THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

Evaluation of separation management algorithms in Class G airspace

Use of Unmanned Aerial Vehicles (UAVs) in support of government applications has already seen significant growth and the potential for use of UAVs in commercial applications is expected to rapidly expand in the near future. However, the issue remains on how such automated or operator-controlled aircraft can be safely integrated into current airspace. If the goal of integration is to be realized, issues regarding safe separation in densely populated airspace must be investigated. This paper investigates automated separation management concepts in uncontrolled airspace that may help prepare for an expected growth of UAVs in Class G airspace. Not only are such investigations helpful for the UAV integration issue, the automated separation management concepts investigated by the authors can also be useful for the development of new or improved Air Traffic Control services in remote regions without any existing infrastructure. The paper will also provide an overview of the Smart Skies program and discuss the corresponding Smart Skies research and development effort to evaluate aircraft separation management algorithms using simulations involving realworld data communication channels, and verified against actual flight trials. This paper presents results from a unique flight test concept that uses real-time flight test data from Australia over existing commercial communication channels to a control center in Seattle for real-time separation management of actual and simulated aircraft. The paper also assesses the performance of an automated aircraft separation manager.

Non-adversarial advocates and gatekeepers : lawyers, FDR practitioners and co-operative post-separation parenting

The compulsory dispute resolution requirements in family law parenting cases create new roles and obligations for both lawyers and family dispute resolution (FDR) practitioners. This article will discuss how the legislative provisions impact on both sets of professionals in practice. It will also highlight the increased non-adversarial role of lawyers and a new role for FDR practitioners as “gatekeepers” to family courts in cases requiring FDR certificates.

High-performance ceramic membranes with a separation layer of metal oxide nanofibers

In conventional fabrication of ceramic separation membranes, the particulate sols are applied onto porous supports. Major structural deficiencies under this approach are pin-holes and cracks, and the dramatic losses of flux when pore sizes are reduced to enhance selectivity. We have overcome these structural deficiencies by constructing hierarchically structured separation layer on a porous substrate using lager titanate nanofibers and smaller boehmite nanofibers. This yields a radical change in membrane texture. The resulting membranes effectively filter out species larger than 60 nm at flow rates orders of magnitude greater than conventional membranes. This reveals a new direction in membrane fabrication.

Ceramic membranes for separation of proteins and DNA by in situ growth of alumina nanofibres with a nanomesh of metal oxide nanofibres

Ceramic membranes were fabricated by in situ synthesis of alumina nanofibres in the pores of an alumina support as a separation layer, and exhibited a high permeation selectivity for bovine serum albumin relative to bovine hemoglobin (over 60 times) and can effectively retain DNA molecules at high fluxes.

Porous PLGA microspheres effectively loaded with BSA protein by electrospraying combined with phase separation in liquid nitrogen

Polymer microspheres loaded with bioactive particles, biomolecules, proteins, and/or growth factors play important roles in tissue engineering, drug delivery, and cell therapy. The conventional double emulsion method and a new method of electrospraying into liquid nitrogen were used to prepare bovine serum albumin (BAS)-loaded poly(lactic-co-glycolic acid) (PLGA) porous microspheres. The particle size, the surface morphology and the internal porous structure of the microspheres were observed using scanning electron microscopy (SEM). The loading efficiency, the encapsulation efficiency, and the release profile of the BSA-loaded PLGA microspheres were measured and studied. It was shown that the microspheres from double emulsion had smaller particle sizes (3-50 m), a less porous structure, a poor loading efficiency (5.2 %), and a poor encapsulation efficiency (43.5%). However, the microspheres from the electrospraying into liquid nitrogen had larger particle sizes (400-600 m), a highly porous structure, a high loading efficiency (12.2%), and a high encapsulation efficiency (93.8%). Thus the combination of electrospraying with freezing in liquid nitrogen and subsequent freeze drying represented a suitable way to produce polymer microspheres for effective loading and sustained release of proteins.

Separation management approaches during periods of communication failure

New air traffic automated separation management concepts are constantly under investigation. Yet most of the automated separation management algorithms proposed over the last few decades have assumed either perfect communication or exact knowledge of all aircraft locations. In realistic environments, these idealized assumptions are not valid and any communication failure can potentially lead to disastrous outcomes. This paper examines the separation performance behavior of several popular algorithms during periods of information loss. This comparison is done through simulation studies. These simulation studies suggest that communication failure can cause the performance of these separation management algorithms to degrade significantly. This paper also describes some preliminary flight tests.

Automated centralised separation management with onboard decision support

This paper proposes a novel automated separation management concept in which onboard decision support is integrated within a centralised air traffic separation management system. The onboard decision support system involves a decentralised separation manager that can overrule air traffic management instructions under certain circumstances. This approach allows the advantages of both centralised and decentralised concepts to be combined (and disadvantages of each separation management approach to be mitigated). Simulation studies are used to illustrate the potential benefits of the combined separation management concept.

Microphone array beamforming approach to blind speech separation

In this paper, we present a microphone array beamforming approach to blind speech separation. Unlike previous beamforming approaches, our system does not require a-priori knowledge of the microphone placement and speaker location, making the system directly comparable other blind source separation methods which require no prior knowledge of recording conditions. Microphone location is automatically estimated using an assumed noise field model, and speaker locations are estimated using cross correlation based methods. The system is evaluated on the data provided for the PASCAL Speech Separation Challenge 2 (SSC2), achieving a word error rate of 58% on the evaluation set.

Modelling cell separation during plant organ abscission

A simple mathematical model is presented to describe the cell separation process that plants undertake in order to deliberately shed organs. The focus here is on modelling the production of the enzyme polygalacturonase, which breaks down pectin that provides natural cell-to-cell adhesion in the localised abscission zone. A coupled system of three ordinary differential equations is given for a single cell, and then extended to hold for a layer of cells in the abscission zone. Simple observations are made based on the results of this preliminary model and, furthermore, a number of opportunities for applied mathematicians to make contributions in this subject area are discussed.

Flight testing of an augmented separation management system providing separation protection during failure of the central communication network

Future air traffic management concepts often involve the proposal of automated separation management algorithms that replaces human air traffic controllers. This paper proposes a new type of automated separation management algorithm (based on the satisficing approach) that utilizes inter-aircraft communication and a track file manager (or bank of Kalman filters) that is capable of resolving conflicts during periods of communication failure. The proposed separation management algorithm is tested in a range of flight scenarios involving during periods of communication failure, in both simulation and flight test (flight tests were conducted as part of the Smart Skies project). The intention of the conducted flight tests was to investigate the benefits of using inter-aircraft communication to provide an extra layer of safety protection in support air traffic management during periods of failure of the communication network. These benefits were confirmed.