The research herein presents an approach to stabilising reactive materials by engineering and designing strategies for forming multi-component materials containing the reactive molecules by use of their non-covalent intermolecular interactions. These interactions may be utilised as part of a design approach to create new materials of more beneficial physical and chemical properties for the desired application. The reactive materials focussed on in this research are organic peroxyacids, in particular peroxyacetic acid, meta-chloroperbenzoic acid and 6-phthalimidoperoxyhexanoic acid. The stabilities of these target materials under different conditions are probed to find a suitable environment for crystallisation experiments. Crystal structures of the materials were isolated and characterised and the peroxyacids were subsequently cocrystallised with materials chosen to interact with the target molecules to form new molecular complexes, including carboxylic acids, π stacking materials and metal salts. A hosting approach was also employed to form multi-component systems containing these materials, crystallising them with larger, stable, structure-generating compounds with the aim of intercalating the reactive molecules in their stable structure. To this end, urea based compounds, cyclodextrins and Montmorillonite clay were investigated as hosting materials. Candidate multi-component materials were synthesised which successfully retain peroxyacid reactivity. A second set of materials studied was agrichemicals, which also frequently have reactive character, in which a change in physical properties was pursued by the method of forming new crystalline complexes. Five new crystalline agrochemical molecular complexes were synthesised and tested for thermal stability in comparison to the original materials to assess for changes in properties of the multi-component materials.

No description available.

No description available.

 Ischemic stroke is the leading cause of death and disability in human diseases all around the world. As effective treatment for ischemic stroke is still absent, seeking for new therapy is of great interest. Currently, several key pathological cascades following cerebral ischemia have been explored to develop further therapies. Among them, reactive nitrogen species (RNS) has been indicated to play a critical role in cerebral ischemia reperfusion injury. As one of the RNS, peroxynitrite contributes to the neural cell death and subsequent brain dysfunction in the process. Thus, development of antioxidants targeting on peroxynitrite could be an important strategy for the treatment of cerebral ischemia-reperfusion injury. Baicalin is a polyphenolic compound isolated from roots of Scutellaria baicalensis. Baicalin exerted protective effects against cerebral ischemia-reperfusion injury but the mechanisms are not clear yet. In this study, we investigated the free radical scavenging ability and neuroprotective effects of baicalin. According to our results, baicalin neutralized DPPH radicals effectively. By using electron paramagnetic resonance (EPR) spin trapping technology and fluorescent probe DAF-2DA, we found that baicalin dose-dependently scavenged superoxide, but had very low effect on elimination of nitric oxide. The immunofluoresent results revealed that baicalin at the concentration of 50 M completely suppressed the nitrotyrosine formation induced by 3-morpholinylsydnoneimine chloride (SIN-1, a peroxynitrite donor) in neuroblastoma SH-SY5Y cells. Mass spetrum provided direct evidence of the peroxynitrite scavenging ability of baicalin. Using MTT assays, we found that baicalin totally reversed peroxynitrite-induced cytotoxicity in SH-SY5Y cells and protected SH-SY5Y cells in oxygen glucose deprivation (OGD) and following reoxygenation injury. Furthermore, in vivo experiments revealed that intravenous injection of baicalin exerted better neuroprotective effect than intraperitoneal administration in rats underwent middle cerebral artery occlusion (MCAO). After cerebral ischemia reperfusion, rats treated with 3 mg/kg of peroxynitrite decomposition catalyst (FeTMPyP) or 25 mg/kg of baicalin revealed a smaller size of infarction volume, suppressed neural cell death and reduced nitrotyrosine formation than MCAO rats. However, baicalin did not alter the expression of tight junction proteins, claudin-5 and ZO-1, in brain endothelial bEnd3 cell line treated with OGD following reoxygenation. In cerebral ischemia reperfusion rats, administration of FeTMPyP at the dosage of 3 mg/kg diminished the Evans blue leakage caused by blood brain barrier disruption, whereas treatment of baicalin did not show significant effect. In conclusion, this study suggests that baicalin can scavenge peroxynitrite and protect neural cells from peroxynitrite-induced injury. Furthermore, baicalin could prevent brains from cerebral ischemia-reperfusion injury and the neuroprotective mechanisms are associated with the scavenging effects on peroxynitrite. These findings provide new insights into the antioxidant and neuroprotective properties of baicalin and indicate the potential application of baicalin for the treatment of ischemic stroke. / published_or_final_version / Chinese Medicine / Master / Master of Philosophy

Visame pasaulyje mėsos poreikis didėja jau nuo 1950 metų. Per šį laikotarpį kiekvienam pasaulio žmogui tenkančios mėsos kiekis padidėjo beveik dvigubai. Taip pat radikaliai pasikeitė ir gyvulių auginimo bei šėrimo technologijos. Jungtinių Tautų maisto ir žemės ūkio organizacija prognozuoja, kad ateinančiais metais mėsos bus suvalgoma dar daugiau. Ir ypač besivystančiose šalyse, nes pastebima, kad industrinių valstybių gyventojai jau persisotino šiuo produktu. Naujausi tyrimai bei mėsos perdirbėjų duomenys liudija, kad šiandien lietuviai dažniausiai mėgaujasi paukštiena ir kiauliena, o jautienai atitenka trečioji vieta. Kauno medicinos Kardiologijos, institute ištyrus mitybos faktorius, turinčius įtakos širdies – kraujagyslių ligoms ir kraujo biocheminei sandarai, paaiškėjo, kad Lietuvos gyventojai vartoja pernelyg daug riebalų, sočiųjų riebalų rūgščių, cholesterolio, cukraus. Riebalai yra ne tik geras energijos pagrindas, bet ir esminių riebalų rūgščių, kurių žmogaus organizmas nesugeba pasigaminti ir jas būtinai turi gauti su maistu, šaltinis. Tačiau šių rūgščių suvartojimas su produktais turi būti ribojamas ir susietas su energijos sąnaudomis, nes šios rūgštys didina bendrą cholesterolio koncentraciją kraujo plazmoje. Dar viena mėsos gaminių problema ─ riebalų oksidacija (apkartimas) ─ kyla biocheminio proceso metu, vykstat reakcijoms tarp riebalų ir deguonies. Šiame procese ilgos riebalinių rūgščių grandinės sutrumpėja ir susiformuoja trumpų grandinių junginiai. Medžiagos... [toliau žr. visą tekstą] / The aim of work: the investigation and analysis of the number of peroxides into products, bearing different oxidation inhibitors. 4 lines of sausages were produced using different oxidation inhibitors: Investigative line I (vitamin C), Investigative line II (mixture „ACELACT“), Investigative III (mixture Presto „MEDITERRAN“) and Control line without any antioxidant. Sausages of all lines were kept under the same conditions: in the refrigerator, freezing chamber and at room temperature. Number of peroxides in products was estimated according to the following schedule: 1, 6, 8, 10, 13, 15 days after producing and 7 days after expiry date. Used measurement devices and computer programs: domestic stirrer „Philips“, thermometer of inner temperature measurement „WEEE DE 21871675”, test tubes shaker „Biosan“, microbiological microscope „Meiji“, thermostat – incubator, Microsoft Office Word, Microsoft Office Excel, Power Point. Following results were fixed: 1. The number of peroxides in 4 lines of sausages, using different components as anti-oxidators: vitamin C, mixtures „ACELACT“, Presto „MEDITERRAN“and in Control line without inhibitor was estimated. At the end of expiry date (15 days after producing) the biggest number of peroxides 2.3664 mekv/kg was set in the specimens of the sausages of Control line, where any anti-oxidator was not included into its composition. The least number of peroxides at the end of expiry date was 1.1287 mekv/kg ─ which was set in the sausages of... [to full text]

New Fourier transform infrared (FTIR) approaches for the quantitative determination of peroxide value (PV) and isolated trans analyses were investigated and developed. The FTIR-PV methods investigated were all based on the stoichiometric reaction of hydroperoxides and triphenylphosphine (TPP) which converts TPP to triphenylphosphine oxide (TPPO). A reference transmission cell (100 mum) method was developed based on the use of a unique TPPO absorption at 542 cm-1. This method covered PV values from 0--15 PV and was shown to be superior in accuracy and reproducibility to the standard American Oil Chemists Society (AOCS) iodometric method. Subsequently, the utility of disposable polyethylene cards, normally used only for qualitative analyses, was investigated for quantitative PV determination. A quantitative IR card method was successfully developed and shown to serve as a very simple, rapid and alternative means of carrying out PV analyses. TPP-impregnated cards were able to reproduce the transmission cell PV results to +/-1.12 PV, while the unimpregnated card was slightly more accurate (+/-0.92 PV). A third FTIR-PV method was developed specifically for the at-line monitoring of high PV fatliquors and employed a germanium attenuated total reflectance sample handling accessory. This method hinged on the use of a TPPO absorption band at 1118 cm-1, normally off scale when pathlengths of >3 mum are used, but is suited to the analysis of oils having very high PVs (>250). The successful quantitative use of the disposable polyethylene IR card to PV led to its study for the quantitative FTIR determination of the isolated trans content of fats and oils and margarines. The polyethylene card was shown to unique and useful properties, tending to inhibit fat crystallization and its inability to retain moisture. These two properties allowed trans determination to be carried out on melted, high trans fats, without heating the polyethylene substrate and also to analyze margarines

Lipid oxidation has important consequences in the edible oil industry, producing compounds with sensory impact and thus reducing the economic value of the products. This work focused on the development of two Fourier transform infrared (FTIR) spectroscopy methods for the measurement of peroxide value (PV) and anisidine value (AV), representing the primary and secondary oxidation products of edible oils. / The infrared method developed for PV determination was based on a mathematical treatment by the partial least squares method of the information contained in the spectral region between 3750 and 3150 cm$ sp{-1}$. / The second method developed considered aldehyde content and anisidine value, a measure of secondary oxidation products. / The two methods developed are rapid ($ sim$2 min/sample) and have the advantage of being automatable. An infrared system coupled to a computer can collect the spectrum of an oil, analyze it and present a report without the need for personnel trained in FTIR spectroscopy. The cost of such a system would rapidly be absorbed through savings on personnel cost, time and chemical reagents required for conventional chemical methods and as such provides a useful advance in quality control methodology for the edible oils sector. (Abstract shortened by UMI.)

Thesis (PhD) -- Macquarie University, Division of Environmental and Life Sciences, Dept. of Chemistry and Biomolecular Sciences, 2007. / Bibliography: leaves 295-322.

Compostos elastoméricos a base de borracha natural (NR) e copolímero de butadieno-estireno (SBR) utilizados na banda de rodagem de pneus são tradicionalmente reticulados com enxofre. O uso de peróxidos e co-agentes na reticulação desses compostos ainda é um desafio a se superar com relação às propriedades viscoelásticas requeridas, de extrema importância para um bom desempenho e vida útil dos pneus. Neste trabalho foi avaliado o uso de peróxidos sem e com co-agentes na reticulação de compostos NR/SBR com o intuito de avaliar a eficiência destes na manutenção das propriedades relevantes em relação a um composto tradicionalmente usado na confecção de banda de rodagem de pneus. Onze formulações com diferentes sistemas de reticulação foram preparadas, sendo uma de referência. Foram avaliadas propriedades físicas como dureza, densidade, tração, resistência ao rasgamento, resiliência, abrasão e DPC, e o comportamento dos compostos de NR/SBR com relação ao inchamento em tolueno. As propriedades dinâmicomecânicas dos compostos NR/SBR foram analisadas por DMA e RPA. Os compostos NR/SBR contendo somente peróxidos não apresentaram propriedades comparáveis ao composto de referência vulcanizado com enxofre. Os compostos contendo os sistemas peróxidos/co-agentes, BIS F 40 A-Retilink T40 (composto 10) e BIS F 40 A-Retilink TA 70 (composto 11) apresentaram os melhores resultados. O composto 10 e o composto de referência (composto 1) apresentaram valores similares de tan d a 60°C e tan d a 0°C (DMA), os quais estão correlacionados às propriedades de resistência ao rolamento e tração no molhado, respectivamente. Os resultados mostraram a possibilidade de uso de certos sistemas peróxido/co-agente em compostos de NR/SBR, em substituição ao sistema com enxofre, sem perda de propriedades, tendo como vantagem a redução de componentes na formulação, redução de tempo de processamento, e consequentemente custo da produção de bandas de rodagem. / Rubber compounds based on natural rubber (NR) and styrene-butadiene rubber (SBR) used on tire tread are traditionally crosslinked with sulfur. The use of peroxides and co-agents in crosslinking of these compounds is still a challenge to be achieved, considering the required viscoelastic properties which are extremely important for a good tire performance and lifetime. In this work it was evaluated the use of peroxide systems with and without co-agents as crosslinking agents for NR/SBR compounds, with the aim of evaluating the efficiency of maintaining the key properties related to the traditionally used in the manufactory of tire tread. Eleven formulations with different systems were prepared, a one as a reference. Physical properties such as hardness, density, tensile strength, tear, resilience, abrasion and compression set and the behavior of NR/SBR compounds in relation of swelling Toluene were evaluated. The dynamic mechanical properties of the NR/SBR cured compounds were analysed by DMA and RPA. The NR/SBR compounds cured with only peroxide had poorer properties when compared to the reference compound vulcanized with sulfur. On the other hand, the compounds cured with proxide/co-agents, BIS F40 plus Retilink T40 (compound 10) or plus T70A (compound 11) showed better results.The compound 10 and the reference compound (compound 1) showed similar results of tan d 60 °C and tan d 0 °C (DMA), which are correlated to rolling resistance and wet traction, respectively. The results demonstrate the possibility of using a peroxide/co-agent as a cure system in NR/SBR compound instead of a sulfur-cured compound for tire tread applications, without the loss of desirable properties, lower processing times and consequently reducing manufacturing costs.

Compostos elastoméricos a base de borracha natural (NR) e copolímero de butadieno-estireno (SBR) utilizados na banda de rodagem de pneus são tradicionalmente reticulados com enxofre. O uso de peróxidos e co-agentes na reticulação desses compostos ainda é um desafio a se superar com relação às propriedades viscoelásticas requeridas, de extrema importância para um bom desempenho e vida útil dos pneus. Neste trabalho foi avaliado o uso de peróxidos sem e com co-agentes na reticulação de compostos NR/SBR com o intuito de avaliar a eficiência destes na manutenção das propriedades relevantes em relação a um composto tradicionalmente usado na confecção de banda de rodagem de pneus. Onze formulações com diferentes sistemas de reticulação foram preparadas, sendo uma de referência. Foram avaliadas propriedades físicas como dureza, densidade, tração, resistência ao rasgamento, resiliência, abrasão e DPC, e o comportamento dos compostos de NR/SBR com relação ao inchamento em tolueno. As propriedades dinâmicomecânicas dos compostos NR/SBR foram analisadas por DMA e RPA. Os compostos NR/SBR contendo somente peróxidos não apresentaram propriedades comparáveis ao composto de referência vulcanizado com enxofre. Os compostos contendo os sistemas peróxidos/co-agentes, BIS F 40 A-Retilink T40 (composto 10) e BIS F 40 A-Retilink TA 70 (composto 11) apresentaram os melhores resultados. O composto 10 e o composto de referência (composto 1) apresentaram valores similares de tan d a 60°C e tan d a 0°C (DMA), os quais estão correlacionados às propriedades de resistência ao rolamento e tração no molhado, respectivamente. Os resultados mostraram a possibilidade de uso de certos sistemas peróxido/co-agente em compostos de NR/SBR, em substituição ao sistema com enxofre, sem perda de propriedades, tendo como vantagem a redução de componentes na formulação, redução de tempo de processamento, e consequentemente custo da produção de bandas de rodagem. / Rubber compounds based on natural rubber (NR) and styrene-butadiene rubber (SBR) used on tire tread are traditionally crosslinked with sulfur. The use of peroxides and co-agents in crosslinking of these compounds is still a challenge to be achieved, considering the required viscoelastic properties which are extremely important for a good tire performance and lifetime. In this work it was evaluated the use of peroxide systems with and without co-agents as crosslinking agents for NR/SBR compounds, with the aim of evaluating the efficiency of maintaining the key properties related to the traditionally used in the manufactory of tire tread. Eleven formulations with different systems were prepared, a one as a reference. Physical properties such as hardness, density, tensile strength, tear, resilience, abrasion and compression set and the behavior of NR/SBR compounds in relation of swelling Toluene were evaluated. The dynamic mechanical properties of the NR/SBR cured compounds were analysed by DMA and RPA. The NR/SBR compounds cured with only peroxide had poorer properties when compared to the reference compound vulcanized with sulfur. On the other hand, the compounds cured with proxide/co-agents, BIS F40 plus Retilink T40 (compound 10) or plus T70A (compound 11) showed better results.The compound 10 and the reference compound (compound 1) showed similar results of tan d 60 °C and tan d 0 °C (DMA), which are correlated to rolling resistance and wet traction, respectively. The results demonstrate the possibility of using a peroxide/co-agent as a cure system in NR/SBR compound instead of a sulfur-cured compound for tire tread applications, without the loss of desirable properties, lower processing times and consequently reducing manufacturing costs.