Denitrosation and nitrosation: a kinetic and mechanistic investigation

Section one of this thesis is concerned with the kinetics and mechanism of the process of denitrosation. At high concentrations of sufficiently reactive nucleophiles the rate of reaction of several N-alkyl-N-nitrosoanilines becomes independent of both the nature and the concentration of such species. This has been intrepreted in terms of a shift in the rate-determining to an earlier one in the reaction pathway, namely the protonation. Support for such a proposal comes from the solvent isotope effects K(_H(_2)O) : K(_D(_2)O) of 1.4 and 0.7, respectively. The denitrosation of D,L-N-acetyl-N-nitrosotryptophan (NANT) has been studied in water in the acid range 4 x 10(^-2) - 1M H(_2)SO(_4) and also at the lower acidities in buffer solution pH 2-6. The reaction was irreversible, giving D,L=N-acetyltryptophan (NAT) and nitrous acid quantitatively. At higher acidities the rate of reaction was independent of added parent amine NAT and also of the addition of various nucleophiles. The kinetic solvent isotope effect k(_H(_2)O) : k(_D(_2)O) was 1.3 and 1.1 at 0.7M H(_2)SO(_4) and 0.1M H(_2)SO(_4), respectively. At pH 6, however, the addition of various nucleophiles did catalyse the reaction, with increasing efficiency along the series C1(^-)<Br(^-)<SCN(^-)< 1(^-)~(^N)3(^-). As the concentration of nucleophile increased the reaction rate constant tended to become independent of the [nucleophile]. The results arc discussed in terms of two acid-catalysed reaction pathways, one predominate in the region pH 4-7 and the other at acidities greater than pH 1, as clearly shown by the pH - rate profile. At the higher acidities, N.ANT was used to nitrosate 4 - nitroaniline but only in the absence of a nitrous acid trap, thereby implicating the intermediacy of free nitrous acid. Section two is concerned with the reverse process, nitrosation. Thioureais shown to be a very efficient catalyst in the nitrosation of morpholine in acid solution. Compared with other known catalysts the order of efficienc

Rainfall as a cause of mechanical damage to Pseudocyphellaria rufovirescens in a New Zealand temperate rainforest

Lichens, like all poikilohydric plants, have a metabolism that is dependent on external moistening from their environment. In the case of green algal lichens high humidities may be sufficient for positive net photosynthesis to occur (Lange et al. 1993a). For these plants water stress is usually taken to mean a lack of water (Kappen 1988; Rundel 1988) but it can also mean an excess of water that leads to depressed CO2 exchange because of increased diffusion resistances at high thallus water contents (Lange & Tenhunen 1981; Kershaw 1985). Rather than this being an unusual occurrence, Lange et al. (19936) found reduced CO2 exchange at thallus supra-saturation to be present over long periods in the temperate rainforest of north-eastern New Zealand

Student musicians' self- and task-theories of musical performance : the influence of primary genre affiliation

165 undergraduate music students studying in Scotland completed a 30-statement Q-sort to describe their self and task-theories of musical performance. Statements reflected the importance of effort, confidence, technical ability, significant others and luck/ chance in determining a successful performance. The Q-sorts were reduced to six underlying sorting patterns, or viewpoints. The relationship between sorting patterns and participants' primary genre affiliation was explored in order to identify whether self and task-theories were a function of genre affiliation. Some intuitive hypotheses of what performers of particular musical genres might think were supported by the data. However, results suggested that there was considerable diversity in self and task-theory of performance within each of the genre affiliation groups, which supports previous research. Other background factors, such as gender, years of playing, chronological age and type of institution, were not significant predictors of self or task-theory of musical performance

Radio pulses from cosmic ray air showers - Boosted Coulomb and Cherenkov fields

High-energy cosmic rays passing through the Earth's atmosphere produce extensive showers whose charges emit radio frequency pulses. Despite the low density of the Earth's atmosphere, this emission should be affected by the air refractive index because the bulk of the shower particles move roughly at the speed of radio waves, so that the retarded altitude of emission, the relativistic boost and the emission pattern are modified. We consider in this paper the contribution of the boosted Coulomb and the Cherenkov fields and calculate analytically the spectrum using a very simplified model in order to highlight the main properties. We find that typically the lower half of the shower charge energy distribution produces a boosted Coulomb field, of amplitude comparable to the levels measured and to those calculated previously for synchrotron emission. Higher energy particles produce instead a Cherenkov-like field, whose amplitude may be smaller because both the negative charge excess and the separation between charges of opposite signs are small at these energies.Comment: 10 figures - Accepted by Astronomy & Astrophysic

Dynamic Forms

The paper describes a method for guiding a dynamic system through a given set of points. The paradigm is a fully automatic aircraft subject to air traffic control (ATC). The ATC provides a sequence of waypoints through which the aircraft trajectory must pass. The waypoints typically specify time, position, and velocity. The guidance problem is to synthesize a system state trajectory that satisfies both the ATC and aircraft constraints. Complications arise because the controlled process is multidimensional, multiaxis, nonlinear, highly coupled, and the state space is not flat. In addition, there is a multitude of operating modes, which may number in the hundreds. Each such mode defines a distinct state space model of the process by specifying the state space coordinatization, the partition of the controls into active controls and configuration controls, and the output map. Furthermore, mode transitions are required to be smooth. The proposed guidance algorithm is based on the inversion of the pure feedback approximation, followed by correction for the effects of zero dynamics. The paper describes the structure and major modules of the algorithm, and the performance is illustrated by several example aircraft maneuvers

Dynamic Forms. Part 1: Functions

The formalism of dynamic forms is developed as a means for organizing and systematizing the design control systems. The formalism allows the designer to easily compute derivatives to various orders of large composite functions that occur in flight-control design. Such functions involve many function-of-a-function calls that may be nested to many levels. The component functions may be multiaxis, nonlinear, and they may include rotation transformations. A dynamic form is defined as a variable together with its time derivatives up to some fixed but arbitrary order. The variable may be a scalar, a vector, a matrix, a direction cosine matrix, Euler angles, or Euler parameters. Algorithms for standard elementary functions and operations of scalar dynamic forms are developed first. Then vector and matrix operations and transformations between parameterization of rotations are developed in the next level in the hierarchy. Commonly occurring algorithms in control-system design, including inversion of pure feedback systems, are developed in the third level. A large-angle, three-axis attitude servo and other examples are included to illustrate the effectiveness of the developed formalism. All algorithms were implemented in FORTRAN code. Practical experience shows that the proposed formalism may significantly improve the productivity of the design and coding process

Overview of physics results from MAST towards ITER/DEMO and the MAST Upgrade

New diagnostic, modelling and plant capability on the Mega Ampere Spherical Tokamak (MAST) have delivered important results in key areas for ITER/DEMO and the upcoming MAST Upgrade, a step towards future ST devices on the path to fusion currently under procurement. Micro-stability analysis of the pedestal highlights the potential roles of micro-tearing modes and kinetic ballooning modes for the pedestal formation. Mitigation of edge localized modes (ELM) using resonant magnetic perturbation has been demonstrated for toroidal mode numbers n = 3, 4, 6 with an ELM frequency increase by up to a factor of 9, compatible with pellet fuelling. The peak heat flux of mitigated and natural ELMs follows the same linear trend with ELM energy loss and the first ELM-resolved T-i measurements in the divertor region are shown. Measurements of flow shear and turbulence dynamics during L-H transitions show filaments erupting from the plasma edge whilst the full flow shear is still present. Off-axis neutral beam injection helps to strongly reduce the redistribution of fast-ions due to fishbone modes when compared to on-axis injection. Low-k ion-scale turbulence has been measured in L-mode and compared to global gyro-kinetic simulations. A statistical analysis of principal turbulence time scales shows them to be of comparable magnitude and reasonably correlated with turbulence decorrelation time. T-e inside the island of a neoclassical tearing mode allow the analysis of the island evolution without assuming specific models for the heat flux. Other results include the discrepancy of the current profile evolution during the current ramp-up with solutions of the poloidal field diffusion equation, studies of the anomalous Doppler resonance compressional Alfven eigenmodes, disruption mitigation studies and modelling of the new divertor design for MAST Upgrade. The novel 3D electron Bernstein synthetic imaging shows promising first data sensitive to the edge current profile and flows

Methods and protocols for incremental exercise testing in tetraplegia, using arm-crank ergometry assisted by Functional Electrical Stimulation

Cervical spinal cord injury (SCI) leads to tetraplegia, with paralysis and loss of sensation in the upper and lower limbs. The associated sedentary lifestyle results in an increased risk of cardiovascular disease. To address this, we require the design of exercise modalities aimed specifically at tetraplegia and methods to assess their efficacy. This paper describes methods for arm-crank ergometry (ACE) assisted by Functional Electrical Stimulation (FES) applied to the biceps and triceps. The instrumented ergometer enables work-rate control during exercise, implemented here for incremental exercise testing during FES-ACE. Detailed protocols for the tests are given. Experimental data collected during exercise tests with tetraplegic volunteers are provided to illustrate the feasibility of the proposed approach to testing and data analysis. Incremental tests enabled calculation of peak power output and peak oxygen uptake. We propose that the high-precision exercise testing protocols described here are appropriate to assess the efficacy of the novel exercise modality, FES-ACE, in tetraplegia

Transcriptomic characterisation and genomic glimpse into the toxigenic dinoflagellate Azadinium spinosum, with emphasis on polykeitde synthase genes

Background: Unicellular dinoflagellates are an important group of primary producers within the marine plankton community. Many of these species are capable of forming harmful algae blooms (HABs) and of producing potent phycotoxins, thereby causing deleterious impacts on their environment and posing a threat to human health. The recently discovered toxigenic dinoflagellate Azadinium spinosum is known to produce azaspiracid toxins. These toxins are most likely produced by polyketide synthases (PKS). Recently, PKS I-like transcripts have been identified in a number of dinoflagellate species. Despite the global distribution of A. spinosum, little is known about molecular features. In this study, we investigate the genomic and transcriptomic features of A. spinosum with a focus on polyketide synthesis and PKS evolution. Results: We identify orphan and homologous genes by comparing the transcriptome data of A. spinosum with a diverse set of 18 other dinoflagellates, five further species out of the Rhizaria Alveolate Stramelopile (RAS)-group, and one representative from the Plantae. The number of orphan genes in the analysed dinoflagellate species averaged 27%. In contrast, within the A. spinosum transcriptome, we discovered 12,661 orphan transcripts (18%). The dinoflagellates toxins known as azaspiracids (AZAs) are structurally polyethers; we therefore analyse the transcriptome of A. spinosum with respect to polyketide synthases (PKSs), the primary biosynthetic enzymes in polyketide synthesis.We find all the genes thought to be potentially essential for polyketide toxin synthesis to be expressed in A. spinosum,whose PKS transcripts fall into the dinoflagellate sub-clade in PKS evolution. Conclusions: Overall, we demonstrate that the number of orphan genes in the A. spinosum genome is relatively small compared to other dinoflagellate species. In addition, all PKS domains needed to produce the azaspiracid carbon backbone are present in A. spinosum. Our study underscores the extraordinary evolution of such gene clusters and, in particular, supports the proposed structural and functional paradigm for PKS Type I genes in dinoflagellates

Optimizing the Readout of Lanthanide-DOTA Complexes for the Detection of Ligand-Bound Copper(I)

The CuAAC ‘click’ reaction was used to couple alkyne-functionalized lanthanide-DOTA complexes to a range of fluorescent antennae. Screening of the antenna components was aided by comparison of the luminescent output of the resultant sensors using data normalized to account for reaction conversion as assessed by IR. A maximum 82-fold enhanced signal:background luminescence output was achieved using a Eu(III)-DOTA complex coupled to a coumarin-azide, in a reaction which is specific to the presence of copper(I). This optimized complex provides a new lead design for lanthanide-DOTA complexes which can act as irreversible ‘turn-on’ catalytic sensors for the detection of ligand-bound copper(I)