Diels-Alder reactions as an efficient route to high purity cyclic polymers

A simple and efficient route for the synthesis of cyclic polymer systems is presented. Linear furan protected α-maleimide-ω-cyclopentadienyl functionalized precursors (poly(methyl methacrylate) and poly(tert-butyl acrylate)) were synthesized via atom transfer radical polymerization (ATRP) and subsequent substitution of the bromine end-group with cyclopentadiene. Upon heating at high dilution, deprotection of the dieneophile occurs followed by an intramolecular Diels–Alder reaction yielding a high purity cyclic product.

Properties of lignin and poly(hydroxybutyrate) blends

The Queensland University of Technology (QUT) allows the presentation of a thesis for the Degree of Doctor of Philosophy in the format of published or submitted papers, where such papers have been published, accepted or submitted during the period of candidature. This thesis is composed of Seven published/submitted papers and one poster presentation, of which five have been published and the other two are under review. This project is financially supported by the QUTPRA Grant. The twenty-first century started with the resurrection of lignocellulosic biomass as a potential substitute for petrochemicals. Petrochemicals, which enjoyed the sustainable economic growth during the past century, have begun to reach or have reached their peak. The world energy situation is complicated by political uncertainty and by the environmental impact associated with petrochemical import and usage. In particular, greenhouse gasses and toxic emissions produced by petrochemicals have been implicated as a significant cause of climate changes. Lignocellulosic biomass (e.g. sugarcane biomass and bagasse), which potentially enjoys a more abundant, widely distributed, and cost-effective resource base, can play an indispensible role in the paradigm transition from fossil-based to carbohydrate-based economy. Poly(3-hydroxybutyrate), PHB has attracted much commercial interest as a plastic and biodegradable material because some its physical properties are similar to those of polypropylene (PP), even though the two polymers have quite different chemical structures. PHB exhibits a high degree of crystallinity, has a high melting point of approximately 180°C, and most importantly, unlike PP, PHB is rapidly biodegradable. Two major factors which currently inhibit the widespread use of PHB are its high cost and poor mechanical properties. The production costs of PHB are significantly higher than for plastics produced from petrochemical resources (e.g. PP costs $US1 kg-1, whereas PHB costs $US8 kg-1), and its stiff and brittle nature makes processing difficult and impedes its ability to handle high impact. Lignin, together with cellulose and hemicellulose, are the three main components of every lignocellulosic biomass. It is a natural polymer occurring in the plant cell wall. Lignin, after cellulose, is the most abundant polymer in nature. It is extracted mainly as a by-product in the pulp and paper industry. Although, traditionally lignin is burnt in industry for energy, it has a lot of value-add properties. Lignin, which to date has not been exploited, is an amorphous polymer with hydrophobic behaviour. These make it a good candidate for blending with PHB and technically, blending can be a viable solution for price and reduction and enhance production properties. Theoretically, lignin and PHB affect the physiochemical properties of each other when they become miscible in a composite. A comprehensive study on structural, thermal, rheological and environmental properties of lignin/PHB blends together with neat lignin and PHB is the targeted scope of this thesis. An introduction to this research, including a description of the research problem, a literature review and an account of the research progress linking the research papers is presented in Chapter 1. In this research, lignin was obtained from bagasse through extraction with sodium hydroxide. A novel two-step pH precipitation procedure was used to recover soda lignin with the purity of 96.3 wt% from the black liquor (i.e. the spent sodium hydroxide solution). The precipitation process is presented in Chapter 2. A sequential solvent extraction process was used to fractionate the soda lignin into three fractions. These fractions, together with the soda lignin, were characterised to determine elemental composition, purity, carbohydrate content, molecular weight, and functional group content. The thermal properties of the lignins were also determined. The results are presented and discussed in Chapter 2. On the basis of the type and quantity of functional groups, attempts were made to identify potential applications for each of the individual lignins. As an addendum to the general section on the development of composite materials of lignin, which includes Chapters 1 and 2, studies on the kinetics of bagasse thermal degradation are presented in Appendix 1. The work showed that distinct stages of mass losses depend on residual sucrose. As the development of value-added products from lignin will improve the economics of cellulosic ethanol, a review on lignin applications, which included lignin/PHB composites, is presented in Appendix 2. Chapters 3, 4 and 5 are dedicated to investigations of the properties of soda lignin/PHB composites. Chapter 3 reports on the thermal stability and miscibility of the blends. Although the addition of soda lignin shifts the onset of PHB decomposition to lower temperatures, the lignin/PHB blends are thermally more stable over a wider temperature range. The results from the thermal study also indicated that blends containing up to 40 wt% soda lignin were miscible. The Tg data for these blends fitted nicely to the Gordon-Taylor and Kwei models. Fourier transform infrared spectroscopy (FT-IR) evaluation showed that the miscibility of the blends was because of specific hydrogen bonding (and similar interactions) between reactive phenolic hydroxyl groups of lignin and the carbonyl group of PHB. The thermophysical and rheological properties of soda lignin/PHB blends are presented in Chapter 4. In this chapter, the kinetics of thermal degradation of the blends is studied using thermogravimetric analysis (TGA). This preliminary investigation is limited to the processing temperature of blend manufacturing. Of significance in the study, is the drop in the apparent energy of activation, Ea from 112 kJmol-1 for pure PHB to half that value for blends. This means that the addition of lignin to PHB reduces the thermal stability of PHB, and that the comparative reduced weight loss observed in the TGA data is associated with the slower rate of lignin degradation in the composite. The Tg of PHB, as well as its melting temperature, melting enthalpy, crystallinity and melting point decrease with increase in lignin content. Results from the rheological investigation showed that at low lignin content (.30 wt%), lignin acts as a plasticiser for PHB, while at high lignin content it acts as a filler. Chapter 5 is dedicated to the environmental study of soda lignin/PHB blends. The biodegradability of lignin/PHB blends is compared to that of PHB using the standard soil burial test. To obtain acceptable biodegradation data, samples were buried for 12 months under controlled conditions. Gravimetric analysis, TGA, optical microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), FT-IR, and X-ray photoelectron spectroscopy (XPS) were used in the study. The results clearly demonstrated that lignin retards the biodegradation of PHB, and that the miscible blends were more resistant to degradation compared to the immiscible blends. To obtain an understanding between the structure of lignin and the properties of the blends, a methanol-soluble lignin, which contains 3× less phenolic hydroxyl group that its parent soda lignin used in preparing blends for the work reported in Chapters 3 and 4, was blended with PHB and the properties of the blends investigated. The results are reported in Chapter 6. At up to 40 wt% methanolsoluble lignin, the experimental data fitted the Gordon-Taylor and Kwei models, similar to the results obtained soda lignin-based blends. However, the values obtained for the interactive parameters for the methanol-soluble lignin blends were slightly lower than the blends obtained with soda lignin indicating weaker association between methanol-soluble lignin and PHB. FT-IR data confirmed that hydrogen bonding is the main interactive force between the reactive functional groups of lignin and the carbonyl group of PHB. In summary, the structural differences existing between the two lignins did not manifest itself in the properties of their blends.

Retrofitting commercial office buildings for sustainability : tenants’ expectations and experiences

Introduction Buildings, which account for approximately half of all annual energy and greenhouse gas emissions, are an important target area for any strategy addressing climate change. Whilst new commercial buildings increasingly address sustainability considerations, incorporating green technology in the refurbishment process of older buildings is technically, financially and socially challenging. This research explores the expectations and experiences of commercial office building tenants, whose building was under-going green refurbishment. Methodology Semi-structured in-depth interviews with seven residents and neighbours of a large case-study building under-going green refurbishment in Melbourne, Australia. Built in 1979, the 7,008m² ‘B’ grade building consists of 11 upper levels of office accommodation, ground floor retail, and a basement area leased as a licensed restaurant. After refurbishment, which included the installation of chilled water pumps, solar water heating, waterless urinals, insulation, disabled toilets, and automatic dimming lights, it was expected that the environmental performance of the building would move from a non-existent zero ABGR (Australian Building Greenhouse Rating) star rating to 3.5 stars, with a 40% reduction in water consumption and 20% reduction in energy consumption. Interviews were transcribed, with responses analysed using a thematic approach, identifying categories, themes and patterns. Results Commercial property tenants are on a journey to sustainability - they are interested and willing to engage in discussions about sustainability initiatives, but the process, costs and benefits need to be clear. Critically, whilst sustainability was an essential and non-negotiable criterion in building selection for government and larger corporate tenants, sustainability was not yet a core business value for smaller organisations – whilst they could see it as an emerging issue, they wanted detailed cost-benefit analyses, pay-back calculations of proposed technologies and, ideally, wished they could trial the technology first-hand in some way. Although extremely interested in learning more, most participants reported relatively minimal knowledge of specific sustainability features, designs or products. In discussions about different sustainable technologies (e.g., waterless urinals, green-rated carpets), participants frequently commented that they knew little about the technology, had not heard of it or were not sure exactly how it worked. Whilst participants viewed sustainable commercial buildings as the future, they had varied expectations about the fate of existing older buildings – most felt that they would have to be retrofitted at some point to meet market expectations and predicted the emergence of a ‘non-sustainability discount’ for residing in a building without sustainable features. Discussion This research offers a beginning point for understanding the difficulty of integrating green technology in older commercial buildings. Tenants currently have limited understandings of technology and potential building performance outcomes, which ultimately could impede the implementation of sustainable initiatives in older buildings. Whilst the commercial property market is interested in learning about sustainability in the built environment, the findings highlight the importance of developing a strong business case, communication and transition plan for implementing sustainability retrofits in existing commercial buildings.

The Commercial Surrogacy Dilemma

In November 2009 the England and Wales High Court (Family Division) granted a parental order pursuant to s30 Human Fertilisation and Embryology Act 1990 in respect of twins who came to be in the custody and control of the applicants (Mr and Mrs A) through a surrogacy arrangement. The particularly unusual and interesting aspect of this case is that, on the evidence, Mr and Mrs A had paid expenses to the surrogate above and beyond those allowed by the legislation, thus creating a commercial surrogacy arrangement. Commercial surrogacy arrangements involve the payment of money to the surrogate mother in excess of those expenses which have been reasonably incurred pursuant to the surrogacy arrangement. This case is relevant to Queensland law because commercial surrogacy arrangements are also prohibited in Queensland and, as in the United Kingdom, the court cannot make a parentage order unless it is satisfied the surrogacy arrangement is not a commercial surrogacy arrangement.

When the shoe doesn't quite fit: Regulating large commercial airports with expanding roles

Airports, whether publicly or privately owned or operated fill both public and private roles. They need to act as public infrastructure providers and as businesses which cover their operating costs. That leads to special governance concerns with respect to consumers and competitors which are only beginning to be addressed. These challenges are highlighted both by shifts in ownership status and by the expansion of roles performed by airports as passenger and cargo volumes continue to increase and as nearby urban areas expand outward towards airports. We survey five ways in which the regulatory shoe doesn‟t quite fit the needs. Our findings suggest that, while ad hoc measures limit political tension, new governance measures are needed.

Estimation of energy saving of commercial building by living wall and green facade in sub-tropical climate of Australia

This paper investigates energy saving potential of commercial building by living wall and green façade system using Envelope Thermal Transfer Value (ETTV) equation in Sub-tropical climate of Australia. Energy saving of four commercial buildings was quantified by applying living wall and green façade system to the west facing wall. A field experimental facility, from which temperature data of living wall system was collected, was used to quantify wall temperatures and heat gain under controlled conditions. The experimental parameters were accumulated with extensive data of existing commercial building to quantify energy saving. Based on temperature data of living wall system comprised of Australian native plants, equivalent temperature of living wall system has been computed. Then, shading coefficient of plants in green façade system has been included in mathematical equation and in graphical analysis. To minimize the air-conditioned load of commercial building, therefore to minimize the heat gain of commercial building, an analysis of building heat gain reduction by living wall and green façade system has been performed. Overall, cooling energy performance of commercial building before and after living wall and green façade system application has been examined. The quantified energy saving showed that only living wall system on opaque part of west facing wall can save 8-13 % of cooling energy consumption where as only green façade system on opaque part of west facing wall can save 9.5-18% cooling energy consumption of commercial building. Again, green façade system on fenestration system on west facing wall can save 28-35 % of cooling energy consumption where as combination of both living wall on opaque part of west facing wall and green façade on fenestration system on west facing wall can save 35-40% cooling energy consumption of commercial building in sub-tropical climate of Australia.

Investigation of cooling energy performance of commercial building in sub-tropical climate through the application of green roof and living wall

This paper investigates cooling energy performance of commercial building before and after green roof and living wall application based on integrated building heat gain model developed from Overall Thermal Transfer Value (OTTV) of building wall and steady state heat transfer process of roof in sub-tropical climate. Using the modelled equation and eQUEST energy simulation tool, commercial building envelope parameters and relevant heat gain parameters have been accumulated to analyse the heat gain and cooling energy consumption of commercial building. Real life commercial building envelope and air-conditioned load data for the sub-tropical climate zone have been collected and compared with the modelled analysis. Relevant temperature data required for living wall and green roof analysis have been collected from experimental setup comprised of both green roof and west facing living wall. Then, Commercial building heat flux and cooling energy performance before and after green roof and living wall application have been scrutinized.

The adoption of residential sustainability programs : lessons from the commercial sector

The article explains and compares sustainability programs available for use by residential and commercial premises; as well as the respective legal tenure frameworks of commercial and residential tenancies. It identifies that while the desire of commercial tenants drive the participation by landlords in these programs, residential tenants appear to be ignorant of sustainable measures. The article contends that the reason for this difference is rooted in the legal and social status of residential tenants. It explores the impact that secure tenure may have in promoting residential sustainability programs and concludes by observing that the lack of involvement of residential tenants in programs stems from the absence of tenure security, which prevents any long term cooperation between the parties.

Australian tax analysis - cases, commentary, commercial applications and questions [7th Ed.]

"Australian Tax Analysis, seventh edition, provides a comprehensive examination of taxation law with a practical commercial perspective. The seventh edition of this text features: two new chapters: "Offsets" and "Superannuation and Employer Responsibilities"; selected case extracts; Tax Commissioner Rulings; thought-provoking commentary; instruction on how to read the Acts; and engaging problem-based practice questions."--Publisher's website.

The composition of sugarcane juices dervied from burnt cane and whole green cane crop

There has been substantial interest within the Australian sugar industry in product diversification as a means to reduce its exposure to fluctuating raw sugar prices and in order to increase its commercial viability. In particular, the industry is looking at fibrous residues from sugarcane harvesting (trash) and from sugarcane milling (bagasse) for cogeneration and the production of biocommodities, as these are complementary to the core process of sugar production. A means of producing surplus residue (biomass) is to process whole sugarcane crop. In this paper, the composition of different juices derived from different harvesting methods, viz. burnt cane with all trash extracted (BE), green cane with half of the trash extracted (GE), and green cane (whole sugarcane crop) with trash unextracted (GU), were investigated and the results and comparison presented. The determination of electrical conductivity, inorganic composition, and organic acids indicate that both GU and GE cane juice contain a higher proportion of soluble inorganic ions and ionisable organic acids, compared to BE cane juice. It is important to note that there are considerably higher levels of Na ions and citric acid, but relatively low P levels in the GU samples. A higher level of reducing sugars was analysed in the GU samples than the BE samples due to the higher proportion of impurities found naturally in sugarcane tops and leaves. The purity of the first expressed juice (FEJ) of GU cane was on average higher than that of FEJ of BE cane. Results also show that GU juices appear to contain higher levels of proteins and polysaccharides, with no significant difference in starch levels.

Reconciling community and commerce? Collaboration between produsage communities and commercial operators

Collaborative user-led content creation by online communities, or produsage (Bruns 2008), has generated a variety of useful and important resources and other valuable outcomes, from open source software through the Wikipedia to a variety of smaller-scale, specialist projects. These are often seen as standing in an inherent opposition to commercial interests, and attempts to develop collaborations between community content creators and commercial partners have had mixed success rates to date. However, such tension between community and commerce is not inevitable, and there is substantial potential for more fruitful exchanges and collaboration. This article contributes to the development of this understanding by outlining the key underlying principles of such participatory community processes and exploring the potential tensions which could arise between these communities and their potential external partners. It also sketches out potential approaches to resolving them.

Identification of bone morphogenetic proteins 2 and 4 in commercial demineralized freeze-dried bone allograft preparations : pilot study

BACKGROUND: Demineralized freeze-dried bone allografts (DFDBAs) have been proposed as a useful adjunct in periodontal therapy to induce periodontal regeneration through the induction of new bone formation. The presence of bone morphogenetic proteins (BMPs) within the demineralized matrix has been proposed as a possible mechanism through which DFDBA may exert its biologic effect. However, in recent years, the predictability of results using DFDBA has been variable and has led to its use being questioned. One reason for the variability in tissue response may be attributed to differences in the processing of DFDBA, which may lead to loss of activity of any bioactive substances within the DFDBA matrix. Therefore, the purpose of this investigation was to determine whether there are detectable levels of bone morphogenetic proteins in commercial DFDBA preparations. METHODS: A single preparation of DFDBA was obtained from three commercial sources. Each preparation was studied in triplicate. Proteins within the DFDBA samples were first extracted with 4M guanidinium HCI for seven days at 40 degrees celsius and the residue was further extracted with 4M guanidinium HCL/EDTA for seven days at 40 degrees celsius. Two anti-human BMP-2 and -4 antibodies were used for the detection of the presence of BMP's in the extracts. RESULTS: Neither BMP-2 nor BMP-4 was detected in any of the extracts. When recombinant human BMP-2 and -4 were added throughout the extraction process of DFDBA extraction, not only were intact proteins detected but smaller molecular weight fragments were also noted in the extract. CONCLUSIONS: These results indicate that all of the DFDBA samples tested had no detectable amounts of BMP-2 and -4. In addition, an unknown substance present in the DFDBA may be responsible for degradation of whatever BMPs might be present.