The relationship between distinctive characteristic fluid-flow regimes and the sound radiation generated by them has been investigated, over a range of Reynolds numbers, for various single plates and two-plate arrays in nominally two-dimensional flows. In preliminary experiments, the characteristics of flow over single plates with rectangular cross-section and faired leading edges and over tandem arrays of an upstream plate with rectangular cross-section and faired leading edges and a downstream plate of rectangular cross-section were investigated, together with the sound radiation produced. However, the main investigation has been concentrated on single plates of rectangular cross-section with various chord-to-thickness ratios C and on arrays of two plates of rectangular cross-section in tandem having various chord-to-thickness ratios C₁ and C₂ and a range of gaps (with gap-to-thickness ratios G) between them. The range of Reynolds number based on plate thickness t and free-stream velocity U, Re[subscript]t = Ut/ν (where ν is the kinematic viscosity of fluid) covered in the measurements is 3.2 x 10[superscript]3 ≤ Re[subscript]t 53 x 10[superscript]3. Spectra of velocity fluctuations in the flow and radiated sound have been measured and their characteristic frequencies related. An attempt has been made to measure force fluctuations on surfaces of the plates in order to relate them to flow characteristics and radiated sound power. Mean and fluctuating pressures associated with the force fluctuations on the plates have also been obtained. The lengths of separation bubbles on long rectangular plates have also been determined. In most cases, the measurements have been complemented by flow-visualisation in a water tunnel to provide additional detailed insight into the flow patterns. Three flow regimes have been identified for single plates of rectangular cross-section. In the first regime (1 ≤ C ≤ 3.13), shear layers separated from the leading edges form a vortex street downstream of the plate without reattachment to it. Associated force fluctuations on the plate are the main source of acoustic radiation. In the second regime (3.05 ≤ C ≤ 9.65), the separated shear layers reattach intermittently to the streamwise plate surfaces. Vortex formation in the shear layer is the dominant cause of sound radiation but the effect becomes weaker as C increases. In the third regime (6.52 ≤ C ≤ 68), the separated shear layers form closed leading-edge separation bubbles. Weak vortex shedding, with only a small contribution to the sound radiation, occurs only at the trailing edges of the plate. Bistable behaviour of the flow over a plate, with random switching between the regimes, occurs for C ≈ 3 and 6.52 ≤ C ≤ 9.65. A proposed classification of possible flow regimes for the flow around two plates of rectangular cross-section in tandem has been confirmed experimentally. For small G, the flow in the gap between the plates is isolated from the external flow. When the gap G between the plates is increased to or beyond a critical value (between 2 and 3.5), the shear layers separated from the upstream plate form a von Karman vortex street in the gap before interacting with the downstream plate. Flow and acoustic measurements indicate that this transition is associated with dramatic changes in the flow character. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320474 / Thesis (Ph.D.) -- University of Adelaide, School of Mechanical Engineering, 2008

This thesis describes the application of mass spectrometry (MS) to glycoprotein and oligosaccharide analysis. Glycosylated proteins are involved in cell-cell and cell-matrix recognition. Applications of trypsin and proteinase K to hydrolyze glycoproteins into glycopeptides that are compatible with MS and MS/MS analysis are investigated. For successful site-specific analysis of glycans, glycopeptides with short peptide (3-8 residues) are needed. Although trypsin is an important enzyme for protein identification, proteinase K is superior for site-specific glycan analysis due to its potential to hydrolyze every glycoprotein to short glycopeptides. The gas-phase dissociation pathways, kinetics and energetics of protonated oligosaccharides are described. The oligosaccharides dissociate via cleavage at the glycosidic linkages during thermal activation. Using double resonance experiments, it was established that oligosaccharides undergo sequential and parallel fragmentation reactions. Furthermore, dissociation of product ions to secondary ions was confirmed. Arrhenius activation parameters, Ea and A for protonated alpha- and beta-linked D-glucopyranose oligosaccharides are reported.

In this study, loss and loading characteristics of compressor tandem blades are evaluated. Whole study was focused on change of the total camber so called turning angle. Effects of camber change were investigated in terms of loss and loading characteristics. Methodology was increasing overall camber first by aligning angular positions of blades and second, if required, using more cambered airfoils. 2-dimensional cascade flow CFD analyses were performed to obtain loss-loading information of different tandem blade combinations. Acquired results were compared with the classical axial compressor blades&rsquo / loading and loss characteristics which were obtained from literature. Results showed that most of the time tandem blade configuration performed better than the single blade counterpart in 2-dimensional cascade flow. Lastly, to clarify the benefit of the study and present the gained performance in numbers, only one cascade flow CFD analysis was performed for a classical single compressor blade. Loss and loading results were compared with the tandem blade counterpart where single and tandem configurations both having the same degree of camber. It was clearly seen that tandem blade performed better again.

No description available.

A set of studies centered around the reactions of the active methine compound 1-carbomethoxy-5-dicyanomethyl-1,3-cyclohexadiene (the "ring-opened adduct"), obtained by base-induced ring-opening of the Diels-Alder adduct of 5,5-dicyanocyclopentadiene and methyl acrylate, has been carried out. A plan was devised for the anionic (at the dicyanomethyl carbon) ring-opened adduct whereby its reaction with electrophiles, for example Michael reactions with double-bond acceptors, would generate reactive intermediates that would undergo cyclization by tandem conjugate addition to the a,ß,?,d-unsaturated ring p-system to generate bicyclic compounds. In practice, reaction with di-<i>tert</i>-butyl methylidenemalonate, methyl vinyl ketone, and cyclopentenone generated intermediates that exhibited greater tandem reactivity than was anticipated: the bicyclic enolates were found to cyclize further by Thorpe-Ziegler-like reaction with the proximal nitrile to generate, after facile acid hydrolysis, substituted known tricyclic skeleta termed homobrendanes, specifically, tricyclo[5. 2. 1. 0^4,8]decenes. An attempt was made to generalize the reaction to other substrates, among them singly-activated Michael acceptors and 1,2-heteroatom electrophiles, but the generalization of the homobrendane forming reaction did not meet with success. Attempted functional group manipulations to probe the conversion of the homobrendane derived from di-<i>tert</i>-butyl methylidenemalonate to the homobrendane natural product 2-isocyanoallopupukeanane revealed the unreactivity of the skeletal double-bond toward electrophiles and the high reactivity of the ring ketone toward nucleophiles, among them mCPBA which brought about Baeyer-Villiger reaction, and chloride and hydroxide, which brought about addition/elimination reactions to cleave the last-formed homobrendane ring. <br /> The ring-opened adduct was also envisaged as a potential substrate in intramolecular Heck reactions. To this end, Heck substrates were generated from the ring-opened adduct anion and iodo- and bromo-benzyl halides. A key observation at this stage pertained to the unexpected acidity of the ring-opened adduct C5 proton, which could be deprotonated by DBU to bring about allylic isomerization, a finding that would provide a key insight to the pattern of reactivity later evidenced with alkyl propiolates. Optimization of the Heck substrate-generating reaction was followed by Heck reactions under Jeffery's conditions, which generated angular tricycles as intended, accompanied by aromatic compounds generated by base-induced HCN elimination/rearrangement and dehydrogenation. The Jeffery's conditions were optimized to limit the production of aromatics. <br /> The possibility of ring-opened adduct-derived vinyl silane intermediates undergoing cationic cyclizations led to a minor study based upon the bromination of allylsilanes and the elimination of TMSBr from 1,2-dibromo-3-trimethylsilyl compounds, accessible compounds unaccounted for in the review literature. It was determined that the combination of HBr and Br₂ (perhaps as HBr₃) was required to eliminate TMSBr, in contravention of the textbook account of electrophilic substitutions being the inherent reactions of allylsilanes and Br₂. <br /> Unexpected tandem reactivity was observed in the reactions of the anionic ring-opened adduct and alkyl propiolates under catalytic DBU conditions. Rather than tandem cyclization or simple adduct formation, the allenolate intermediates were determined to undergo extremely facile formal allenolate Cope rearrangements involving the ?,d-double-bond of the parent ring. Excess base intercepted the allenolate by deprotonating ring C5 and effecting 1,2-vinyl transfer by 3-<i>exo</i>-trig addition-elimination. The chemistry of the highly delocalized side-chain carbanion in the Cope product was studied in detail.

A set of studies centered around the reactions of the active methine compound 1-carbomethoxy-5-dicyanomethyl-1,3-cyclohexadiene (the "ring-opened adduct"), obtained by base-induced ring-opening of the Diels-Alder adduct of 5,5-dicyanocyclopentadiene and methyl acrylate, has been carried out. A plan was devised for the anionic (at the dicyanomethyl carbon) ring-opened adduct whereby its reaction with electrophiles, for example Michael reactions with double-bond acceptors, would generate reactive intermediates that would undergo cyclization by tandem conjugate addition to the a,ß,?,d-unsaturated ring p-system to generate bicyclic compounds. In practice, reaction with di-<i>tert</i>-butyl methylidenemalonate, methyl vinyl ketone, and cyclopentenone generated intermediates that exhibited greater tandem reactivity than was anticipated: the bicyclic enolates were found to cyclize further by Thorpe-Ziegler-like reaction with the proximal nitrile to generate, after facile acid hydrolysis, substituted known tricyclic skeleta termed homobrendanes, specifically, tricyclo[5. 2. 1. 0^4,8]decenes. An attempt was made to generalize the reaction to other substrates, among them singly-activated Michael acceptors and 1,2-heteroatom electrophiles, but the generalization of the homobrendane forming reaction did not meet with success. Attempted functional group manipulations to probe the conversion of the homobrendane derived from di-<i>tert</i>-butyl methylidenemalonate to the homobrendane natural product 2-isocyanoallopupukeanane revealed the unreactivity of the skeletal double-bond toward electrophiles and the high reactivity of the ring ketone toward nucleophiles, among them mCPBA which brought about Baeyer-Villiger reaction, and chloride and hydroxide, which brought about addition/elimination reactions to cleave the last-formed homobrendane ring. <br /> The ring-opened adduct was also envisaged as a potential substrate in intramolecular Heck reactions. To this end, Heck substrates were generated from the ring-opened adduct anion and iodo- and bromo-benzyl halides. A key observation at this stage pertained to the unexpected acidity of the ring-opened adduct C5 proton, which could be deprotonated by DBU to bring about allylic isomerization, a finding that would provide a key insight to the pattern of reactivity later evidenced with alkyl propiolates. Optimization of the Heck substrate-generating reaction was followed by Heck reactions under Jeffery's conditions, which generated angular tricycles as intended, accompanied by aromatic compounds generated by base-induced HCN elimination/rearrangement and dehydrogenation. The Jeffery's conditions were optimized to limit the production of aromatics. <br /> The possibility of ring-opened adduct-derived vinyl silane intermediates undergoing cationic cyclizations led to a minor study based upon the bromination of allylsilanes and the elimination of TMSBr from 1,2-dibromo-3-trimethylsilyl compounds, accessible compounds unaccounted for in the review literature. It was determined that the combination of HBr and Br₂ (perhaps as HBr₃) was required to eliminate TMSBr, in contravention of the textbook account of electrophilic substitutions being the inherent reactions of allylsilanes and Br₂. <br /> Unexpected tandem reactivity was observed in the reactions of the anionic ring-opened adduct and alkyl propiolates under catalytic DBU conditions. Rather than tandem cyclization or simple adduct formation, the allenolate intermediates were determined to undergo extremely facile formal allenolate Cope rearrangements involving the ?,d-double-bond of the parent ring. Excess base intercepted the allenolate by deprotonating ring C5 and effecting 1,2-vinyl transfer by 3-<i>exo</i>-trig addition-elimination. The chemistry of the highly delocalized side-chain carbanion in the Cope product was studied in detail.

Nonribosomal peptides (NRP) are highlighted in pharmacological studies as novel NRPs are often promising substances for new drug development. To effectively discover novel NRPs from microbial fermentations, a crucial step is to identify known NRPs in an early stage and exclude them from further investigation. This so-called dereplication step ensures the scarce resource is only spent on the novel NRPs in the following up experiments. Tandem mass spectrometry has been routinely used for NRP dereplication. However, few bioinformatics tools have been developed to computationally identify NRP compounds from mass spectra, while manual identification is currently the roadblock hindering the throughput of novel NRP discovery. In this thesis, we review the nature of nonribosomal peptides and investigate the challenges in computationally solving the identification problem. After that, iSNAP software is proposed as an automated and high throughput solution for tandem mass spectrometry based NRP identification. The algorithm has been evolved from the traditional database search approach for identifying sequential peptides, to one that is competent at handling complicated NRP structures. It is designed to be capable of identifying mixtures of NRP compounds from LC-MS/MS of complex extract, and also finding structural analogs which differ from an identified known NRP compound with one monomer. Combined with an in-house NRP structural database of 1107 compounds, iSNAP is tested to be an effective tool for mass spectrometry based NRP identification. The software is available as a web service at http://monod.uwaterloo.ca/isnap for the research community.

Recently, tandem white organic light-emitting diodes are attracting a great deal of interest due to their potential illumination applications. A tandem structure is a mean two or more electroluminescence units that joined together through connecting units in series. So, we can make sense that the connecting unit has play an important role in this particular structure. In my paper research, the functions of connecting units are usually being considered with two aspects: charge transporting and charge generation. But, it was rarely discussed which function is the key point. Three devices were fabricated in this study : (¢¹) unit device, (¢º) tandem device 1 with connecting layers of Alq3:Li/MoO3 and (¢») tandem device 2 with connecting layers of Alq3:Li/HAT-CN. Base on this two connecting unit structure, we can get a quantifiable data from adopting, carrier transporting and carrier generation and figure out which function of connecting unit in tandem device is the main factor. The unit device has outstanding performance comparing to others fluorescence white OLED. It exhibits a maximum luminance of 49820 cd/m2 at 1755 mA/cm2, the power efficiency of 2.52 lm/W at 20 mA/cm2 and CIE (0.33, 0.33). But the power efficiency decreased to 2.07 lm/W at 20 mA/cm2 in tandem device 1. In order to improve device performance, we choose new material HAT-CN to replace to MoO3. From our result, the tandem device 2 have increase power efficiency from 2.07 lm/W to 2.24 lm/W at 20 mA/cm2, and the maximum luminance reach 71790 cd/m2 at 650 mA/cm2 with CIE(0.30, 0.39). We want to figure out why the power efficiency increased after using HAT-CN in tandem device. So we further designed and fabricated the hole only device, electron only device and capacitance device to figure out the charge transporting and charge generation behavior between these two connecting unit constructed based on Alq3:Li/MoO3 and Alq3:Li/HAT-CN. After analyzing the results of these devices, we found that the charge generating plays a major role in tandem OLED¡¦s performance. In other words, if the more carriers can be generated in the connecting layers, the higher power efficiency in tandem device can be realized.

OLEDs for display and lighting applications were studied. Both RGB and color filter technologies were discussed in the display section; meanwhile, RGB white light and tendem white light were discussed in the lighting section. A high performance RGB white display using 1,3,5-tri(1-pyrenyl) benzene (TPB3), C545T (166000 cd/m2) and DCJTB (70600 cd/m2) has been prepared with a 53.3% color gamut. For the color display using PLED technology, a glycerol modified PEDOT (G-PEDOT) is used as buffer layer material. Luminance of the white PLED display increases significantly from 11580 cd/m2 to 16040 cd/m2. A 54.5% color gamut color display is prepared using the white PLED device with a color filter. RGB white device with maximum luminance of 55800 cd/m2, maximum luminance efficiency of 4.55 cd/A, maximum power efficiency of 3.85 lm/W, and CIE coordinate of (0.33, 0.32) is prepared with a device structure of ITO(1300A)/NPB(500A)/TPB3(200A)/DPVBi¡G2% DSB(150A)/Alq3¡G2% DCJTB (150A)/ Alq3(350A)/LiF(8A)/Al(2000A). A high performance single emission layer white OLED device is also prepared. This single-layer device achieves a maximum luminance of 95200 cd/m2, maximum luminance efficiency of 5.9 cd/A, maximum power efficiency of 4.06 lm/W, and CIE coordinate of (0.34, 0.39) with a device structure of ITO(1300A)/NPB(650A)/TPB3:6% DSB:0.6% DCJTB(400A)/Alq3(300A)/LiF(8A)/Al(2000A). Optimization of a tandem OLED device is conducted using a Alq3¡GLi/ HAT-CN interlayer. It is found that turn-on voltage is reduced effectively using the Alq3¡GLi/ HAT-CN interlayer at 20 mA/cm2. Power efficiency is increased to 2.24 lm/W, and maximum luminance of 71790 cd/m2 is achieved with a CIE coordinate of (0.30, 0.39).

High-throughput techniques are currently some of the most promising methods to study molecular biology, with the potential to improve medicine and enable new biological applications. In proteomics, the large scale study of proteins, the leading method is mass spectrometry. At present researchers can routinely identify and quantify thousands of proteins in a single experiment with the technique called shotgun proteomics. A challenge of these experiments is the computational analysis and the interpretation of the mass spectra. A shotgun proteomics experiment easily generates tens of thousands of spectra, each thought to represent a peptide from a protein. Due to the immense biological and technical complexity, however, our computational tools often misinterpret these spectra and derive incorrect peptides. As a consequence, the biological interpretation of the experiment relies heavily on the statistical confidence that we estimate for the identifications. In this thesis, I have included four articles from my research on the accuracy of the statistical confidence estimates in shotgun proteomics, how to accomplish and evaluate it. In the first two papers a new method to use pre-characterized protein samples to evaluate this accuracy is presented. The third paper deals with how to avoid statistical inaccuracies when using machine learning techniques to analyze the data. In the fourth paper, we present a new tool for analyzing shotgun proteomics results, and evaluate the accuracy of  its statistical estimates using the method from the first papers. The work I have included here can facilitate the development of new and accurate computational tools in mass spectrometry-based proteomics. Such tools will help making the interpretation of the spectra and the downstream biological conclusions more reliable.