Dietary supplementation with vitamin C but not vitamin E reduces constitutive expression of ICAM-1 in peripheral blood monocytes of normal subjects with low plasma vitamin C levels

Monocytes play a central role in inflammatory responses through systemic antigen presentation and cytokine secretion. Regulation of monocyte adhesion molecule and inflammatory gene expression is via redox sensitive transcription factors. Therefore we have investigated the hypothesis that dietary antioxidant supplementation with vitamins C (250mg/d) or E (400iU/d) for six weeks can modulate monocyte ICAM-1 expression in healthy male subjects with low plasma vitamin C at baseline. In a randomised, double-blind, crossover study, ICAM-1 mRNA and protein was analysed using quantitative RTPCR with ELISA measurement of PCR products and by flow cytometry and ELISA respectively. Monocyte numbers were unaltered by supplementation. Subjects with low plasma vitamin C (<50uM) prior to supplementation expressed higher levels of monocyte ICAM-1 mRNA, and showed a significant (50%) reduction in ICAM-1 mRNA expression after 6 weeks of 250mg/d vitamin C supplementation compared to subjects with normal plasma vitamin C. This was paralleled by a reduction in plasma sICAM-1. Vitamin E supplementation had no effect on ICAM-1 expression. For the first time, these results show that dietary vitamin C can modulate monocyte ICAM-1 gene expression in vivo, where regulation of gene expression represents a novel mechanism for benefit from dietary antioxidants.

Hopping transport on a fractal: ac conductivity of porous silicon

We have measured the frequency dependence of the conductivity and the dielectric constant of various samples of porous Si in the regime 1 Hz-100 kHz at different temperatures. The conductivity data exhibit a strong frequency dependence. When normalized to the dc conductivity, our data obey a universal scaling law, with a well-defined crossover, in which the real part of the conductivity sigma' changes from an sqrt(omega) dependence to being proportional to omega. We explain this in terms of activated hopping in a fractal network. The low-frequency regime is governed by the fractal properties of porous Si, whereas the high-frequency dispersion comes from a broad distribution of activation energies. Calculations using the effective-medium approximation for activated hopping on a percolating lattice give fair agreement with the data.

Interplay between the charge transport phenomena and the charge-transfer phase transition in RbxMn[Fe(CN)6]y.zH2O

Charge transport and dielectric measurements were carried out on compacted powder and single-crystal samples of bistable RbxMn[Fe(CN)6]y·zH2O in the two valence-tautomeric forms (MnIIFeIII and MnIIIFeII) as a function of temperature (120-350 K) and frequency (10-2-106 Hz). The complex conductivity data reveal universal conductivity behavior and obey the Barton-Nakajima-Namikawa relationship. The charge transport is accompanied by dielectric relaxation that displays the same thermal activation energy as the conductivity. Surprisingly, the activation energy of the conductivity was found very similar in the two valence-tautomeric forms (0.55 eV), and the conductivity change between the two phases is governed mainly by the variation of the preexponential factor in each sample. The phase transition is accompanied by a large thermal hysteresis of the conductivity and the dielectric constant. In the hysteresis region, however, a crossover occurs in the charge transport mechanism at T < 220 K from an Arrhenius-type to a varying activation energy behavior, conferring an unusual “double-loop” shape to the hysteresis.

Representation and parameterisation issues in genetic algorithms

A multi-chromosome GA (Multi-GA) was developed, based upon concepts from the natural world, allowing improved flexibility in a number of areas including representation, genetic operators, their parameter rates and real world multi-dimensional applications. A series of experiments were conducted, comparing the performance of the Multi-GA to a traditional GA on a number of recognised and increasingly complex test optimisation surfaces, with promising results. Further experiments demonstrated the Multi-GA's flexibility through the use of non-binary chromosome representations and its applicability to dynamic parameterisation. A number of alternative and new methods of dynamic parameterisation were investigated, in addition to a new non-binary 'Quotient crossover' mechanism. Finally, the Multi-GA was applied to two real world problems, demonstrating its ability to handle mixed type chromosomes within an individual, the limited use of a chromosome level fitness function, the introduction of new genetic operators for structural self-adaptation and its viability as a serious real world analysis tool. The first problem involved optimum placement of computers within a building, allowing the Multi-GA to use multiple chromosomes with different type representations and different operators in a single individual. The second problem, commonly associated with Geographical Information Systems (GIS), required a spatial analysis location of the optimum number and distribution of retail sites over two different population grids. In applying the Multi-GA, two new genetic operators (addition and deletion) were developed and explored, resulting in the definition of a mechanism for self-modification of genetic material within the Multi-GA structure and a study of this behaviour.

Soliton propagation through a disordered system:statistics of the transmission delay

We have studied the soliton propagation through a segment containing random pointlike scatterers. In the limit of small concentration of scatterers when the mean distance between the scatterers is larger than the soliton width, a method has been developed for obtaining the statistical characteristics of the soliton transmission through the segment. The method is applicable for any classical particle traversing through a disordered segment with the given velocity transformation after each act of scattering. In the case of weak scattering and relatively short disordered segment the transmission time delay of a fast soliton is mostly determined by the shifts of the soliton center after each act of scattering. For sufficiently long segments the main contribution to the delay is due to the shifts of the amplitude and velocity of a fast soliton after each scatterer. Corresponding crossover lengths for both cases of light and heavy solitons have been obtained. We have also calculated the exact probability density function of the soliton transmission time delay for a sufficiently long segment. In the case of weak identical scatterers the latter is a universal function which depends on a sole parameter—the mean number of scatterers in a segment.

Observation of a 331 K (58 °C) spin transition for bis[hydrotris(1,2,4-triazol-1-yl)borate]iron(II) by variable temperature infrared spectroscopy and magnetic susceptibility measurements

Fe{HB(CHN)} is observed by variable temperature infrared and magnetic studies to have a spin transition between the low spin S = 0 and high spin S = 2 states at 331 K (58 °C) with thermal hysteresis of ~1.5 K. Changes in the triazole ligand IR absorptions demonstrate that distant non-metal-ligand vibrations are altered upon the change in electronic structure associated with the spin-crossover can be used to monitor the the spin-crossover transition.

Evolutionary neural networks : models and applications

The scaling problems which afflict attempts to optimise neural networks (NNs) with genetic algorithms (GAs) are disclosed. A novel GA-NN hybrid is introduced, based on the bumptree, a little-used connectionist model. As well as being computationally efficient, the bumptree is shown to be more amenable to genetic coding lthan other NN models. A hierarchical genetic coding scheme is developed for the bumptree and shown to have low redundancy, as well as being complete and closed with respect to the search space. When applied to optimising bumptree architectures for classification problems the GA discovers bumptrees which significantly out-perform those constructed using a standard algorithm. The fields of artificial life, control and robotics are identified as likely application areas for the evolutionary optimisation of NNs. An artificial life case-study is presented and discussed. Experiments are reported which show that the GA-bumptree is able to learn simulated pole balancing and car parking tasks using only limited environmental feedback. A simple modification of the fitness function allows the GA-bumptree to learn mappings which are multi-modal, such as robot arm inverse kinematics. The dynamics of the 'geographic speciation' selection model used by the GA-bumptree are investigated empirically and the convergence profile is introduced as an analytical tool. The relationships between the rate of genetic convergence and the phenomena of speciation, genetic drift and punctuated equilibrium arc discussed. The importance of genetic linkage to GA design is discussed and two new recombination operators arc introduced. The first, linkage mapped crossover (LMX) is shown to be a generalisation of existing crossover operators. LMX provides a new framework for incorporating prior knowledge into GAs.Its adaptive form, ALMX, is shown to be able to infer linkage relationships automatically during genetic search.

Global non-dynamic refinement of radial orbit error for altimetric earth satellites

The accuracy of altimetrically derived oceanographic and geophysical information is limited by the precision of the radial component of the satellite ephemeris. A non-dynamic technique is proposed as a method of reducing the global radial orbit error of altimetric satellites. This involves the recovery of each coefficient of an analytically derived radial error correction through a refinement of crossover difference residuals. The crossover data is supplemented by absolute height measurements to permit the retrieval of otherwise unobservable geographically correlated and linearly combined parameters. The feasibility of the radial reduction procedure is established upon application to the three day repeat orbit of SEASAT. The concept of arc aggregates is devised as a means of extending the method to incorporate longer durations, such as the 35 day repeat period of ERS-1. A continuous orbit is effectively created by including the radial misclosure between consecutive long arcs as an infallible observation. The arc aggregate procedure is validated using a combination of three successive SEASAT ephemerides. A complete simulation of the 501 revolution per 35 day repeat orbit of ERS-1 is derived and the recovery of the global radial orbit error over the full repeat period is successfully accomplished. The radial reduction is dependent upon the geographical locations of the supplementary direct height data. Investigations into the respective influences of various sites proposed for the tracking of ERS-1 by ground-based transponders are carried out. The potential effectiveness on the radial orbital accuracy of locating future tracking sites in regions of high latitudinal magnitude is demonstrated.

Various techniques and procedures for refining ERS-1 orbits

The satellite ERS-1 was launched in July 1991 in a period of high solar activity. Sparse laser tracking and the failure of the experimental microwave system (PRARE) compounded the orbital errors which resulted from mismodelling of atmospheric density and hence surface forces. Three attempts are presented here to try and refine the coarse laser orbits of ERS-1, made prior to the availability of the full altimetric dataset. The results of the first attempt indicate that by geometrically modelling the satellite shape some improvement in orbital precision may be made for any satellite; especially one where no area tables already exist. The second and third refinement attempts are based on the introduction of data from some second satellite; in these examples SPOT-2 and TOPEX/Poseidon are employed. With SPOT-2 the method makes use of the orbital similarities to produce along-track corrections for the more fully tracked SPOT-2. Transferring these corrections to ERS-1 produces improvements in the precise orbits thus determined. With TOPEX/Poseidon the greater altitude results in a more precise orbit (gravity field and atmospheric errors are of less importance). Thus, by computing height differences at crossover points of the TOPEX/Poseidon and ERS-1 ground tracks the poorer orbit of ERS-1 may be improved by the addition of derived radial corrections. In the positive light of all three results several potential modification are suggested and some further avenues of investigation indicated.

Precise orbit determination and analysis from satellite altimetry and laser ranging

For optimum utilization of satellite-borne instrumentation, it is necessary to know precisely the orbital position of the spacecraft. The aim of this thesis is therefore two-fold - firstly to derive precise orbits with particular emphasis placed on the altimetric satellite SEASAT and secondly, to utilize the precise orbits, to improve upon atmospheric density determinations for satellite drag modelling purposes. Part one of the thesis, on precise orbit determinations, is particularly concerned with the tracking data - satellite laser ranging, altimetry and crossover height differences - and how this data can be used to analyse errors in the orbit, the geoid and sea-surface topography. The outcome of this analysis is the determination of a low degree and order model for sea surface topography. Part two, on the other hand, mainly concentrates on using the laser data to analyse and improve upon current atmospheric density models. In particular, the modelling of density changes associated with geomagnetic disturbances comes under scrutiny in this section. By introducing persistence modelling of a geomagnetic event and solving for certain geomagnetic parameters, a new density model is derived which performs significantly better than the state-of-the-art models over periods of severe geomagnetic storms at SEASAT heights. This is independently verified by application of the derived model to STARLETTE orbit determinations.

The use of ERS-1 crossovers and TOPEX/Poseidon repeat pass data for global sea surface variability studies

In previous sea-surface variability studies, researchers have failed to utilise the full ERS-1 mission due to the varying orbital characteristics in each mission phase, and most have simply ignored the Ice and Geodetic phases. This project aims to introduce a technique which will allow the straightforward use of all orbital phases, regardless of orbit type. This technique is based upon single satellite crossovers. Unfortunately the ERS-1 orbital height is still poorly resolved (due to higher air drag and stronger gravitational effects) when compared with that of TOPEX/Poseidon (T/P), so to make best use of the ERS-1 crossover data corrections to the ERS-1 orbital heights are calculated by fitting a cubic-spline to dual-crossover residuals with T/P. This correction is validated by comparison of dual satellite crossovers with tide gauge data. The crossover processing technique is validated by comparing the extracted sea-surface variability information with that from T/P repeat pass data. The two data sets are then combined into a single consistent data set for analysis of sea-surface variability patterns. These patterns are simplified by the use of an empirical orthogonal function decomposition which breaks the signals into spatial modes which are then discussed separately. Further studies carried out on these data include an analysis of the characteristics of the annual signal, discussion of evidence for Rossby wave propagation on a global basis, and finally analysis of the evidence for global mean sea level rise.

Combination of altimetry data from different satellite missions

Substantial altimetry datasets collected by different satellites have only become available during the past five years, but the future will bring a variety of new altimetry missions, both parallel and consecutive in time. The characteristics of each produced dataset vary with the different orbital heights and inclinations of the spacecraft, as well as with the technical properties of the radar instrument. An integral analysis of datasets with different properties offers advantages both in terms of data quantity and data quality. This thesis is concerned with the development of the means for such integral analysis, in particular for dynamic solutions in which precise orbits for the satellites are computed simultaneously. The first half of the thesis discusses the theory and numerical implementation of dynamic multi-satellite altimetry analysis. The most important aspect of this analysis is the application of dual satellite altimetry crossover points as a bi-directional tracking data type in simultaneous orbit solutions. The central problem is that the spatial and temporal distributions of the crossovers are in conflict with the time-organised nature of traditional solution methods. Their application to the adjustment of the orbits of both satellites involved in a dual crossover therefore requires several fundamental changes of the classical least-squares prediction/correction methods. The second part of the thesis applies the developed numerical techniques to the problems of precise orbit computation and gravity field adjustment, using the altimetry datasets of ERS-1 and TOPEX/Poseidon. Although the two datasets can be considered less compatible that those of planned future satellite missions, the obtained results adequately illustrate the merits of a simultaneous solution technique. In particular, the geographically correlated orbit error is partially observable from a dataset consisting of crossover differences between two sufficiently different altimetry datasets, while being unobservable from the analysis of altimetry data of both satellites individually. This error signal, which has a substantial gravity-induced component, can be employed advantageously in simultaneous solutions for the two satellites in which also the harmonic coefficients of the gravity field model are estimated.

Application of ERS-1 and Topex/Poseidon altimetry using precise orbits

The work described in this thesis concerns the application of radar altimetry, collected from the ERS-1 and TOPEX/POSEIDON missions, to precise satellite orbits computed at Aston University. The data is analysed in a long arc fashion to determine range biases, time tag biases, sea surface topographies and to assess the radial accuracy of the generated orbits through crossover analysis. A sea surface variability study is carried out for the North Sea using repeat altimeter profiles from ERS-1 and TOPEX/POSEIDON in order to verify two local U.K. models for ocean tide and storm surge effects. An on-side technique over the English Channel is performed to compute the ERS-1, TOPEX and POSEIDON altimeter range biases by using a combination of altimetry, precise orbits determined by short arc methods, tide gauge data, GPS measurements, geoid, ocean tide and storm surge models. The remaining part of the thesis presents some techniques for the short arc correction of long arc orbits. Validation of this model is achieved by way of comparison with actual SEASAT short arcs. Simulations are performed for the ERS-1 microwave tracking system, PRARE, using the range data to determine time dependent orbit corrections. Finally, a brief chapter is devoted to the recovery of errors in station coordinates by the use of multiple short arcs.

Orbit and altimetric corrections for the ERS satellites through analysis of single and dual satellite crossovers

Due to the failure of PRARE the orbital accuracy of ERS-1 is typically 10-15 cm radially as compared to 3-4cm for TOPEX/Poseidon. To gain the most from these simultaneous datasets it is necessary to improve the orbital accuracy of ERS-1 so that it is commensurate with that of TOPEX/Poseidon. For the integration of these two datasets it is also necessary to determine the altimeter and sea state biases for each of the satellites. Several models for the sea state bias of ERS-1 are considered by analysis of the ERS-1 single satellite crossovers. The model adopted consists of the sea state bias as a percentage of the significant wave height, namely 5.95%. The removal of ERS-1 orbit error and recovery of an ERS-1 - TOPEX/Poseidon relative bias are both achieved by analysis of dual crossover residuals. The gravitational field based radial orbit error is modelled by a finite Fourier expansion series with the dominant frequencies determined by analysis of the JGM-2 co-variance matrix. Periodic and secular terms to model the errors due to atmospheric density, solar radiation pressure and initial state vector mis-modelling are also solved for. Validation of the dataset unification consists of comparing the mean sea surface topographies and annual variabilities derived from both the corrected and uncorrected ERS-1 orbits with those derived from TOPEX/Poseidon. The global and regional geographically fixed/variable orbit errors are also analysed pre and post correction, and a significant reduction is noted. Finally the use of dual/single satellite crossovers and repeat pass data, for the calibration of ERS-2 with respect to ERS-1 and TOPEX/Poseidon is shown by calculating the ERS-1/2 sea state and relative biases.

Gold nanoparticles decorated with oligo(ethylene glycol) thiols:kinetics of colloid aggregation driven by depletion forces

We have studied the kinetics of the phase-separation process of mixtures of colloid and protein in solutions by real-time UV-vis spectroscopy. Complementary small-angle X-ray scattering (SAXS) was employed to determine the structures involved. The colloids used are gold nanoparticles functionalized with protein resistant oligo(ethylene glycol) (OEG) thiol, HS(CH(2))(11)(OCH(2)CH(2))(6)OMe (EG6OMe). After mixing with protein solution above a critical concentration, c*, SAXS measurements show that a scattering maximum appears after a short induction time at q = 0.0322 angstrom(-1) stop, which increases its intensity with time but the peak position does not change with time, protein concentration and salt addition. The peak corresponds to the distance of the nearest neighbor in the aggregates. The upturn of scattering intensities in the low q-range developed with time indicating the formation of aggregates. No Bragg peaks corresponding to the formation of colloidal crystallites could be observed before the clusters dropped out from the solution. The growth kinetics of aggregates is followed in detail by real-time UV-vis spectroscopy, using the flocculation parameter defined as the integral of the absorption in the range of 600-800 nm wavelengths. At low salt addition (<0.5 M), a kinetic crossover from reaction-limited cluster aggregation (RLCA) to diffusion-limited cluster aggregation (DLCA) growth model is observed, and interpreted as being due to the effective repulsive interaction barrier between colloids within the depletion potential. Above 0.5 M NaCl, the surface charge of proteins is screened significantly, and the repulsive potential barrier disappeared, thus the growth kinetics can be described by a DLCA model only.