Synthesis of new vegetable oil-based polymeric materials

A crescente procura de recursos fosseis a que se tem assistido nos ultimos anos, tem resultado num crescimento sem precedentes dos precos, com consequencias imprevisiveis e que levara, no espaco de decadas, ao seu inevitavel esgotamento. A procura de um modelo de desenvolvimento sustentavel, baseado em recursos renovaveis e o grande desafio que se coloca a civilizacao no seculo XXI. A biomassa vegetal, atraves das designadas gBio-refinarias h, e uma alternativa logica para a producao de produtos quimicos e de materiais mas tambem de combustiveis e energia. Os oleos vegetais constituem uma das fracoes da biomassa vegetal, cuja exploracao tem merecido redobrada atencao nos ultimos anos, como fonte de materiais e de combustiveis. Assim, a presente dissertacao tem por objetivo o desenvolvimento de novos materiais polimericos derivados de oleos vegetais, seguindo duas abordagens distintas, nomeadamente a preparacao de polimeros atraves de polimerizacao por etapas e polimerizacao em cadeia (Parte B e C, respetivamente). Em primeiro lugar, foram sintetizados poliesteres alifaticos de cadeia longa a partir de monomeros provenientes do oleo de colza (Capitulo III). A auto-metatese do acido erucico com catalisadores de rutenio, seguida de hidrogenacao da ligacao dupla, originou o acido 1,26-hexacosanodioico, que por sua vez foi convertido em hexacosano-1,26-diol. Subsequentemente, a policondensacao do acido ƒ¿,ƒÖ-dicarboxilico de cadeia longa com o hexacosano-1,26-diol originou o poliester 26,26. O diacido C26 foi tambem polimerizado com outros alcano-diois de cadeia curta, nomeadamente o dodecano-1,12-diol e o butano-1,2-diol, produzindo, respetivamente, os poliesteres 12,26 e 4,26. Estes poliesteres de fontes 100% renovaveis possuem valores de Mn na ordem dos 8-14 kDa e valores de PDI entre 2.1 e 2.7. As propriedades destes poliesteres alifaticos foram avaliadas atraves de varias tecnicas, revelando elevada cristalinidade (com uma estrutura cristalina como a do polietileno) e elevadas temperaturas de fusao (74-104 ‹C), cristalizacao (68-92 ‹C) e degradacao (323-386 ‹C). Em segundo lugar, foram sintetizados polimeros lineares termo-reversiveis a partir de derivados do oleo de ricinio (Capitulo IV). Para tal foram preparados monomeros que incorporam aneis furanicos inseridos atraves do acoplamento tiol-eno, e que posteriormente foram polimerizados pela reacao de Diels-Alder (DA) entre os grupos furano (dieno A) e estruturas complementares do tipo maleimida (dienofilo B). Para as polimerizacoes DA foram consideradas duas abordagens diferentes, nomeadamente (i) o uso de monomeros com dois aneis furanicos terminais em conjunto com uma bismaleimida (sistemas AA+BB) e (ii) a utilizacao de um monomero que incorpora ambos os grupos reativos, furano e maleimida, na sua estrutura (sistema AB). Este estudo demonstrou claramente que ambas as estratégias foram bem sucedidas embora com diferentes resultados em termos da natureza dos produtos obtidos. Estes polímeros lineares apresentam valores relativamente baixos de Tg (-40 to -2 °C) devido à natureza flexível dos grupos separadores das funções reativas, e de Mn (4.5-9.0 kDa) dada a observada tendência de ciclização associada a concentrações baixas de monómero. A aplicação da reação de retro-DA aos polímeros em causa confirmou o seu caráter reversível, ou seja, a possibilidade de promover, em condições controladas, a despolimerização com recuperação dos monómeros de partida. Esta particularidade abre caminhos para materiais macromoleculares originais com aplicações promissoras tais como auto-reparação e reciclabilidade. Em terceiro lugar, sintetizaram-se polímeros não-lineares termo-reversíveis a partir de derivados do óleo de ricínio (Capítulo V). Para tal foram preparados monómeros trifuncionais e posteriormente polimerizados através da reação de DA entre os grupos reativos complementares furano/maleimida. Foram consideradas três abordagens distintas para preparar estes polímeros não-lineares, nomeadamente através da utilização de (i) um monómero bisfurânico em combinação com uma trismaleimida (sistema A2+B3) e (ii) um monómero trisfurânico em conjunto com uma bismaleimida (sistema A3+B2) que originaram materiais ramificados ou reticulados, e ainda (iii) a utilização de monómeros assimetricamente substituídos do tipo A2B ou AB2 capazes de originar estruturas macromoleculares hiper-ramificadas. Todos os sistemas apresentaram valores de Tg perto de 0 °C, o que era de esperar para estes materiais não-lineares. A aplicação da reação de retro-DA comprovou mais uma vez o caráter termo-reversível das polimerizações em causa. Em quarto lugar e último lugar, foram preparados copolímeros de acetato de vinilo (VAc) com monómeros derivados de óleo de girassol (Capítulo VI). Ésteres vinílicos de ácidos gordos (FAVE) foram sintetizados por transvinilação dos ácidos oleico e linoleico com VAc catalisada por um complexo de irídio. Os monómeros vinílicos preparados foram caracterizados e posteriormente homopolimerizados e copolimerizados com VAc através do uso dos grupos vinílicos terminais como função inicial de polimerização. A variação do tipo e quantidade de monómero FAVE e da quantidade de iniciador radicalar originou copolímeros de VAc com valores de Mn na gama de 1.2-3.0 kDa e valores de Tg de -5 a 16 °C. Os copolímeros foram avaliados em testes de cura oxidativa através das insaturações nas suas cadeias alifáticas para formar materiais reticulados, e os resultados sugerem que eles podem ser sistemas efetivos de cura para aplicações como tintas, vernizes e outros tipos de revestimento. Todos os materiais poliméricos preparados ao longo deste trabalho constituem contribuições atrativas para a área dos polímeros oriundos de recursos renováveis e representam uma prova indiscutível de que os óleos vegetais são percursores promissores de materiais macromoleculares com potenciais aplicações.

E-Cigarettes: A Review of New Trends in Cannabis Use.

The emergence of electronic cigarettes (e-cigs) has given cannabis smokers a new method of inhaling cannabinoids. E-cigs differ from traditional marijuana cigarettes in several respects. First, it is assumed that vaporizing cannabinoids at lower temperatures is safer because it produces smaller amounts of toxic substances than the hot combustion of a marijuana cigarette. Recreational cannabis users can discretely "vape" deodorized cannabis extracts with minimal annoyance to the people around them and less chance of detection. There are nevertheless several drawbacks worth mentioning: although manufacturing commercial (or homemade) cannabinoid-enriched electronic liquids (e-liquids) requires lengthy, complex processing, some are readily on the Internet despite their lack of quality control, expiry date, and conditions of preservation and, above all, any toxicological and clinical assessment. Besides these safety problems, the regulatory situation surrounding e-liquids is often unclear. More simply ground cannabis flowering heads or concentrated, oily THC extracts (such as butane honey oil or BHO) can be vaped in specially designed, pen-sized marijuana vaporizers. Analysis of a commercial e-liquid rich in cannabidiol showed that it contained a smaller dose of active ingredient than advertised; testing our laboratory-made, purified BHO, however, confirmed that it could be vaped in an e-cig to deliver a psychoactive dose of THC. The health consequences specific to vaping these cannabis preparations remain largely unknown and speculative due to the absence of comprehensive, robust scientific studies. The most significant health concerns involve the vaping of cannabinoids by children and teenagers. E-cigs could provide an alternative gateway to cannabis use for young people. Furthermore, vaping cannabinoids could lead to environmental and passive contamination.

Mortality of Migratory Birds from Marine Commercial Fisheries and Offshore Oil and Gas Production in Canada

There is an imminent need for conservation and best-practice management efforts in marine ecosystems where global-scale declines in the biodiversity and biomass of large vertebrate predators are increasing and marine communities are being altered. We examine two marine-based industries that incidentally take migratory birds in Canada: (1) commercial fisheries, through bycatch, and (2) offshore oil and gas exploration, development, and production. We summarize information from the scientific literature and technical reports and also present new information from recently analyzed data to assess the magnitude and scope of mortality. Fisheries bycatch was responsible for the highest levels of incidental take of migratory bird species; estimated combined take in the longline, gillnet, and bottom otter trawl fisheries within the Atlantic, including the Gulf of St. Lawrence, and Pacific regions was 2679 to 45,586 birds per year. For the offshore oil and gas sector, mortality estimates ranged from 188 to 4494 deaths per year due to the discharge of produced waters resulting in oil sheens and collisions with platforms and vessels; however these estimates for the oil and gas sector are based on many untested assumptions. In spite of the uncertainties, we feel levels of mortality from these two industries are unlikely to affect the marine bird community in Canada, but some effects on local populations from bycatch are likely. Further research and monitoring will be required to: (1) better estimate fisheries-related mortality for vulnerable species and populations that may be impacted by local fisheries, (2) determine the effects of oil sheens from produced waters, and attraction to platforms and associated mortality from collisions, sheens, and flaring, so that better estimates of mortality from the offshore oil and gas sector can be obtained, and (3) determine impacts associated with accidental spills, which are not included in our current assessment. With a better understanding of the direct mortality of marine birds from industry, appropriate mitigation and management actions can be implemented. Cooperation from industry for data collection, research to fill knowledge gaps, and implementation of mitigation approaches will all be needed to conserve marine birds in Canada.

Synthesis and Biological Evaluation of New Ozonides with Improved Plant Growth Regulatory Activity

The iron oxyallyl carbocation generated from 2,7-dibromocycloheptanone was induced to undergo [4 + 3] cycloaddition reactions with various furans, affording a series of 12-oxatricyclo-[4.4.1.1(2,5)]-dodec-3-en-11-one adducts. Similar methodology was used to prepare two additional cycloadducts using menthofuran and two homologous aliphatic dibromoketones. Dipolar cycloaddition of ozone to the adducts afforded the corresponding secondary ozonides (i.e., 1,2,4-trioxolanes) in variable yields. Ozonides were investigated by quantum mechanics at the B3LYP/6-31+G* level to study structural features including close contacts which may be responsible for enhancing ozonide stability. The effect of these ozonides and their corresponding precursor cycloadducts upon radicle growth of both Sorghum bicolor and Cucumis sativus was evaluated at 5.0 x 10(-4) mol L-1. The most active cycloadducts and ozonides were also evaluated against the weed species Ipomoea grandifolia and Brachiaria decumbens, and the results are discussed. Compared to ozonides previously synthesized in our laboratory, the new ozonides described herein present improved plant growth regulatory activity.

Building post crisis watchtowers: investment management Systems and new institutional logics for regulatory compliance

The financial crisis of 2007-2009 has precipitated large scale regulatory change. Tight deadlines for implementation require organizations to start working on remediation projects before final drafts of regulations are crystalized. Firms are faced with engaging in complex and costly change management programs at a time when profits are diminished. As a consequence of these factors, pre-crisis logics for organizing compliance practices are being questioned and new approaches introduced. Our study explores the use of Investment Management Systems (IMS) in facilitating compliance arrangements. Our motivation is to understand the new logics and the part played by IMS in supporting these approaches. The study adopts an institutional logics perspective to explore the use of such systems at eight financial organizations. The study found new logics for organizing compliance include consolidation, centralization, harmonization and consistency and that the IMS plays an important role in supporting and enabling related activities.

Parabens can enable hallmarks and characteristics of cancer in human breast epithelial cells: a review of the literature with reference to new exposure data and regulatory status

A framework for understanding the complexity of cancer development was established by Hanahan and Weinberg in their definition of the hallmarks of cancer. In this review, we consider the evidence that parabens can enable development in human breast epithelial cells of 4/6 of the basic hallmarks, 1/2 of the emerging hallmarks and 1/2 of the enabling characteristics. Hallmark 1: parabens have been measured as present in 99% of human breast tissue samples, possess oestrogenic activity and can stimulate sustained proliferation of human breast cancer cells at concentrations measurable in the breast. Hallmark 2: parabens can inhibit the suppression of breast cancer cell growth by hydroxytamoxifen, and through binding to the oestrogen-related receptor gamma (ERR) may prevent its deactivation by growth inhibitors. Hallmark 3: in the 10nM to 1M range, parabens give a dose-dependent evasion of apoptosis in high-risk donor breast epithelial cells. Hallmark 4: long-term exposure (>20weeks) to parabens leads to increased migratory and invasive activity in human breast cancer cells, properties which are linked to the metastatic process. Emerging hallmark: methylparaben has been shown in human breast epithelial cells to increase mTOR, a key regulator of energy metabolism. Enabling characteristic: parabens can cause DNA damage at high concentrations in the short term but more work is needed to investigate long-term low-doses of mixtures. The ability of parabens to enable multiple cancer hallmarks in human breast epithelial cells provides grounds for regulatory review of the implications of the presence of parabens in human breast tissue.

Regulatory and enabling approaches to corporate law enforcement : patterns of litigation 1986-2002 and the effect of recent reforms in New Zealand, Australia and the United Kingdom

Enforcement of corporate rights and duties may follow either a ‘regulatory’ or ‘enabling’ model. If a regulatory approach is taken, enforcement action will generally be undertaken by regulatory agencies such as, in New Zealand, the Registrar of Companies and Securities Commission, the Australian Securities and Investments Commission (ASIC) or the Department of Trade and Industry (DTI) in the United Kingdom. If an enabling approach is chosen, enforcement action will more often be by private parties such as company shareholders, directors or creditors. When New Zealand's company law was reformed in 1993, a primarily private enforcement regime was adopted, consisting of a list of statutory directors' duties and an enhanced collection of shareholder remedies, based in part upon North American models and including a statutory derivative action. Public enforcement was largely confined to administrative matters and the enforcement of the disclosure requirements of New Zealand's securities law. While the previous enforcement regime was similarly reliant on private action, the law on directors' duties was less accessible, and shareholder action was hindered by the majority rule principle and the rule in Foss v Harbottle. This approach is in contrast with that used in Australia and the United Kingdom, where public agencies have a much more prominent enforcement role despite recent and proposed reforms to directors' duties and shareholder remedies. These reforms are designed to improve the ability of private parties to enforce corporate rights and duties. A survey of enforcement litigation in New Zealand since 1986 indicates that the object of a primarily enabling enforcement regime seems to have been achieved, and may well have been achieved even without the 1993 reform package. Private enforcement has, in fact, been much more prevalent than public enforcement since well before the enactment of the new legislation. Most enforcement action both before and after the reform was commenced by shareholders and shareholder/directors, and most involved closely held companies. Public enforcement was largely undertaken in areas such as securities law, where the wider public interest was affected. Similar surveys of Australian and United Kingdom enforcement litigation reveal a proportionally much greater reliance on public bodies to enforce corporate rights and duties, indicating a more regulatory approach. The ASIC and DTI enforced a wider range of provisions, affecting both closely and widely held companies, than those subject to public enforcement in New Zealand. Publicly enforced provisions in Australia and the United Kingdom include directors' duties and provisions dealing with disqualification from managing companies, as well as securities law requirements.

A new method to warm up lubricating oil to improve the fuel efficiency during cold start

Cold start driving cycles exhibit an increase in friction losses due to the low temperatures of metal and media compared to normal operating engine conditions. These friction losses are responsible for up to 10% penalty in fuel economy over the official drive cycles like the New European Drive Cycle (NEDC), where the temperature of the oil even at the end of the 1180 s of the drive cycle is below the fully warmed up values of between 100°C and 120°C. At engine oil temperatures below 100°C the water from the blow by condensates and dilutes the engine oil in the oil pan which negatively affects engine wear. Therefore engine oil temperatures above 100°C are desirable to minimize engine wear through blow by condensate. The paper presents a new technique to warm up the engine oil that significantly reduces the friction losses and therefore also reduces the fuel economy penalty during a 22°C cold start NEDC. Chassis dynamometer experiments demonstrated fuel economy improvements of over 7% as well as significant emission reductions by rapidly increasing the oil temperature. Oil temperatures were increased by up to 60°C during certain parts of the NEDC. It is shown how a very simple sensitivity analysis can be used to assess the relative size or efficiency of different heat transfer passes and the resulting fuel economy improvement potential of different heat recovery systems system. Due to its simplicity the method is very fast to use and therefore also very cost effective. The method demonstrated a very good correlation for the fuel consumption within ±1% compared to measurements on a vehicle chassis roll.

New crevice corrosion testing method and its use in the investigation of oil stain

A new electrochemical method was developed to investigate crevice corrosion and its inhibitors. A wire beam electrode was used to allow electrochemical parameters to be measured directly from the crevice area. As an example, oil stain was investigated using this method.

Do oil prices predict economic growth? New global evidence

In this paper, we test whether oil price predicts economic growth for 28 developed and 17 developing countries. We use predictability tests that account for the key features of the data, namely, persistency, endogeneity, and heteroskedasticity. Our analysis considers a large number of countries, shows evidence of more out-of-sample predictability with nominal than real oil prices, finds in-sample predictability to be independent of the use of nominal and real prices, and reveals greater evidence of predictability for developed countries.

Lipase-catalysed incorporation of EPA into emu oil: formation and characterisation of new structured lipids

Partial hydrolysis of emu oil was performed using Thermomyces lanuginosus lipase to remove some shorter chain fatty acids. Then eicosapentaenoic acid (EPA) was incorporated into the modified emu oil using either Lipozyme RMIM or Lipozyme TLIM to produce new EPA enriched structured lipids. Using Isooctane as a reaction solvent increased the level of EPA incorporation, which was higher with RMIM than with TLIM. TLIM incorporated EPA almost exclusively into the sn-1,3 positions, whereas RMIM incorporated EPA at sn-1,3 and sn-2 positions in an almost statistical ratio. Both structured lipids were less oxidatively stable than emu oil.