuführen, lässt sich anhand eines besonderen Cim-Modells verdeutlichen, dessen letzter Arbeitsschritt das Auswählen von Hardware und Software ist.