Development of novel NMR pulse sequences

To elucidate the structures of orgamc molecules in solution using pulse FT NMR, heteronuclear pulse sequence experiments to probe carbon-13 (13C) and proton (1H) spin systems are invaluable. The one-dimensional insensitive nucleus detected PENDANT experiment finds popular use for structure determination via one-bond 13C-1H scalar couplings. PENDANT facilitates the desired increase in 13C signal-to-noise ratio, and unlike many other pulse sequence experiments (e.g., refocused INEPT and DEPT), allows the simultaneous detection of 13C quaternary nuclei. The tlrst chapter herein details the characterisation of PENDANT and the successful rectification of spectral anomalies that occur when it is used without proton broadband decoupling. Multiple-bond (long-range) l3C-1H scalar coupling correlations can yield important bonding information. When the molecule under scrutiny is devoid of proton spectral crowding, and more sensitive 'inverse' pulse sequence experiments are not available, one may use insensitive nucleus detected long-range selective one-dimensional correlation methods, rather than more time consuming and insensitive multidimensional analogues. To this end a novel long-range selective one-dimensional correlation pulse sequence experiment has been invented. Based on PENDANT, the new experiment is shown to rival the popular selective INEPT technique because it can determine the same correlations while simultaneously detecting isolated 13C quaternary nuclei. INEPT cannot facilitate this, potentially leaving other important quaternary nuclei undetected. The novel sequence has been modified further to yield a second novel experiment that simultaneously yields selective 13C transient nOe data. Consequently, the need to perform the two experiments back-to-back is conveniently removed, and the experimental time reduced. Finally, the SNARE pulse sequence was further developed. SNARE facilitates the reduction of experimental time by accelerating the relaxation of protons upon which pulse sequences, to which SNARE is appended, relies. It is shown, contrary to the original publication, that reiaxation time savings can be derived from negative nOes.

Nuclear magnetic resonance spectroscopy and ultrasound

The work described in this thesis is directed to the examination of the hypothesis that ultrasound may be used to perturb molecular motion in the liquid phase. These changes can then be detected by nuclear magnetic resonance (NMR) in spin-lattice and spin-spin relaxation times. The objective being to develop a method capable of reducing the pulsed NMR acquisition times of slowly relaxing nuclei. The thesis describes the theoretical principles underlying both NMR spectroscopy and ultrasonics with particular attention being paid to factors that impinge on testing the above hypothesis. Apparatus has been constructed to enable ultrasound at frequencies between 1 and 10 mega-hertz with a variable power up to 100W/cm-2 to be introduced in the NMR sample. A broadband high frequency generator is used to drive PZT piezo-electric transducer via various transducer to liquid coupling arrangements. A commercial instrument of 20 kilo-hertz has also been employed to test the above hypothesis and also to demonstrate the usefulness of ultrasound in sonochemistry. The latter objective being, detection of radical formation in monomer and polymer ultrasonic degradation. The principle features of the results obtained are: Ultrasonic perturbation of T1 is far smaller for pure liquids than is for mixtures. The effects appear to be greater on protons (1H) than on carbon-13 nuclei (13C) relaxation times. The observed effect of ultrasonics is not due to temperature changes in the sample. As the power applied to the transducer is progressively increased T1 decreases to a minimum and then increases. The T1's of the same nuclei in different functional groups are influenced to different extents by ultrasound. Studies of the 14N resonances from an equimolar mixture of N, N-dimethylformamide and deuterated chloroform with ultrasonic frequencies at 1.115, 6, 6.42 and 10 MHz show that as the frequency is increased the NMR signal to noise ratio decreases to zero at the Larmor frequency of 6.42 MHz and then again rises. This reveals the surprising indication that an effect corresponding to nuclear acoustic saturation in the liquid may be observable. Ultrasonic irradiation of acidified ammonium chloride solution at and around 6.42 MHz appears to cause distinctive changes in the proton-nitrogen J coupling resonance at 89.56 MHz. Ultrasonic irradiation of N, N-dimethylacetamide at 2 KHz using the lowest stable power revealed the onset of coalescence in the proton spectrum. The corresponding effect achieved by direct heating required a temperature rise of approximately 30oC. The effects of low frequency (20 KHz) on relaxation times appear to be nil. Detection of radical formation proved difficult but is still regarded as the principle route for monomer and polymer degradation. The initial hypothesis is considered proven with the results showing significant changes in the mega-hertz region and none at 20 KHz.

Analytical first order comparison of amplitude and phase noise in single and dual Mach-Zehnder interferometer detection schemes for DQPSK transmission systems

An analytical first order calculation of the impact of Gaussian white noise on a novel single Mach-Zehnder Interferometer demodulation scheme for DQPSK reveals a constant Q factor ratio to the conventional scheme.

Noise generated at the tyre/road interface

The work described in this thesis is directed towards the reduction of tyre/road interface noise and embodies a study of the factors involved in its generation. These factors comprise: (a) materials and construction of tyres and road surfaces (b) the spectral distribution of the noise. The importance of this work has become greater with reduction in engine noise. A review of the literature shows what has been achieved so far, and stresses the importance of maintaining other desirable tyre properties such as adhesion in wet conditions. The work has involved an analysis of mechanical factors in tyre construction and the behaviour of road surfaces. Measurements on noise have been carried out under practical conditions and also on replica surfaces in the laboratory, and in addition tests of wet road adhesion have been carried out with a variety of road surfaces. Consideration has been given to the psychological effects of the spectral distribution of noise. A major part of the work under-taken has been the development of a computer program, the results of which have made it possible to design a tyre tread block pattern to give an optimum spectral distribution. Sample tyres built to this design have been subjected to noise measurements and these have been shown to agree closely with the theoretical prediction and other properties of this tyre have proved to be satisfactory.

An experimental study of the effects of noise upon short term memory

The overall aim of this study was to examine experimentally the effects of noise upon short-term memory tasks in the hope of shedding further light upon the apparently inconsistent results of previous research in the area. Seven experiments are presented. The first chapter of the thesis comprised a comprehensive review of the literature on noise and human performance while in the second chapter some theoretical questions concerning the effects of noise were considered in more detail follovred by a more detailed examination of the effects of noise upon memory. Chapter 3 described an experiment which examined the effects of noise on attention allocation in short-term memory as a function of list length. The results provided only weak evidence of increased selectivity in noise. In further chapters no~effects Here investigated in conjunction vrith various parameters of short-term memory tasks e.g. the retention interval, presentation rate. The results suggested that noise effects were significantly affected by the length of the retention interval but not by the rate of presentation. Later chapters examined the possibility of differential noise effects on the mode of recall (recall v. recognition) and the type of presentation (sequential v. simultaneous) as well as an investigation of the effect of varying the point of introduction of the noise and the importance of individual differences in noise research. The results of this study were consistent with the hypothesis that noise at presentation facilitates phonemic coding. However, noise during recall appeared to affect the retrieval strategy adopted by the subject.

Quasi-lossless spans for broadband transmission and data processing

We present the first experimental implementation of a recently designed quasi-lossless fibre span with strongly reduced signal power excursion. The resulting fibre waveguide medium can be advantageously used both in lightwave communications and in all-optical nonlinear data processing.

Spatial contrast sensitivity and external noise: applications to optical and neural modulation transfer functions

The thesis will show how to equalise the effect of quantal noise across spatial frequencies by keeping the retinal flux (If-2) constant. In addition, quantal noise is used to study the effect of grating area and spatial frequency on contrast sensitivity resulting in the extension of the new contrast detection model describing the human contrast detection system as a simple image processor. According to the model the human contrast detection system comprises low-pass filtering due to ocular optics, addition of light dependent noise at the event of quantal absorption, high-pass filtering due to the neural visual pathways, addition of internal neural noise, after which detection takes place by a local matched filter, whose sampling efficiency decreases as grating area is increased. Furthermore, this work will demonstrate how to extract both the optical and neural modulation transfer functions of the human eye. The neural transfer function is found to be proportional to spatial frequency up to the local cut-off frequency at eccentricities of 0 - 37 deg across the visual field. The optical transfer function of the human eye is proposed to be more affected by the Stiles-Crawford -effect than generally assumed in the literature. Similarly, this work questions the prevailing ideas about the factors limiting peripheral vision by showing that peripheral optical acts as a low-pass filter in normal viewing conditions, and therefore the effect of peripheral optics is worse than generally assumed.

Effects of pixel noise and stimulus structure on visual detection performance

This thesis consisted of two major parts, one determining the masking characteristics of pixel noise and the other investigating the properties of the detection filter employed by the visual system. The theoretical cut-off frequency of white pixel noise can be defined from the size of the noise pixel. The empirical cut-off frequency, i.e. the largest size of noise pixels that mimics the effect of white noise in detection, was determined by measuring contrast energy thresholds for grating stimuli in the presence of spatial noise consisting of noise pixels of various sizes and shapes. The critical i.e. minimum number of noise pixels per grating cycle needed to mimic the effect of white noise in detection was found to decrease with the bandwidth of the stimulus. The shape of the noise pixels did not have any effect on the whiteness of pixel noise as long as there was at least the minimum number of noise pixels in all spatial dimensions. Furthermore, the masking power of white pixel noise is best described when the spectral density is calculated by taking into account all the dimensions of noise pixels, i.e. width, height, and duration, even when there is random luminance only in one of these dimensions. The properties of the detection mechanism employed by the visual system were studied by measuring contrast energy thresholds for complex spatial patterns as a function of area in the presence of white pixel noise. Human detection efficiency was obtained by comparing human performance with an ideal detector. The stimuli consisted of band-pass filtered symbols, uniform and patched gratings, and point stimuli with randomised phase spectra. In agreement with the existing literature, the detection performance was found to decline with the increasing amount of detail and contour in the stimulus. A measure of image complexity was developed and successfully applied to the data. The accuracy of the detection mechanism seems to depend on the spatial structure of the stimulus and the spatial spread of contrast energy.

Reduction of noise levels in vaccum cleaners

The work described in this thesis is directed towards the reduction of noise levels in the Hoover Turbopower upright vacuum cleaner. The experimental work embodies a study of such factors as the application of noise source identification techniques, investigation of the noise generating principles for each major source and evaluation of the noise reducing treatments. It was found that the design of the vacuum cleaner had not been optimised from the standpoint of noise emission. Important factors such as noise `windows', isolation of vibration at the source, panel rattle, resonances and critical speeds had not been considered. Therefore, a number of experimentally validated treatments are proposed. Their noise reduction benefit together with material and tooling costs are presented. The solutions to the noise problems were evaluated on a standard Turbopower and the sound power level of the cleaner was reduced from 87.5 dB(A) to 80.4 db(A) at a cost of 93.6 pence per cleaner.The designers' lack of experience in noise reduction was identified as one of the factors for the low priority given to noise during design of the cleaner. Consequently, the fundamentals of acoustics, principles of noise prediction and absorption and guidelines for good acoustical design were collated into a Handbook and circulated at Hoover plc.Mechanical variations during production of the motor and the cleaner were found to be important. These caused a vast spread in the noise levels of the cleaners. Subsequently, the manufacturing processes were briefly studied to identify their source and recommendations for improvement are made.Noise of a product is quality related and a high level of noise is considered to be a bad feature. This project suggested that the noise level be used constructively both as a test on the production line to identify cleaners above a certain noise level and also to promote the product by `designing' the characteristics of the sound so that the appliance is pleasant to the user. This project showed that good noise control principles should be implemented early in the design stage.As yet there are no mandatory noise limits or noise-labelling requirements for household appliances. However, the literature suggests that noise-labelling is likely in the near future and the requirement will be to display the A-weighted sound power level. However, the `noys' scale of perceived noisiness was found more appropriate to the rating of appliance noise both as it is linear and therefore, a sound level that seems twice as loud is twice the value in noys and also takes into consideration the presence of pure tones, which even in the absence of a high noise level can lead to annoyance.

Projection and interpolation based techniques for structured and impulsive noise filtering

In this chapter we present the relevant mathematical background to address two well defined signal and image processing problems. Namely, the problem of structured noise filtering and the problem of interpolation of missing data. The former is addressed by recourse to oblique projection based techniques whilst the latter, which can be considered equivalent to impulsive noise filtering, is tackled by appropriate interpolation methods.

A novel binaural pitch elicited by phase-modulated noise:MEG and psychophysical observations

Binaural pitches are auditory percepts that emerge from combined inputs to the ears but that cannot be heard if the stimulus is presented to either ear alone. Here, we describe a binaural pitch that is not easily accommodated within current models of binaural processing. Convergent magnetoencephalography (MEG) and psychophysical measurements were used to characterize the pitch, heard when band-limited noise had a rapidly changing interaural phase difference. Several interesting features emerged: First, the pitch was perceptually lateralized, in agreement with the lateralization of the evoked changes in MEG spectral power, and its salience depended on dichotic binaural presentation. Second, the frequency of the pure tone that matched the binaural pitch lay within a lower spectral sideband of the phase-modulated noise and followed the frequency of that sideband when the modulation frequency or center frequency and bandwidth of the noise changed. Thus, the binaural pitch depended on the processing of binaural information in that lower sideband.

Noise characterization and transmission evaluation of unrepeated Raman amplified DP-16QAM link

Impairments characterization and performance evaluation of Raman amplified unrepeated DP-16QAM transmissions are conducted. Experimental results indicate that small gain in forward direction enhance the system signal-to-noise ratio for longer reach without introducing noticeable penalty.