27 resultados para Physical and Theoretical Chemistry

em Aston University Research Archive


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This thesis presents details on both theoretical and experimental aspects of UV written fibre gratings. The main body of the thesis deals with the design, fabrication and testing of telecommunication optical fibre grating devices, but also an accurate theoretical analysis of intra-core fibre gratings is presented. Since more than a decade, fibre gratings have been extensively used in the telecommunication field (as filters, dispersion compensators, and add/drop multiplexers for instance). Gratings for telecommunication should conform to very high fabrication standards as the presence of any imperfection raises the noise level in the transmission system compromising its ability of transmitting intelligible sequence of bits to the receiver. Strong side lobes suppression and high and sharp reflection profile are then necessary characteristics. A fundamental part of the theoretical and experimental work reported in this thesis is about apodisation. The physical principle of apodisation is introduced and a number of apodisation techniques, experimental results and numerical optimisation of the shading functions and all the practical parameters involved in the fabrication are detailed. The measurement of chromatic dispersion in fibres and FBGs is detailed and an estimation of its accuracy is given. An overview on the possible methods that can be implemented for the fabrication of tunable fibre gratings is given before detailing a new dispersion compensator device based on the action of a distributed strain onto a linearly chirped FBG. It is shown that tuning of second and third order dispersion of the grating can be obtained by the use of a specially designed multipoint bending rig. Experiments on the recompression of optical pulses travelling long distances are detailed for 10 Gb/s and 40 Gb/s. The characterisation of a new kind of double section LPG fabricated on a metal-clad coated fibre is reported. The fabrication of the device is made easier by directly writing the grating through the metal coating. This device may be used to overcome the recoating problems associated with standard LPGs written in step-index fibre. Also, it can be used as a sensor for simultaneous measurements of temperature and surrounding medium refractive index.

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The relative dominance of gratings engaged in binocular rivalry can be influenced by their surroundings. One striking example occurs when surrounding motion is congruent with one but not the other grating (C. L. Paffen, S. F. te Pas, R. Kanai, M. J. van der Smagt, & F. A. Verstraten, 2004). However, such center-surround stimulus configurations can also modulate perceived speed, via a directionally tuned process (H. P. Norman, J. F. Norman, J. T. Todd, & D. T. Lindsey, 1996). We recorded rivalry for Gabor patches embedded in a drifting noise texture. Gratings whose directions opposed the background motion tended to dominate more, and vice versa, consistent with previous findings. Observers then matched the speed of a drifting noise-embedded Gabor to that of a Gabor surrounded by mean luminance. Surround motion produced substantial changes in perceived speed, by at least a factor of two for all observers. We then asked whether perceived speed could account for the contextual effects on dominance. We measured the effects of speed on rivalry dominance by changing the physical speeds of rivaling gratings, as determined by the matching data. We found the same pattern of dominance as for the context experiment, indicating that perceived and true speed influence rivalry in the same manner. We propose a Bayesian interpretation of the perceived speed illusion.

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Transglutaminases have the ability to incorporate primary amines and to graft peptides (containing glutamine or lysine residues) into proteins. These properties enable transglutaminases to be used in the grafting of a range of compounds including peptides and/or proteins onto wool fibres, altering their functionality. In this paper we investigated the transglutaminase mediated grafting of silk proteins into wool and its effect on wool properties. A commercial hydrolysed silk preparation was compared with silk sericin. The silk sericin protein was labelled with a fluorescent probe which was used to demonstrate the efficiency of the TGase grafting of such proteins into wool fibres. The TGase mediated grafting of these proteins led to a significant effect on the properties of wool yarn and fabric, resulting in increased bursting strength, as well as reduced levels of felting shrinkage and improved fabric softness. Also observed was an accumulation of deposits on the surface of the treated wool fibres when monitored by SEM and alterations in the thermal behaviour of the modified fibres, in particular for mTGase/sericin treated fibres which, with the confocal studies, corroborate the physical changes observed on the treated wool fabric. © 2006 Elsevier Inc. All rights reserved.

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AIMS: To investigate the influence of chemical and physical factors on the rate and extent of germination of Clostridium difficile spores. METHODS AND RESULTS: Germination of C. difficile spores following exposure to chemical and physical germinants was measured by loss of either heat or ethanol resistance. Sodium taurocholate and chenodeoxycholate initiated germination together with thioglycollate medium at concentrations of 0.1-100 mmol l(-1) and 10-100 mmol l(-1) respectively. Glycine (0.2% w/v) was a co-factor required for germination with sodium taurocholate. There was no significant difference in the rate of germination of C. difficile spores in aerobic and anaerobic conditions (P > 0.05) however, the initial rate of germination was significantly increased at 37 degrees C compared to 20 degrees C (P < 0.05). The optimum pH range for germination was 6.5-7.5, with a decreased rate and extent of germination occurring at pH 5.5 and 8.5. CONCLUSIONS: This study demonstrates that sodium taurocholate and chenodeoxycholate initiate germination of C. difficile spores and is concentration dependant. Temperature and pH influence the rate and extent of germination. SIGNIFICANCE AND IMPACT OF THE STUDY: This manuscript enhances the knowledge of the factors influencing the germination of C. difficile spores. This may be applied to the development of potential novel strategies for the prevention of C. difficile infection.

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The factors influencing the stream segregation of discrete tones and the perceived continuity of discrete tones as continuing through an interrupting masker are well understood as separate phenomena. Two experiments tested whether perceived continuity can influence the build-up of stream segregation by manipulating the perception of continuity during an induction sequence and measuring streaming in a subsequent test sequence comprising three triplets of low and high frequency tones (LHL-…). For experiment 1, a 1.2-s standard induction sequence comprising six 100-ms L-tones strongly promoted segregation, whereas a single extended L-inducer (1.1 s plus 100-ms silence) did not. Segregation was similar to that following the single extended inducer when perceived continuity was evoked by inserting noise bursts between the individual tones. Reported segregation increased when the noise level was reduced such that perceived continuity no longer occurred. Experiment 2 presented a 1.3-s continuous inducer created by bridging the 100-ms silence between an extended L-inducer and the first test-sequence tone. This configuration strongly promoted segregation. Segregation was also increased by filling the silence after the extended inducer with noise, such that it was perceived like a bridging inducer. Like physical continuity, perceived continuity can promote or reduce test-sequence streaming, depending on stimulus context.

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A range of well-defined hydrophilic methacrylic macromonomers has been synthesized by the judicious combination of atom transfer radical polymerization (ATRP) and copper-catalyzed 1,3-dipolar cycloaddition (azide-alkyne click chemistry). An azido a-functionalized ATRP initiator was used to produce well-defined homopolymers with terminal azide functionality via ATRP in protic media at 20 °C, with generally good control being achieved over both target molecular weight and final polydispersity (Mw/Mn = 1.10-1.35). Suitable methacrylic monomers include 2-aminoethyl methacrylate hydrochloride, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-(methacryloyloxy)ethyl phosphorylcholine, glycerol monomethacrylate, potassium 3-sulfopropyl methacrylate, and quaternized 2-(dimethylamino)ethyl methacrylate. These homopolymer precursors were then efficiently clicked using either propargyl methacrylate or propargyl acrylate to yield near-monodisperse (meth)acrylate-capped macromonomers with either cationic, anionic, nonionic, or zwitterionic character. Moreover, this generic route to well-defined hydrophilic macromonomers is also suitable for “one-pot” syntheses, as exemplified for 2-hydroxyethyl methacrylate and glycerol monomethacrylate-based macromonomers.

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Metallocene catalyzed linear low density polyethylene (m-LLDPE) is a new generation of olefin copolymer. Based on the more recently developed metallocene-type catalysts, m-LLDPE can be synthesized with exactly controlled short chain branches and stereo-regular microstructure. The unique properties of these polymers have led to their applications in many areas. As a result, it is important to have a good understanding of the oxidation mechanism of m-LLDPE during melt processing in order to develop more effective stabilisation systems and continue to increase the performance of the material. The primary objectives of this work were, firstly, to investigate the oxidative degradation mechanisms of m-LLDPE polymers having different comonomer (I-octene) content during melt processing. Secondly, to examine the effectiveness of some commercial antioxidants on the stabilisation of m-LLDPE melt. A Ziegler-polymerized LLDPE (z-LLDPE) based on the same comonomer was chosen and processed under the same conditions for comparison with the metallocene polymers. The LLDPE polymers were processed using an internal mixer (torque rheometer, TR) and a co-rotating twin-screw extruder (TSE). The effects of processing variables (time, temperature) on the rheological (MI, MWD, rheometry) and molecular (unsaturation type and content, carbonyl compounds, chain branching) characteristics of the processed polymers were examined. It was found that the catalyst type (metallocene or Ziegler) and comonomer content of the polymers have great impact on their oxidative degradation behavior (crosslinking or chain scission) during melt processing. The metallocene polymers mainly underwent chain scission at lower temperature (<220°C) but crosslinking became predominant at higher temperature for both TR and TSE processed polymers. Generally, the more comonomers the m-LLDPE contains, a larger extent of chain scission can be expected. In contrast, crosslinking reactions were shown to be always dominant in the case of the Ziegler LLDPE. Furthermore, it is clear that the molecular weight distribution (MWD) of all LLDPE became broader after processing and tended generally to be broader at elevated temperatures and more extrusion passes. So, it can be concluded that crosslinking and chain scission are temperature dependent and occur simultaneously as competing reactions during melt processing. Vinyl is considered to be the most important unsaturated group leading to polymer crosslinking as its concentration in all the LLDPE decreased after processing. Carbonyl compounds were produced during LLDPE melt processing and ketones were shown to be the most imp0l1ant carbonyl-containing products in all processed polymers. The carbonyl concentration generally increased with temperature and extrusion passes, and the higher carbonyl content fonned in processed z-LLDPE and m-LLDPE polymers having higher comonomer content indicates their higher susceptibility of oxidative degradation. Hindered phenol and lactone antioxidants were shown to be effective in the stabilization of m-LLDPE melt when they were singly used in TSE extrusion. The combination of hindered phenol and phosphite has synergistic effect on m-LLDPE stabilization and the phenol-phosphite-Iactone mixture imparted the polymers with good stability during extrusion, especially for m-LLDPE with higher comonomer content.

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Results are reported from recent research on the use of the Brillouin gain/loss mechanism for distributed sensing. A theoretical model of the interaction of the pulsed and CW beams is described and compared with experiments. Results from a system with a 51 km sensing length are presented. We finally investigate issues related to the variation within the sensing fiber of the polarizations of the two beams.

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The extent to which the surface parameters of Progressive Addition Lenses (PALs) affect successful patient tolerance was investigated. Several optico-physical evaluation techniques were employed, including a newly constructed surface reflection device which was shown to be of value for assessing semi-finished PAL blanks. Detailed physical analysis was undertaken using a computer-controlled focimeter and from these data, iso-cylindrical and mean spherical plots were produced for each PAL studied. Base curve power was shown to have little impact upon the distribution of PAL astigmatism. A power increase in reading addition primarily caused a lengthening and narrowing of the lens progression channel. Empirical measurements also indicated a marginal steepening of the progression power gradient with an increase in reading addition power. A sample of the PAL wearing population were studied using patient records and questionnaire analysis (90% were returned). This subjective analysis revealed the reading portion to be the most troublesome lens zone and showed that patients with high astigmatism (> 2.00D) adapt more readily to PALs than those with spherical or low cylindrical (2.00D) corrections. The psychophysical features of PALs were then investigated. Both grafting visual acuity (VA) and contrast sensitivity (CS) were shown to be reduced with an increase in eccentricity from the central umbilical line. Two sample populations (N= 20) of successful and unsuccessful PAL wearers were assessed for differences in their visual performance and their adaptation to optically induced distortion. The possibility of dispensing errors being the cause of poor patient tolerance amongst the unsuccessful wearer group was investigated and discounted. The contrast sensitivity of the successful group was significantly greater than that of the unsuccessful group. No differences in adaptation to or detection of curvature distortion were evinced between these presbyopic groups.

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We demonstrate the first experimental implementation of a 3.9-Gb/s differential binary phase-shift keying (DBPSK)-based double sideband (DSB) optical fast orthogonal frequency-division-multiplexing (FOFDM) system with a reduced subcarrier spacing equal to half the symbol rate over 300m of multimode fiber (MMF) using intensity-modulation and direct-detection (IM/DD). The required received optical power at a bit-error rate (BER) of 10(-3) was measured to be similar to -14.2 dBm with a receiver sensitivity penalty of only similar to 0.2 dB when compared to the back-to-back case. Experimental results agree very well with the theoretical predictions.