482 resultados para Irish Studies
Resumo:
Existing research and best practice were utilized to develop the Project Management, Stakeholder Engagement and Change Facilitation (PSC) approach to road safety infrastructure projects. Two case studies involving Queensland Transport and Main Roads demonstrated that use of the PSC has potential to create synergies for projects undertaken by multi-disciplinary road safety groups, and to complement Safe System projects and philosophy. The case studies were the North West Road Safety Alliance project, and the implementation of Road Safety Audit policy, and utilised a mix of qualitative and quantitative methods including interviews and surveys.
Resumo:
Aflatoxin B1, a potently carcinogenic fungal metabolite, is converted to the biologically active form by chemical oxidation using dimethyldioxirane and enzymatically by cytochrome P450 mixed-function oxidases. Both processes give rise to mixtures of the exo- and endo-8,9-epoxides. Methanolysis studies reveal exclusive trans opening of both epoxides under neutral conditions in CH3OH and CH3OH/H2O mixtures; an SN2 mechanism is postulated. Under acidic conditions, the exo isomer gives mixtures of trans and cis solvolysis products, suggesting that the reaction is, at least in part, SN1; the endo isomer gives only the trans product. The exo isomer reacts with DNA by attack of the nitrogen atom at the 7 position of guanine on C8 of the epoxide to give the trans adduct; the endo epoxide fails to form an adduct at this or any other site in DNA. The exo isomer is strongly mutagenic in a base-pair reversion assay employing Salmonella typhimurium; the endo isomer is essentially nonmutagenic. Aflatoxin B1 and its derivatives intercalate in DNA. These results are consistent with a mechanism in which intercalation of the exo epoxide optimally orients the epoxide for an SN2 reaction with guanine but intercalation of the endo isomer places the epoxide in an orientation which precludes reaction. Thus, while the exo epoxide is a potent mutagen, the endo epoxide fails to react with DNA.
Hydrolysis of genotoxic methyl-substituted oxiranes : Experimental kinetic and semiempirical studies
Resumo:
The kinetics of acid-catalyzed hydrolysis of seven methylated aliphatic epoxides - R1R2C(O)CR3R4 (A: R1=R2=R3=R4=H; B: R1=R2=R3=H, R4=Me; C: R1=R2=H, R3=R4=Me; D: R1=R3=H, R2=R4=Me(trans); E: R1=R3=H, R2=R4=Me(cis); F: R1=R3=R4=Me, R2=H; G: R1=R2=R3=R4=Me) - has been studied at 36 ± 1.5°C. Compounds with two methyl groups at the same carbon atom of the oxirane ring exhibit highest rate constants (k(eff) in reciprocal molar concentration per second: 11.0 ± 1.3 for C, 10.7 ± 2.1 for F, and 8.7 ± 0.7 for G as opposed to 0.124 ± 0.003 for B, 0.305 ± 0.003 for D, and 0.635 ± 0.036 for E). Ethylene oxide (A) displays the lowest rate of hydrolysis (0.027 M-1 s-1). The results are consistent with literature data available for compounds A, B, and C. To model the reactivities we have employed quantum chemical calculations (MNDO, AM1, PM3, and MINDO/3) of the main reaction species. There is a correlation of the logarithm k(eff) with the total energy of epoxide ring opening. The best correlation coefficients (r) were obtained using the AM1 and MNDO methods (0.966 and 0.957, respectively). However, unlike MNDO, AM1 predicts approximately zero energy barriers for the oxirane ring opening of compounds B, C, E and G, which is not consistent with published kinetic data. Thus, the MNDO method provides a preferential means of modeling the acidic hydrolysis of the series of methylated oxiranes. The general ranking of mutagenicity in vitro, A > B > C, is in line with the concept that this sequence also gradually leaves the expoxide reactivity optimal for genotoxicity toward reactivities leading to higher biological detoxifications.
Resumo:
The growing knowledge of the genetic polymorphisms of enzymes metabolising xenobiotics in humans and their connections with individual susceptibility towards toxicants has created new and important interfaces between human epidemiology and experimental toxicology. The results of molecular epidemiological studies may provide new hypotheses and concepts, which call for experimental verification, and experimental concepts may obtain further proof by molecular epidemiological studies. If applied diligently, these possibilities may be combined to lead to new strategies of human-oriented toxicological research. This overview will present some outstanding examples for such strategies taken from the practically very important field of occupational toxicology. The main focus is placed on the effects of enzyme polymorphisms of the xenobiotic metabolism in association with the induction of bladder cancer and renal cell cancer after exposure to occupational chemicals. Also, smoking and induction of head and neck squamous cell cancer are considered.
Resumo:
XRF spectrometry was applied to provenance studies of Iron Age pottery specimens that originated from the Mngeni river area in South Africa. Ten transition metals (Sc to Zn) mere determined in 107 potsherds, excavated from four different sites. The data were subjected to a computerized mathematical technique (correspondence analysis), which was used to group the samples according to the similarity of their elemental distributions. The groupings were interpreted in terms of social or cultural interaction between the sites. (C) 1997 by John Wiley & Sons, Ltd.
Resumo:
Provenance studies of iron-age pottery specimens originating from the Mngeni river area in South Africa was carried out by applying XRF spectrometry. A total of sixteen major and trace elements were analysed in a batch of 107 potsherds, excavated from four different archaeological sites in the aforementioned area. A multivariate statistical programme Correspondence Analysis was used in this study to obtain the relevant clustering patterns according to the similarity of the elemental distributions. Differences and similarities in the clusters obtained for the majors and trace elements are discussed.
Resumo:
Cool roof coatings are identified by their solar reflectance index. They have been reported to have multiple benefits, the extent of which are strongly dependent on the peculiarities of the local climate, building stock and electricity network. This paper presents measured and simulated data from residential, educational and commercial buildings involved in recent field trials in Australia. The purpose of the field trials was to evaluate the impact of such coatings on electricity demand and load and to assess their potential application to improve comfort whilst avoiding the need for air conditioners. Measured reductions in temperature, power (kW) and energy (kWh) were used to develop a predictive model that correlates ambient temperature distribution profiles, building demand reduction profiles and electricity network peak demand times. Combined with simulated data, the study indicates the types of buildings that could be targeted in Demand Management programs for the mutual benefit of electricity networks and building occupants.
Resumo:
Self-assembled monolayer (SAM) of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) was prepared on indium tin oxide (ITO) electrode by spontaneous adsorption from dimethylformamide (DMF) solution containing 4α-CoIITAPc. The SAM of 4α-CoIITAPc formed on ITO electrode was characterized by cyclic voltammetry, Raman and UV–visible spectroscopic techniques. The cyclic voltammogram (CV) of 4α-CoIITAPc SAM shows two pairs of well-defined redox peaks corresponding to CoIII/CoII and CoIIIPc−1/CoIIIPc−2. The surface coverage (Γ) was calculated by integrating the charge under the anodic wave corresponding to CoII oxidation and it was found to be 2.25 × 10−10 mol cm−2. Raman spectrum obtained for the SAM of 4α-CoIITAPc on ITO surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Further, the –NH2 bending mode of vibration was absent for the SAM of 4α-CoIITAPc on ITO surface which indirectly confirmed that all the amino groups of 4α-CoIITAPc are involved in bonding with ITO surface. UV–visible spectrum for the SAM of 4α-CoIITAPc on ITO surface shows an intense B-band, Q-band and n–π∗ transition with slight broadening when compared to that of 4α-CoIITAPc in DMF.
Resumo:
This work describes recent extensions to the GPFlow scientific workflow system in development at MQUTeR (www.mquter.qut.edu.au), which facilitate interactive experimentation, automatic lifting of computations from single-case to collection-oriented computation and automatic correlation and synthesis of collections. A GPFlow workflow presents as an acyclic data flow graph, yet provides powerful iteration and collection formation capabilities.
Resumo:
Strengthening of metallic structures using carbon fibre reinforced polymer (CFRP) has become a smart strengthening option over the conventional strengthening method. Transverse impact loading due to accidental vehicular collision can lead to the failure of existing steel hollow tubular columns. However, knowledge is very limited on the behaviour of CFRP strengthened steel members under dynamic impact loading condition. This paper deals with the numerical simulation of CFRP strengthened square hollow section (SHS) steel columns under transverse impact loading to predict the behaviour and failure modes. The transverse impact loading is simulated using finite element (FE) analysis based on numerical approach. The accuracy of the FE modelling is ensured by comparing the predicted results with available experimental tests. The effects of impact velocity, impact mass, support condition, axial loading and CFRP thickness are examined through detail parametric study. The impact simulation results indicate that the strengthening technique shows an improved impact resistance capacity by reducing lateral displacement of the strengthened column about 58% compared to the bare steel column. Axial loading plays an important role on the failure behaviour of tubular column.
Resumo:
Understanding the natural variability of the Earth's climate system and accurately identifying potential anthropogenic influences requires long term, geographically distributed records of key climate indicators, such as temperature and precipitation that extend prior to the last 400. years of the Holocene. Reef corals provide an excellent source of high resolution climate records, and importantly represent the tropical marine environment where palaeoclimate data are urgently required. Recent decades have seen significant improvement in our understanding of coral biomineralisation, the associated uptake of geochemical proxies and methods of identifying and understanding the effects of both early and late, post depositional diagenetic alteration. These processes all have significant implications for interpreting geochemical proxies relevant to palaeoclimatic reconstructions. This paper reviews the current 'state of the art' in terms of coral based palaeoclimate reconstructions and highlights a key remaining problem. The majority of coral based palaeoclimate research has been derived from massive colonies of Porites. However, massive Porites are not globally abundant and may not provide material of a particular age of interest in those regions where they are present. Therefore, there is great potential for alternate coral genera to act as complimentary climate archives. While it remains critical to consider five key factors - vital effects, differential growth morphologies, geochemical heterogeneity in the skeletal ultrastructure, transfer equation selection and diagenetic screening of skeletal material - in order to allow the highest level of accuracy in coral palaeoclimate reconstructions, it is also important to develop alternate taxa for palaeoclimate studies in regions where Porites colonies are absent or rare. Currently as many as nine genera other than Porites have proven at least limited utility in palaeothermometry, most of which are found in the Atlantic/Caribbean region where massive Porites do not exist. Even branching taxa such as Acropora have significant potential to preserve environmental archives. Increasing this capability will greatly expand the number of potential geochemical archives available for longer term temporal records of palaeoclimate.
Resumo:
When preparing this special issue,1 our discussions with the editorial board of the International Journal of Cultural Studies (IJCS) included a moment of simultaneous surprise and reflection, which we would like to use as a starting point for our introduction to the articles appearing here. This occurred during communications about the number and length of the articles required for a special issue. The board’s representative stipulated that a specific number of articles were to be written by Indonesian scholars. The request surprised us. We had neither discussed nor anticipated ethnic or national quotas for authorial participation. But although the request caught us off guard it also stimulated us to think about the two disciplinary terrains traversed in the articles to follow.