The effect of Fe doping on adsorption of CO2/N2within carbon nanotubes : a density functional theory study with dispersion corrections

An ab initio density functional theory (DFT) study with correction for dispersive interactions was performed to study the adsorption of N2 and CO2 inside an (8, 8) single-walled carbon nanotube. We find that the approach of combining DFT and van der Waals correction is very effective for describing the long-range interaction between N2/CO2 and the carbon nanotube (CNT). Surprisingly, exohedral doping of an Fe atom onto the CNT surface will only affect the adsorption energy of the quadrupolar CO2 molecule inside the CNT (20–30%), and not that of molecular N2. Our results suggest the feasibility of enhancement of CO2/N2 separation in CNT-based membranes by using exohedral doping of metal atoms.

The catalytic role of an isolated-Ti atom in the hydrogenation of Ti-doped Al(001) surface : An ab initio density functional theory calculation

Recent work [S. Chaudhuri, J.T. Muckerman, J. Phys. Chem. B 109 (2005) 6952] reported that two Ti-substituted atoms on an Al(0 0 1) surface can form a catalytically active site for the dissociation of H2, but the diffusion barrier of atomic H away from Ti site is as high as 1.57 eV. By using ab initio density functional calculations, we found that two hydrogen molecules can dissociate on isolated-Ti atom doped Al(0 0 1) surface with small activation barriers (0.21 and 0.235 eV for first and second H2, respectively). Additionally, the diffusion barrier of atomic H away from Ti site is also moderate (0.47 eV). These results contribute further towards understanding the improved kinetics observed in recycling of hydrogen with Ti-doped NaAlH4.

Role of charge in destabilizing AlH4 and BH4 complex anions for hydrogen storage applications : Ab initio density functional calculations

NaAlH4 and LiBH4 are potential candidate materials for mobile hydrogen storage applications, yet they have the drawback of being highly stable and desorbing hydrogen only at elevated temperatures. In this letter, ab initio density functional theory calculations reveal how the stabilities of the AlH4 and BH4 complex anions will be affected by reducing net anionic charge. Tetrahedral AlH4 and BH4 complexes are found to be distorted with the decrease of negative charge. One H-H distance becomes smaller and the charge density will overlap between them at a small anion charge. The activation energies to release of H2 from AlH4 and BH4 complexes are thus greatly decreased. We demonstrate that point defects such as neutral Na vacancies or substitution of a Na atom with Ti on the NaAlH4(001) surface can potentially cause strong distortion of neighboring AlH4 complexes and even induce spontaneous dehydrogenation. Our results help to rationalize the conjecture that the suppression of charge transfer to AlH4 and BH4 anion as a consequence of surface defects should be very effective for improving the recycling performance of H2 in NaAlH4 and LiBH4. The understanding gained here will aid in the rational design and development of hydrogen storage materials based on these two systems.

Van der Waals-corrected density functional theory : benchmarking for hydrogen–nanotube and nanotube–nanotube interactions

Density functional theory (DFT) is a powerful approach to electronic structure calculations in extended systems, but suffers currently from inadequate incorporation of long-range dispersion, or Van der Waals (VdW) interactions. VdW-corrected DFT is tested for interactions involving molecular hydrogen, graphite, single-walled carbon nanotubes (SWCNTs), and SWCNT bundles. The energy correction, based on an empirical London dispersion term with a damping function at short range, allows a reasonable physisorption energy and equilibrium distance to be obtained for H2 on a model graphite surface. The VdW-corrected DFT calculation for an (8, 8) nanotube bundle reproduces accurately the experimental lattice constant. For H2 inside or outside an (8, 8) SWCNT, we find the binding energies are respectively higher and lower than that on a graphite surface, correctly predicting the well known curvature effect. We conclude that the VdW correction is a very effective method for implementing DFT calculations, allowing a reliable description of both short-range chemical bonding and long-range dispersive interactions. The method will find powerful applications in areas of SWCNT research where empirical potential functions either have not been developed, or do not capture the necessary range of both dispersion and bonding interactions.

Adatom CCV Auger rates via the local density of states

In this letter the core-core-valence Auger transitions of an atomic impurity, both in bulk or adsorbed on a jellium-like surface, are computed within a DFT framework. The Auger rates calculated by the Fermi golden rule are compared with those determined by an approximate and simpler expression. This is based on the local density of states (LDOS) with a core hole present, in a region around the impurity nucleus. Different atoms, Na and Mg, solids, Al and Ag, and several impurity locations are considered. We obtain an excellent agreement between KL1V and KL23V rates worked out with the two approaches. The radius of the sphere in which we calculate the LDOS is the relevant parameter of the simpler approach. Its value only depends on the atomic species regardless of the location of the impurity and the type of substrate. (C) 2003 Elsevier B.V. All rights reserved.

Effect of CT electron density identification on Monte Carlo simulations of radiotherapeutic treatments

Introduction: The accurate identification of tissue electron densities is of great importance for Monte Carlo (MC) dose calculations. When converting patient CT data into a voxelised format suitable for MC simulations, however, it is common to simplify the assignment of electron densities so that the complex tissues existing in the human body are categorized into a few basic types. This study examines the effects that the assignment of tissue types and the calculation of densities can have on the results of MC simulations, for the particular case of a Siemen’s Sensation 4 CT scanner located in a radiotherapy centre where QA measurements are routinely made using 11 tissue types (plus air). Methods: DOSXYZnrc phantoms are generated from CT data, using the CTCREATE user code, with the relationship between Hounsfield units (HU) and density determined via linear interpolation between a series of specified points on the ‘CT-density ramp’ (see Figure 1(a)). Tissue types are assigned according to HU ranges. Each voxel in the DOSXYZnrc phantom therefore has an electron density (electrons/cm3) defined by the product of the mass density (from the HU conversion) and the intrinsic electron density (electrons /gram) (from the material assignment), in that voxel. In this study, we consider the problems of density conversion and material identification separately: the CT-density ramp is simplified by decreasing the number of points which define it from 12 down to 8, 3 and 2; and the material-type-assignment is varied by defining the materials which comprise our test phantom (a Supertech head) as two tissues and bone, two plastics and bone, water only and (as an extreme case) lead only. The effect of these parameters on radiological thickness maps derived from simulated portal images is investigated. Results & Discussion: Increasing the degree of simplification of the CT-density ramp results in an increasing effect on the resulting radiological thickness calculated for the Supertech head phantom. For instance, defining the CT-density ramp using 8 points, instead of 12, results in a maximum radiological thickness change of 0.2 cm, whereas defining the CT-density ramp using only 2 points results in a maximum radiological thickness change of 11.2 cm. Changing the definition of the materials comprising the phantom between water and plastic and tissue results in millimetre-scale changes to the resulting radiological thickness. When the entire phantom is defined as lead, this alteration changes the calculated radiological thickness by a maximum of 9.7 cm. Evidently, the simplification of the CT-density ramp has a greater effect on the resulting radiological thickness map than does the alteration of the assignment of tissue types. Conclusions: It is possible to alter the definitions of the tissue types comprising the phantom (or patient) without substantially altering the results of simulated portal images. However, these images are very sensitive to the accurate identification of the HU-density relationship. When converting data from a patient’s CT into a MC simulation phantom, therefore, all possible care should be taken to accurately reproduce the conversion between HU and mass density, for the specific CT scanner used. Acknowledgements: This work is funded by the NHMRC, through a project grant, and supported by the Queensland University of Technology (QUT) and the Royal Brisbane and Women's Hospital (RBWH), Brisbane, Australia. The authors are grateful to the staff of the RBWH, especially Darren Cassidy, for assistance in obtaining the phantom CT data used in this study. The authors also wish to thank Cathy Hargrave, of QUT, for assistance in formatting the CT data, using the Pinnacle TPS. Computational resources and services used in this work were provided by the HPC and Research Support Group, QUT, Brisbane, Australia.

Pixel value to electron density conversion for a Megavoltage Cone Beam CT System

Introduction: The motivation for developing megavoltage (and kilovoltage) cone beam CT (MV CBCT) capabilities in the radiotherapy treatment room was primarily based on the need to improve patient set-up accuracy. There has recently been an interest in using the cone beam CT data for treatment planning. Accurate treatment planning, however, requires knowledge of the electron density of the tissues receiving radiation in order to calculate dose distributions. This is obtained from CT, utilising a conversion between CT number and electron density of various tissues. The use of MV CBCT has particular advantages compared to treatment planning with kilovoltage CT in the presence of high atomic number materials and requires the conversion of pixel values from the image sets to electron density. Therefore, a study was undertaken to characterise the pixel value to electron density relationship for the Siemens MV CBCT system, MVision, and determine the effect, if any, of differing the number of monitor units used for acquisition. If a significant difference with number of monitor units was seen then pixel value to ED conversions may be required for each of the clinical settings. The calibration of the MV CT images for electron density offers the possibility for a daily recalculation of the dose distribution and the introduction of new adaptive radiotherapy treatment strategies. Methods: A Gammex Electron Density CT Phantom was imaged with the MVCB CT system. The pixel value for each of the sixteen inserts, which ranged from 0.292 to 1.707 relative electron density to the background solid water, was determined by taking the mean value from within a region of interest centred on the insert, over 5 slices within the centre of the phantom. These results were averaged and plotted against the relative electron densities of each insert with a linear least squares fit was preformed. This procedure was performed for images acquired with 5, 8, 15 and 60 monitor units. Results: The linear relationship between MVCT pixel value and ED was demonstrated for all monitor unit settings and over a range of electron densities. The number of monitor units utilised was found to have no significant impact on this relationship. Discussion: It was found that the number of MU utilised does not significantly alter the pixel value obtained for different ED materials. However, to ensure the most accurate and reproducible MV to ED calibration, one MU setting should be chosen and used routinely. To ensure accuracy for the clinical situation this MU setting should correspond to that which is used clinically. If more than one MU setting is used clinically then an average of the CT values acquired with different numbers of MU could be utilized without loss in accuracy. Conclusions: No significant differences have been shown between the pixel value to ED conversion for the Siemens MV CT cone beam unit with change in monitor units. Thus as single conversion curve could be utilised for MV CT treatment planning. To fully utilise MV CT imaging for radiotherapy treatment planning further work will be undertaken to ensure all corrections have been made and dose calculations verified. These dose calculations may be either for treatment planning purposes or for reconstructing the delivered dose distribution from transit dosimetry measurements made using electronic portal imaging devices. This will potentially allow the cumulative dose distribution to be determined through the patient’s multi-fraction treatment and adaptive treatment strategies developed to optimize the tumour response.

Urban transit quality of service : user perception and behaviour

Despite its potential multiple contributions to sustainable policy objectives, urban transit is generally not widely used by the public in terms of its market share compared to that of automobiles, particularly in affluent societies with low-density urban forms like Australia. Transit service providers need to attract more people to transit by improving transit quality of service. The key to cost-effective transit service improvements lies in accurate evaluation of policy proposals by taking into account their impacts on transit users. If transit providers knew what is more or less important to their customers, they could focus their efforts on optimising customer-oriented service. Policy interventions could also be specified to influence transit users’ travel decisions, with targets of customer satisfaction and broader community welfare. This significance motivates the research into the relationship between urban transit quality of service and its user perception as well as behaviour. This research focused on two dimensions of transit user’s travel behaviour: route choice and access arrival time choice. The study area chosen was a busy urban transit corridor linking Brisbane central business district (CBD) and the St. Lucia campus of The University of Queensland (UQ). This multi-system corridor provided a ‘natural experiment’ for transit users between the CBD and UQ, as they can choose between busway 109 (with grade-separate exclusive right-of-way), ordinary on-street bus 412, and linear fast ferry CityCat on the Brisbane River. The population of interest was set as the attendees to UQ, who travelled from the CBD or from a suburb via the CBD. Two waves of internet-based self-completion questionnaire surveys were conducted to collect data on sampled passengers’ perception of transit service quality and behaviour of using public transit in the study area. The first wave survey is to collect behaviour and attitude data on respondents’ daily transit usage and their direct rating of importance on factors of route-level transit quality of service. A series of statistical analyses is conducted to examine the relationships between transit users’ travel and personal characteristics and their transit usage characteristics. A factor-cluster segmentation procedure is applied to respodents’ importance ratings on service quality variables regarding transit route preference to explore users’ various perspectives to transit quality of service. Based on the perceptions of service quality collected from the second wave survey, a series of quality criteria of the transit routes under study was quantitatively measured, particularly, the travel time reliability in terms of schedule adherence. It was proved that mixed traffic conditions and peak-period effects can affect transit service reliability. Multinomial logit models of transit user’s route choice were estimated using route-level service quality perceptions collected in the second wave survey. Relative importance of service quality factors were derived from choice model’s significant parameter estimates, such as access and egress times, seat availability, and busway system. Interpretations of the parameter estimates were conducted, particularly the equivalent in-vehicle time of access and egress times, and busway in-vehicle time. Market segmentation by trip origin was applied to investigate the difference in magnitude between the parameter estimates of access and egress times. The significant costs of transfer in transit trips were highlighted. These importance ratios were applied back to quality perceptions collected as RP data to compare the satisfaction levels between the service attributes and to generate an action relevance matrix to prioritise attributes for quality improvement. An empirical study on the relationship between average passenger waiting time and transit service characteristics was performed using the service quality perceived. Passenger arrivals for services with long headways (over 15 minutes) were found to be obviously coordinated with scheduled departure times of transit vehicles in order to reduce waiting time. This drove further investigations and modelling innovations in passenger’ access arrival time choice and its relationships with transit service characteristics and average passenger waiting time. Specifically, original contributions were made in formulation of expected waiting time, analysis of the risk-aversion attitude to missing desired service run in the passengers’ access time arrivals’ choice, and extensions of the utility function specification for modelling passenger access arrival distribution, by using complicated expected utility forms and non-linear probability weighting to explicitly accommodate the risk of missing an intended service and passenger’s risk-aversion attitude. Discussions on this research’s contributions to knowledge, its limitations, and recommendations for future research are provided at the concluding section of this thesis.

Matrix metalloproteinase biosensor based on a porous silicon reflector

Matrix metalloproteinases (MMPs) are proteolytic enzymes important to wound healing. In non-healing wounds, it has been suggested that MMP levels become dysfunctional, hence it is of great interest to develop sensors to detect MMP biomarkers. This study presents the development of a label-free optical MMP biosensor based on a functionalised porous silicon (pSi) thin film. The biosensor is fabricated by immobilising a peptidomimetic MMP inhibitor in the porous layer using hydrosilylation followed by amide coupling. The binding of MMP to the immobilised inhibitor translates into a change of effective optical thickness (EOT) over the time. We investigate the effect of surface functionalisation on the stability of pSi surface and evaluate the sensing performance. We successfully demonstrate MMP detection in buffer solution and human wound fluid at physiologically relevant concentrations. This biosensor may find application as a point-of-care device that is prognostic of the healing trajectory of chronic wounds.

Development of a large scale flexible LED display matrix for the screen industry

This project addresses the viability of lightweight, low power consumption, flexible, large format LED screens. The investigation encompasses all aspects of the electrical and mechanical design, individually and as a system, and achieves a successful full scale prototype. The prototype implements novel techniques to achieve large displacement colour aliasing, a purely passive thermal management solution, a rapid deployment system, individual seven bit LED current control with two way display communication, auto-configuration and complete signal redundancy, all of which are in direct response to industry needs.

Traffic density estimation of signalised arterials with stop line detector and probe data

This research aims to develop a reliable density estimation method for signalised arterials based on cumulative counts from upstream and downstream detectors. In order to overcome counting errors associated with urban arterials with mid-link sinks and sources, CUmulative plots and Probe Integration for Travel timE estimation (CUPRITE) is employed for density estimation. The method, by utilizing probe vehicles’ samples, reduces or cancels the counting inconsistencies when vehicles’ conservation is not satisfied within a section. The method is tested in a controlled environment, and the authors demonstrate the effectiveness of CUPRITE for density estimation in a signalised section, and discuss issues associated with the method.

Matrix metalloproteinase localisation by in situ-RT-PCR in archival human breast biopsy material

Utilising archival human breast cancer biopsy material we examined the stromal/epithelial interactions of several matrix metalloproteinases (MMPs) using in situ-RT-PCR (IS-RT-PCR). In breast cancer, the stromal/epithelial interactions that occur, and the site of production of these proteases, are central to understanding their role in invasive and metastatic processes. We examined MT1-MMP (MMP-14, membrane type-1-MMP), MMP-1 (interstitial collagenase) and MMP-3 (stromelysin-1) for their localisation profile in progressive breast cancer biopsy material (poorly differentiated invasive breast carcinoma (PDIBC), invasive breast carcinomas (IBC) and lymph node metastases (LNM)). Expression of MT1-MMP, MMP-1 and MMP-3 was observed in both the tumour epithelial and surrounding stromal cells in most tissue sections examined. MT1-MMP expression was predominantly localised to the tumour component in the pre-invasive lesions. MMP-1 gene expression was relatively well distributed between both tissue compartments, while MMP-3 demonstrated highest expression levels in the stromal tissue surrounding the epithelial tumour cells. The results demonstrate the ability to distinguish compartmental gene expression profiles using IS-RT-PCR. Further, we suggest a role for MT1-MMP in early tumour progression, expression of MMP-1 during metastasis and focal expression pattern of MMP-3 in areas of expansion. These expression profiles may provide markers for early breast cancer diagnoses and present potential therapeutic targets.

Investigation of the low-density lipoprotein receptor gene and cholesterol as a risk factor for migraine

The Low-Density Lipoprotein Receptor (LDLR) gene is a cell surface receptor that plays an important role in cholesterol homeostasis. We investigated the (TA)n polymorphism in exon 18 of the LDLR gene on chromosome 19p13.2 performing an association analysis in 244 typical migraine-affected patients, 151 suffering from migraine with aura (MA), 96 with migraine without aura (MO) and 244 unaffected controls. The populations consisted of Caucasians only, and controls were age- and sex-matched. The results showed no significant difference between groups for allele frequency distributions of the (TA)n polymorphism even after separation of the migraine-affected individuals into subgroups of MA and MO affected patients. This is in contradiction to Mochi et al. who found a positive association of this variant with MO. Our study discusses possible differences between the two studies and extends this research by investigating circulating cholesterol levels in a migraine-affected population.

Marked association of a RFLP for the low density lipoprotein receptor gene with obesity in essential hypertensives

RFLPs at the low density lipoprotein receptor locus (LDLR) display marked linkage disequilibrium between each other. Cross-sectional analysis of a bi-alleleic ApaLI RFLP of LDLR showed that the 9.4- and 6.6-kb alleles were present in similar frequency between a group of 84 Caucasian essential hypertensive (HT) and a group of 96 normotensive subjects whose parents each had a similar blood pressure status at age > or = 50. After subdividing HTs into lean and obese, however, the frequency of the 6.6-kb allele in the 27 HTs with BMI > or = 26 kg/m2 was 0.63, compared with 0.39 for HTs with BMI < 26 (chi 2 = 8.8; P = 0.004). The difference in genotype frequencies was even more striking (chi 2 = 23; P = 0.00008), with a virtual absence of 9.4-kb homozygotes in the obese HT group (1 vs 22). Genetic variation at LDLR (19p13.2) is thus associated with obesity in HT.

Association of a low density lipoprotein receptor microsatellite variant with obesity

OBJECTIVE To determine whether a microsatellite polymorphism located towards the 3' end of the low density lipoprotein receptor gene (LDLR) is associated with obesity. DESIGN A cross-sectional case-control study. SUBJECTS One hundred and seven obese individuals, defined as a body mass index (BMI) ≤ 26 kg/m2, and 163 lean individuals, defined as a BMI < 26 kg/m2. MEASUREMENTS BMI, blood pressure, serum lipids, alleles of LDLR microsatellite (106 bp, 108 bp and 112 bp). RESULTS There was a significant association between variants of the LDLR microsatellite and obesity, in the overall tested population, due to a contributing effect in females (χ2 = 12.3, P = 0.002), but not in males (χ2 = 0.3, P = 0.87). In females, individuals with the 106 bp allele were more likely to be lean, while individuals with the 112 bp and/or 108 bp alleles tended to be obese. CONCLUSIONS These results suggest that in females, LDLR may play a role in the development of obesity.