894 resultados para Nucleophilic addition to carbonyl


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For over a century, the Canadian state funded a church-run system of residential schools designed to assimilate Aboriginal children into Euro-Canadian culture. In addition to the problems associated with its ethnocentric philosophy, the school system was also characterised by terrible health conditions and physical and sexual abuse of the students was widespread. Recently, the schools have been the object of the most successful struggle for redress in Canadian history. One particularly puzzling aspect about the school system is that it persisted for so long, despite that many of its failings were known very early in its operation. In this article, this puzzle is addressed via a cultural analysis of a political struggle over the residential schools that occurred within Canadian Anglicanism at the outset of the twentieth century. The article concludes that the meaning of the school system as a sacred enterprise contributed to its persistence.

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he intrinsic gas-phase reactivity of cyclic N-alkyl- and N-acyliminium ions toward addition of allyltrimethylsilane (ATMS) has been compared using MS2 and MS3 pentaquadrupole mass spectrometric experiments. An order of electrophilic reactivity has been derived and found to agree with orders of overall reactivity in solution. The prototype five-membered ring N-alkyliminium ion 1a and its N-CH3 analogue 1b, as well as their six-membered ring analogues 1c and 1d, lack N-acyl activation and they are, accordingly, inert toward ATMS addition. The five- and six-membered ring N-acyliminium ions with N-COCH3 exocycclic groups, 3a and 3b, respectively, are also not very reactive. The N-acyliminium ions 2a and 2c, with s-trans locked endocyclic N-carbonyl groups, are the most reactive followed closely by 3c and 3d with exocyclic (and unlocked) N-CO2CH3 groups. The five-membered ring N-acyliminium ions are more reactive than their six-membered ring analogues, that is:  2a > 2c and 3c > 3d. In contrast with the high reactivity of 2a, its N-CH3 analogue 2b is inert toward ATMS addition. For the first time, the transient intermediates of a Mannich-type condensation reaction were isolatedthe β-silyl cations formed by ATMS addition to N-acyliminium ionsand their intrinsic gas-phase behavior toward dissociation and reaction with a nucleophile investigated. When collisionally activated, the β-silyl cations dissociate preferentially by Grob fragmentation, that is, by retro-addition. With pyridine, they react competitively and to variable extents by proton transfer and by trimethylsilylium ion abstractionthe final and key step postulated for α-amidoalkylation. Becke3LYP/6-311G(d,p) reaction energetics, charge densities on the electrophilic C-2 site, and AM1 LUMO energies have been used to rationalize the order of intrinsic gas-phase electrophilic reactivity of cyclic iminium and N-acyliminium ions.

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Introduction Compounds exhibiting antioxidant activity have received much interest in the food industry because of their potential health benefits. Carotenoids such as lycopene, which in the human diet mainly derives from tomatoes (Solanum lycopersicum), have attracted much attention in this aspect and the study of their extraction, processing and storage procedures is of importance. Optical techniques potentially offer advantageous non-invasive and specific methods to monitor them. Objectives To obtain both fluorescence and Raman information to ascertain if ultrasound assisted extraction from tomato pulp has a detrimental effect on lycopene. Method Use of time-resolved fluorescence spectroscopy to monitor carotenoids in a hexane extract obtained from tomato pulp with application of ultrasound treatment (583 kHz). The resultant spectra were a combination of scattering and fluorescence. Because of their different timescales, decay associated spectra could be used to separate fluorescence and Raman information. This simultaneous acquisition of two complementary techniques was coupled with a very high time-resolution fluorescence lifetime measurement of the lycopene. Results Spectroscopic data showed the presence of phytofluene and chlorophyll in addition to lycopene in the tomato extract. The time-resolved spectral measurement containing both fluorescence and Raman data, coupled with high resolution time-resolved measurements, where a lifetime of ~5 ps was attributed to lycopene, indicated lycopene appeared unaltered by ultrasound treatment. Detrimental changes were, however, observed in both chlorophyll and phytofluene contributions. Conclusion Extracted lycopene appeared unaffected by ultrasound treatment, while other constituents (chlorophyll and phytofluene) were degraded.

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Depuis que la haute énantiopureté est nécessaire dans l’industrie pharmaceutique, les études visant à découvrir les mécanismes pour l’hydrogénation énantiosélective de cétones ou céto-esters sur les surfaces, et à rechercher de nouveaux et plus performants catalyseurs asymétriques, sont d’une grande importance. La microscopie à effet tunnel (STM), la spectroscopie infrarouge de réflexion-absorption, la spectroscopie de désorption à température programmée et la spectrométrie de photoélectrons induits par rayons X sont des méthodes performantes facilitant la compréhension des mécanismes de réaction. En plus de nous permettre de comprendre les mécanismes réactionnels, les études peuvent fournir des informations sur la dynamique des réactions en catalyse hétérogène ainsi que sur le développement de la théorie de la fonctionnelle de la densité (DFT) afin de calculer des interactions faibles dans les processus de surface. D’autres parts, les calculs DFT fournissent une aide essentielle à l’interprétation des données de STM et spectroscopie de surface. Dans cette thèse, certains cétones et céto-esters sur la surface de platine sont étudiées par les techniques sophistiquées mentionnées ci-dessus. Mes études démontrent que la combinaison de l’utilisation de la spectroscopie de routine, des nanotechnologies et de nombreux calculs élaborés, est une méthode efficace pour étudier les réactions à la surface car ces techniques explorent les différents aspects de la surface ainsi que s’entraident mutuellement lors de certaines interprétations.

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This thesis is an edition of the correspondence of the Yorkshirean Wentworth family. The aim of the edition is to provide these handwritten manuscripts to a wider audience by transcribing them. The material has been acquired from the Folger Shakespeare Library, and the transcriptions presented in this thesis are a part of their database called Early Modern Manuscripts Online. My material consists of fifteen documents from the early modern period which have been sent to or sent by members of the Wentworth family. Fourteen of these documents are letters, and one is a warrant written in the form of a letter. In the Folger Shakespeare Library the documents form the section 2.1. Correspondence of the Wentworth family in a larger collection called Papers of the Cavendish-Talbot family. The documents have been transcribed diplomatically in order to retain the character of the original manuscripts. In addition to the transcriptions, background chapters on letter writing, the historical and linguistic context, and palaeography are provided. Furthermore, each text includes a commentary containing a brief summary of the text and a description of the manuscript. Notes concerning specific words or concepts are also provided to make the texts easier to understand. Additionally, the transcriptions are encoded in XML for the purposes of the Folger Shakespeare Library. These earlier unedited manuscripts reassert the status of the Wentworth family in the early modern English society and provide information about letter writing conventions, language, and palaeographical conventions in early modern England. This edition can be used in further studies, for example as part of a larger corpus.

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Abstract. The use of artificial immune systems in intrusion detection is an appealing concept for two reasons. Firstly, the human immune system provides the human body with a high level of protection from invading pathogens, in a robust, self-organised and distributed manner. Secondly, current techniques used in computer security are not able to cope with the dynamic and increasingly complex nature of computer systems and their security. It is hoped that biologically inspired approaches in this area, including the use of immune-based systems will be able to meet this challenge. Here we collate the algorithms used, the development of the systems and the outcome of their implementation. It provides an introduction and review of the key developments within this field, in addition to making suggestions for future research.

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This dissertation explores why some states consistently secure food imports at prices higher than the world market price, thereby exacerbating food insecurity domestically. I challenge the idea that free market economics alone can explain these trade behaviors, and instead argue that states take into account political considerations when engaging in food trade that results in inefficient trade. In particular, states that are dependent on imports of staple food products, like cereals, are wary of the potential strategic value of these goods to exporters. I argue that this consideration, combined with the importing state’s ability to mitigate that risk through its own forms of political or economic leverage, will shape the behavior of the importing state and contribute to its potential for food security. In addition to cross-national analyses, I use case studies of the Gulf Cooperation Council states and Jordan to demonstrate how the political tools available to these importers affect their food security. The results of my analyses suggest that when import dependent states have access to forms of political leverage, they are more likely to trade efficiently, thereby increasing their potential for food security.

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Bovine respiratory disease (BRD) is the most important cause of clinical disease and death in feedlot cattle. Respiratory viral infections are key components in predisposing cattle to the development of this disease. To quantify the contribution of four viruses commonly associated with BRD, a case-control study was conducted nested within the National Bovine Respiratory Disease Initiative project population in Australian feedlot cattle. Effects of exposure to Bovine viral diarrhoea virus 1 (BVDV-1), Bovine herpesvirus 1 (BoHV-1), Bovine respiratory syncytial virus (BRSV) and Bovine parainfluenza virus 3 (BPIV-3), and to combinations of these viruses, were investigated. Based on weighted seroprevalences at induction (when animals were enrolled and initial samples collected), the percentages of the project population estimated to be seropositive were 24% for BoHV-1, 69% for BVDV-1, 89% for BRSV and 91% for BPIV-3. For each of the four viruses, seropositivity at induction was associated with reduced risk of BRD (OR: 0.6–0.9), and seroincrease from induction to second blood sampling (35–60 days after induction) was associated with increased risk of BRD (OR: 1.3–1.5). Compared to animals that were seropositive for all four viruses at induction, animals were at progressively increased risk with increasing number of viruses for which they were seronegative; those seronegative for all four viruses were at greatest risk (OR: 2.4). Animals that seroincreased for one or more viruses from induction to second blood sampling were at increased risk (OR: 1.4–2.1) of BRD compared to animals that did not seroincrease for any viruses. Collectively these results confirm that prior exposure to these viruses is protective while exposure at or after feedlot entry increases the risk of development of BRD in feedlots. However, the modest increases in risk associated with seroincrease for each virus separately, and the progressive increases in risk with multiple viral exposures highlights the importance of concurrent infections in the aetiology of the BRD complex. These findings indicate that, while efficacious vaccines could aid in the control of BRD, vaccination against one of these viruses would not have large effects on population BRD incidence but vaccination against multiple viruses would be expected to result in greater reductions in incidence. The findings also confirm the multifactorial nature of BRD development, and indicate that multifaceted approaches in addition to efficacious vaccines against viruses will be required for substantial reductions in BRD incidence.

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The concept of equal opportunity for all students is deeply embedded in the Serbian constitution and in education laws. On that level, there is no doubt that everyone is ensured an opportunity to receive quality education. Many measures in education policy have been created specifically to achieve this objective and make the system fair and inclusive. The Coleman Report was linked to a wave of optimism that certain educational measures would help in achieving these noble goals. This aim is a high priority in education in a democratic country, and due to its importance needs to be re-examined. Thus, the present research examines the equity of students in the Serbian education system, detecting areas on all educational levels that could be (or already are) systemic sources of inequity (e.g., criteria for preschool institution enrolment, the system of student awards, rationalisation of the school network, the concept of entrance exams to secondary school or university, etc.). A number of measures have already been taken in the system specifically to deal with inequity (e.g., the Preschool Preparatory Programme, dropout measures, inclusion, scholarships, etc.). The effects of these measures in particular are analysed in the present work. In addition to an analysis of the systemic sources of inequity in the Serbian education system, the article also makes recommendations for their overcoming. (DIPF/Orig.)

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Composts can provide a source of organic carbon and nutrients for soil biota and increase soil fertility as well as provide other biological and structural benefits hence compost addition to cotton soils is seen as a way to improve cotton soil biological health and fertility. In a six month incubation experiment we analysed the changes in microbial populations and activities related to C and N cycling following the application of feedlot, poultry manure and gin trash compost materials. A significant variation in the chemical composition, e.g. major nutrients and trace elements, was found between the three compost products. The feedlot compost generally contained higher levels of dissolved organic carbon, total nitrogen and bicarbonate extractable phosphorus whereas the Gin trash compost had lower carbon and nutrient concentrations. The effect of compost addition @ 5 and 10t/ha generally increased microbial activity but the effect was only evident during the first two weeks of incubation. Composts effects on the abundance of total bacteria (16S), nitrifying (amoA), nitrogen fixing (nifH) and denitrifying bacteria (nosZ) and total fungi (ITS gene) varied between different composts. The addition of feedlot and poultry compost material significantly increased the levels of dissolved organic carbon (DOC) and nitrogen (DON) in soil compared to that in control soils while ‘Gin trash’ compost had no effect. These differences reflected in the microbial catabolic diversity changes in the compost amended soils. Therefore, chemical analysis of the compost material before application is recommended to more fully consider its’ potential benefits.

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Microplankton plays a vital part in marine ecosystems and its importance has been recognised by the inclusion of microplankton community composition in regulatory frameworks such as the European Water Framework Directive and the Marine Strategy Framework Directive as an indicator of ecological status. Quantitative techniques are therefore required to assess the environmental status of the microplankton in a water body. Here we demonstrate the use of a method known as the Microplankton Index PI(mp) to evaluate changes in the microplankton community of the West coast Scottish Sea Loch Creran. Microplankton in this fjord has been studied since the 1970’s providing a data set spanning four decades. Our analysis compares an arbitrarily chosen reference period between 1979 and 1981 with a period between 2011 and 2013 and demonstrates that between these two periods community structure has changed considerably with a substantial drop in the numbers of observed diatoms accompanied by a rise in the number of autotrophic/mixotrophic dinoflagellates as well as an increase in the potentially toxin producing genus Pseudo-nitzschia and that these are related to changes in both the intensity and timing of local patterns of precipitation. The PI(mp) is shown to be a useful and robust method to visualise and quantify changes in the underlying structure of the microplankton community and is a powerful addition to the toolbox of techniques needed to determine the health of our seas.

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The use of artificial immune systems in intrusion detection is an appealing concept for two reasons. Firstly, the human immune system provides the human body with a high level of protection from invading pathogens, in a robust, self-organised and distributed manner. Secondly, current techniques used in computer security are not able to cope with the dynamic and increasingly complex nature of computer systems and their security. It is hoped that biologically inspired approaches in this area, including the use of immune-based systems will be able to meet this challenge. Here we review the algorithms used, the development of the systems and the outcome of their implementation. We provide an introduction and analysis of the key developments within this field, in addition to making suggestions for future research.

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Nowadays there is a huge evolution in the technological world and in the wireless networks. The electronic devices have more capabilities and resources over the years, which makes the users more and more demanding. The necessity of being connected to the global world leads to the arising of wireless access points in the cities to provide internet access to the people in order to keep the constant interaction with the world. Vehicular networks arise to support safety related applications and to improve the traffic flow in the roads; however, nowadays they are also used to provide entertainment to the users present in the vehicles. The best way to increase the utilization of the vehicular networks is to give to the users what they want: a constant connection to the internet. Despite of all the advances in the vehicular networks, there were several issues to be solved. The presence of dedicated infrastructure to vehicular networks is not wide yet, which leads to the need of using the available Wi-Fi hotspots and the cellular networks as access networks. In order to make all the management of the mobility process and to keep the user’s connection and session active, a mobility protocol is needed. Taking into account the huge number of access points present at the range of a vehicle for example in a city, it will be beneficial to take advantage of all available resources in order to improve all the vehicular network, either to the users and to the operators. The concept of multihoming allows to take advantage of all available resources with multiple simultaneous connections. This dissertation has as objectives the integration of a mobility protocol, the Network-Proxy Mobile IPv6 protocol, with a host-multihoming per packet solution in order to increase the performance of the network by using more resources simultaneously, the support of multi-hop communications, either in IPv6 or IPv4, the capability of providing internet access to the users of the network, and the integration of the developed protocol in the vehicular environment, with the WAVE, Wi-Fi and cellular technologies. The performed tests focused on the multihoming features implemented on this dissertation, and on the IPv4 network access for the normal users. The obtained results show that the multihoming addition to the mobility protocol improves the network performance and provides a better resource management. Also, the results show the correct operation of the developed protocol in a vehicular environment.

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In a survey on 524 specimens from 18 different species belonging to the Carangidae family collected from The Persian Gulf, otolithes (Sagittae) are extracted from under gills region. After washing, their morphometric parameters measured. These parameters are otolith length, width, weight and length of antirostrum, width and length of rostrum, width in right and left sagittae. In addition to the otolith outline, mode position and mode opening of the Sulcus acusticus was examined. Data indicate correlation between most of the parameters (P<0.05). This shows correlation between total length and weight of fish, otolith length and weight of otolith in most of specimens. There was correlation in most species between otolith length and total length of studies fishes, otolith weight and weight of fish, otolith weight and total length, otolith length and weight of fish, length of right and left otolith. Otolith had very diveres outline types (fusiform, sagitiform, lanceolated, iregular). There were most of variety about status dentates in dorsal margin and ventral margin of the otolith. As result of this analysis it is possible to identify species from the Carangidae family by the otolith characters.