Pt(II) bipyridyl complexes bearing substituted fluorenyl motif on the bipyridyl and acetylide ligands : synthesis, photophysics, and reverse saturable absorption

A series of Pt(II) diimine complexes bearing benzothiazolylfluorenyl (BTZ-F8), diphenylaminofluorenyl (NPh2- F8), or naphthalimidylfluorenyl (NI-F8) motifs on the bipyridyl or acetylide ligands (Pt-4−Pt-8), (i.e., {4,4′-bis[7-R1-F8-(≡)n-]bpy}Pt(7- R2-F8- ≡ -)2, where F8 = 9,9′-di(2-ethylhexyl)fluorene, bpy = 2,2′- bipyridine, Pt-4: R1 = R2 = BTZ, n = 0; Pt-5: R1 = BTZ, R2 = NI, n = 0; Pt-6: R1 = R2 = BTZ, n = 1; Pt-7: R1 = BTZ, R2 = NPh2, n = 1; Pt- 8: R1 = NPh2, R2 = BTZ, n = 1) were synthesized. Their ground-state and excited-state properties and reverse saturable absorption performances were systematically investigated. The influence of these motifs on the photophysics of the complexes was investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). The intense absorption bands below 410 nm for these complexes is assigned to predominantly 1π,π* transitions localized on either the bipyridine or the acetylide ligands; while the broad low-energy absorption bands between 420 and 575 nm are attributed to essentially 1MLCT (metal-to-ligand charge transfer)/ 1LLCT (ligand-to-ligand charge transfer) transitions, likely mixed with some 1ILCT (intraligand charge transfer) transition for Pt-4−Pt-7, and predominantly 1ILCT transition admixing with minor 1MLCT/1LLCT characters for Pt-8. The different substituents on the acetylide and bipyridyl ligands, and the degrees of π-conjugation in the bipyridyl ligand influence both the 1π,π* and charge transfer transitions pronouncedly. All complexes are emissive at room temperature. Upon excitation at their respective absorption band maxima, Pt-4, Pt-6, and Pt-8 exhibit acetylide ligand localized 1π,π* fluorescence and 3MLCT/3LLCT phosphorescence in CH2Cl2, while Pt-5 manifests 1ILCT fluorescence and 3ILCT phosphorescence. However, only 1LLCT fluorescence was observed for Pt-7 at room temperature. The nanosecond transient absorption study was carried out for Pt-4−Pt-8 in CH3CN. Except for Pt-7 that contains NPh2 at the acetylide ligands, Pt-4−Pt-6 and Pt-8 all exhibit weak to moderate excited-state absorption in the visible spectral region. Reverse saturable absorption (RSA) of these complexes was demonstrated at 532 nm using 4.1 ns laser pulses in a 2 mm cuvette. The strength of RSA follows this trend: Pt-4 > Pt-5 > Pt-7 > Pt-6 > Pt-8. Incorporation of electron-donating substituent NPh2 on the bipyridyl ligand significantly decreases the RSA, while shorter π-conjugation in the bipyridyl ligand increases the RSA. Therefore, the substituent at either the acetylide ligands or the bipyridyl ligand could affect the singlet and triplet excited-state characteristics significantly, which strongly influences the RSA efficiency.

Novel polymer synthesis methodologies using combination of thermally and photochemically-induced nitroxide mediated polymerisation

The combination of thermally- and photochemically-induced polymerization using light sensitive alkoxyamines was investigated. The thermally driven polymerizations were performed via the cleavage of the alkoxyamine functionality, whereas the photochemically-induced polymerizations were carried out either by nitroxide mediated photo-polymerization (NMP2) or by a classical type II mechanism, depending on the structure of the light-sensitive alkoxyamine employed. Once the potential of the various structures as initiators of thermally- and photo-induced polymerizations was established, their use in combination for block copolymer syntheses was investigated. With each alkoxyamine investigated, block copolymers were successfully obtained and the system was applied to the post-modification of polymer coatings for application in patterning and photografting.

Synthesis of biodegradable polymer-mesoporous silica composite microspheres for DNA prime-protein boost vaccination

DNA vaccines or proteins are capable of inducing specific immunity; however, the translation to the clinic has generally been problematic, primarily due to the reduced magnitude of immune response and poor pharmacokinetics. Herein we demonstrate a composite microsphere formulation, composed of mesoporous silica spheres (MPS) and poly(d,l-lactide-co-glycolide) (PLGA), enables the controlled delivery of a prime-boost vaccine via the encapsulation of plasmid DNA (pDNA) and protein in different compartments. Method with modified dual-concentric-feeding needles attached to a 40 kHz ultrasonic atomizer was studied. These needles focus the flow of two different solutions, which passed through the ultrasonic atomizer. The process synthesis parameters, which are important to the scale-up of composite microspheres, were also studied. These parameters include polymer concentration, feed flowrate, and volumetric ratio of polymer and pDNA-PEI/MPS-BSA. This fabrication technique produced composite microspheres with mean D[4,3] ranging from 6 to 34 μm, depending upon the microsphere preparation. The resultant physical morphology of composite microspheres was largely influenced by the volumetric ratio of pDNA-PEI/MPS-BSA to polymer, and this was due to the precipitation of MPS at the surface of the microspheres. The encapsulation efficiencies were predominantly in the range of 93-98% for pDNA and 46-68% for MPS. In the in vitro studies, the pDNA and protein showed different release kinetics in a 40 day time frame. The dual-concentric-feeding in ultrasonic atomization was shown to have excellent reproducibility. It was concluded that this fabrication technique is an effective method to prepare formulations containing a heterologous prime-boost vaccine in a single delivery system.

Large-volume methacrylate monolith for plasmid purification : process engineering approach to synthesis and application

The extent of exothermicity associated with the construction of large-volume methacrylate monolithic columns has somewhat obstructed the realisation of large-scale rapid biomolecule purification especially for plasmid-based products which have proven to herald future trends in biotechnology. A novel synthesis technique via a heat expulsion mechanism was employed to prepare a 40 mL methacrylate monolith with a homogeneous radial pore structure along its thickness. Radial temperature gradient was recorded to be only 1.8 °C. Maximum radial temperature recorded at the centre of the monolith was 62.3 °C, which was only 2.3 °C higher than the actual polymerisation temperature. Pore characterisation of the monolithic polymer showed unimodal pore size distributions at different radial positions with an identical modal pore size of 400 nm. Chromatographic characterisation of the polymer after functionalisation with amino groups displayed a persistent dynamic binding capacity of 15.5 mg of plasmid DNA/mL. The maximum pressure drop recorded was only 0.12 MPa at a flow rate of 10 mL/min. The polymer demonstrated rapid separation ability by fractionating Escherichia coli DH5α-pUC19 clarified lysate in only 3 min after loading. The plasmid sample collected after the fast purification process was tested to be a homogeneous supercoiled plasmid with DNA electrophoresis and restriction analysis.

Process engineering approach to large-volume methacrylate monolith synthesis for plasmid purification

The construction of large?volume methacrylate monolithic columns for preparative-scale plasmid purification is obstructed by the enormous release of exotherms, thus introducing structural heterogeneity in the monolith pore system. A remarkable radial temperature gradient develops along the monolith thickness, reaching a terminal temperature that supersedes the maximum temperature required for the preparation of a structurally homogeneous monolith. A novel heat expulsion technique is employed to overcome the heat build-up during the synthesis process. The enormous heat build-up is perceived to encompass the heat associated with initiator decomposition and the heat released from free radical-monomer and monomer-monomer interactions. The heat resulting from the initiator decomposition was expelled along with some gaseous fumes before commencing polymerisation in a gradual addition fashion. Characteristics of a 50 mL monolith synthesized using this technique showed an improved uniformity in the pore structure radially along the length on the monolith. Chromatographic characterization of this adsorbent displayed a persistent binding capacity of 14.5 mg pDNA/mL of the adsorbent. The adsorbent was able to fractionate a clarified bacteria lysate in only 3 min (after loading) into RNA, protein and pDNA respectively. The pDNA fraction obtained was analyzed to be a homogeneous supercoiled pDNA.

Practical path planning and obstacle avoidance for autonomous mowing

There is a need for systems which can autonomously perform coverage tasks on large outdoor areas. Unfortunately, the state-of-the-art is to use GPS based localization, which is not suitable for precise operations near trees and other obstructions. In this paper we present a robotic platform for autonomous coverage tasks. The system architecture integrates laser based localization and mapping using the Atlas Framework with Rapidly-Exploring Random Trees path planning and Virtual Force Field obstacle avoidance. We demonstrate the performance of the system in simulation as well as with real world experiments.

Tech Ed students strut their stuff: information literacy and a practical assignment

This reports a study that seeks to explore the experience of students majoring in technology and design in an undergraduate education degree. It examines their experiences in finding and using information for a practical assignment. In mapping the variation of the students' experience, the study uses a qualitative, interpretive approach to analyse the data, which was collected via one-to-one interviews. The analysis yielded five themes through which technology education students find and use information: interaction with others; experience (past and new); formal educational learning; the real world; and incidental occurrences. The intentions and strategies that form the students' approaches to finding and using information are discussed. So too are the implications for teaching practice.

Synthesis of novel interlocked architectures in solution and solid phase

Mechanically interlocked molecules, such as catenanes and rotaxanes, are fascinating due to their unique sensing and catalytic properties and their potential to act as molecular motors or switches. Traditionally their synthesis has been laborious and expensive, however this research project endeavoured to overcome this challenge by exploring novel ways of preparing mechanically interlocked molecules both in solution and on surfaces. A series of disulfide-linked macrocycles, [2]catenanes and [2]rotaxanes were synthesised in solution using reversible dynamic covalent chemistry. Subsequently, the interlocked architectures were adapted into solid-tethered systems via attachment to swelling polystyrene resins.

Bayesian networks for information synthesis in complex systems

This thesis introduces a method of applying Bayesian Networks to combine information from a range of data sources for effective decision support systems. It develops a set of techniques in development, validation, visualisation, and application of Complex Systems models, with a working demonstration in an Australian airport environment. The methods presented here have provided a modelling approach that produces highly flexible, informative and applicable interpretations of a system's behaviour under uncertain conditions. These end-to-end techniques are applied to the development of model based dashboards to support operators and decision makers in the multi-stakeholder airport environment. They provide highly flexible and informative interpretations and confidence in these interpretations of a system's behaviour under uncertain conditions.

Practical linkages between cultural policy and education policy in promoting a creative workforce for youth in Tanzania

The broad aim of of this thesis is to contribute to understanding how the relationships between culture, employment and education can help Tanzania's young people secure jobs, and survive in the creative workforce so as to better their future. Based on a range of interviews and other data in Tanzania, the study considers how to integrate cultural expressions into arts education (education in art and education through art) as a tool for nurturing young people's creative talents for their future sustainable employment in Tanzania.

Practical implementation of species' recovery plans - Lessons from the White-backed Woodpecker Action Plan in Sweden

Successful biodiversity conservation requires safeguarding viable populations of species. To work with this challenge Sweden has introduced a concept of Action Plans, which focus on the recovery of one or more species; while keeping in mind the philosophy of addressing ecosystems in a more comprehensive way, following the umbrella concept. In this paper we investigate the implementationprocess of the ActionPlanfor one umbrella species, the White-backed Woodpecker (WBW) Dendrocopos leucotos. We describe the plan's organisation and goals, and investigate its implementation and accomplishment of particular targets, based on interviewing and surveying the key actors. The achievement of the targets in 2005-2008 was on average much lower than planned, explained partially by the lack of knowledge/data, experienced workers, and administrative flexibility. Surprisingly, the perceived importance of particular conservation measures, the investment priority accorded to them, the money available and various practical obstacles all failed to kg? explain the target levels achieved. However qualitative data from both the interviews and the survey highlight possible implementation obstacles: competing interests with other conservation actions and the level of engagement of particular implementing actors. Therefore we suggest that for successful implementation of recovery plans, there is aneed for initial and inclusive scoping prior to embarking on the plan, where not only issues like ecological knowledge and practical resources are considered, but also possible conflicts and synergies with other conservation actions. An adaptive approach with regular review of the conservation process is essential, particularly in the case of such complex action plans as the one for the WBW.

Navigating the methodological mire : practical epistemology in design research

The field of design research is a marketplace of methodological diversity. It isn't just that there are many different research methods in the field, but that there are many different methodological 'foundations' - principles for how research can and should be done, for how contributions to knowledge ought to be pursued. This is not particularly surprising given how broadly 'design' is often conceptualised. Herbert Simon (1996) suggested "the proper study of mankind is the science of design"; Nigel Cross has identified a principal difference between humankind and the animal kingdom to be our ability to design. In light of such encompassing notions of design it is difficult to imagine how the field of design research should exhibit any less diversity than that found within and among the arts, humanities, the human and social sciences.

Practical attack on NLM-MAC scheme

The NLM stream cipher designed by Hoon Jae Lee, Sang Min Sung, Hyeong Rag Kim is a strengthened version of the LM summation generator that combines linear and non-linear feedback shift registers. In recent works, the NLM cipher has been used for message authentication in lightweight communication over wireless sensor networks and for RFID authentication protocols. The work analyses the security of the NLM stream cipher and the NLM-MAC scheme that is built on the top of the NLM cipher. We first show that the NLM cipher suffers from two major weaknesses that lead to key recovery and forgery attacks. We prove the internal state of the NLM cipher can be recovered with time complexity about nlog7×2, where the total length of internal state is 2⋅n+22⋅n+2 bits. The attack needs about n2n2 key-stream bits. We also show adversary is able to forge any MAC tag very efficiently by having only one pair (MAC tag, ciphertext). The proposed attacks are practical and break the scheme with a negligible error probability.