Toisen jäte on toisen raaka-aine – Kierrätys ja uudelleenvalmistus taloudellisesti ja ekologisesti kestävänä liiketoimintamahdollisuutena

Toisen jäte on toisen raaka-aine – Kierrätys ja uudelleenvalmistus taloudellisesti ja ekologisesti kestävänä liiketoimintamahdollisuutena Väitöskirjatutkimus tarkastelee kierrätystä ja uudelleenvalmistusta sekä siihen perustuvaa kierrätysliiketoimintaa taloudellisesti ja ekologisesti kestävänä liiketoimintamahdollisuutena. Tässä kestävyys tarkoittaa jätekysymysten ratkaisemista tavalla, joka mahdollistaa kestävän kehityksen periaatteiden mukaisen yhteiskunnan kehittymisen. Jätteisiin liittyvät taloudelliset ja ekolo- giset kysymykset ovat merkittävä yhteiskunnallinen haaste. Tämä luo tarpeen tutkimukselle, jonka lähtökohtana on jätekysymysten moniulotteinen tarkas- telu ja yksittäisen yrityksen toiminnan suhteuttaminen osaksi laajempaa kokonaisuutta. Tässä tutkimuksessa jätteen hyödyntämistä materiaalina lähestytään sekä empiirisesti yrityksen näkökulmasta että teoreettisesti systeemiajattelun tarjoamasta laajemmasta perspektiivistä. Tutkimuksen tavoitteena on ymmär- tää kierrätystä ja uudelleenvalmistusta liiketoimintamahdollisuutena, niiden merkitystä yrityksessä, alueella ja kierrätystaloudessa sekä näiden vuorovai- kutteista suhdetta taloudelliseen ja ekologiseen kestävyyteen nähden. Tutki- muskysymys on tärkeä, koska siihen vastaamalla syvennetään ymmärrystä yrityksissä tapahtuvan kierrätyksen ja uudelleenvalmistuksen merkityksestä kestävämmän yhteiskunnan rakentumisessa. Tutkimuksen teoriaperusta pohjautuu teollisen ekologian kirjallisuuteen ja ekoteollisen kehityksen tutkimukseen. Kierrätysliiketoiminnan kestävyyden tarkastelu rakentuu tutkimuksessa teollisen ekologian ja ekoteollisen kehityk- sen lähtökohtana olevaan win-win-ajatteluun, jonka mukaan hyvä ympäristö- suorituskyky ja hyvä taloudellinen suorituskyky voivat vahvistaa toisiaan. Kierrätysliiketoiminnan teoreettisessa tarkastelussa keskeisiä elementtejä ovat kierrätystalouden malli, teollisen ekologian alueelliset systeemit, ekoteolliset verkostot ja yrityksen rooli teollista ekologiaa soveltavana toimijana. Tutki- muksen keskeisenä kontribuutiona on yritysnäkökulman integroiminen aiem- paa vahvemmin osaksi teollisen ekologian diskursseja. Kierrätysliiketoiminnan taloudelliseen ja ekologiseen kannattavuuteen ja sen myötä kestävyyteen liittyviä kysymyksiä on lähestytty tekemällä yritys- haastatteluja ja hyödyntämällä valmista haastatteluaineistoa. Tutkimusta varten haastattelin 10 kierrätysliiketoimintaa harjoittavaa yritystä vuosina 2007 ja 2008. Tämän lisäksi tutkimuksessa on hyödynnetty Turun ammatti- korkeakoulun ja Turku Science Parkin toteuttamassa RESU-hankkeessa (Kierrätysliiketoiminta ja resurssitehokkuus Varsinais-Suomen vahvuudeksi – RESU) vuosina 2013 ja 2014 kerättyä aineistoa. Hankkeessa haastateltiin yhteensä 25 jätemateriaalia hyödyntävää ja/tai tuottavaa yritystä. Aineistojen analysointimenetelmänä on sisällönanalyysi. Analyysin tulok- sena muodostettiin yhteensä viisi pääteemaa ja 12 alateemaa. Teemat kuvaavat kierrätysliiketoimintaa aiempaa moniulotteisemmin ja näin syventävät ymmär- rystä ilmiön merkityksestä kestävämmän yhteiskunnan rakentumisessa. Teolli- sen ekologian alaan kuuluvat kvalitatiiviset tutkimukset ovat melko harvinai- sia, joten tämän väitöstutkimuksen ilmeisenä vahvuutena on laadullisen tutkimusmenetelmän hyödyntäminen. Tutkimuksen tuloksena voidaan todeta, että kierrätystalouden kehittymistä edistävä kierrätysliiketoiminta on monimuotoista ja sisältää erilaisia liiketoi- mintamahdollisuuksia sekä arvoketjuja. Paikallistuntemus ja keskeinen sijainti jätemateriaalien tuottajien suhteen on tärkeä kriteeri kierrätysliiketoiminnassa, mutta jätemateriaaleja myös kuljetetaan pitkiä matkoja. Paikallisia tai alueelli- sia jätevirtoja hyödyntävä kierrätysliiketoiminta voi tukea alueellista kestä- vyyttä, mutta toisinaan myös keskitetty hyödyntäminen voi olla kestävä vaih- toehto. Yhteistyöverkostot ovat tärkeitä jätemateriaalin laadun ja saatavuuden näkökulmasta. Tutkimus osoittaa, että kierrätysliiketoimintaa harjoittavat yritykset ovat samalla sekä kierrätystalouden käytännön toimeenpanijoita että uuden toimintakulttuurin luojia. Tutkimuksen tulosten perusteella voidaan esittää johtopäätös, että kierrä- tysliiketoiminta on taloudellisesti ja ekologisesti kannattava liiketoimintamah- dollisuus. Win-win-ratkaisut eivät kuitenkaan takaa kierrätysliiketoiminnan kestävyyttä. Kierrätysliiketoiminnan kestävyyden arvioiminen edellyttää laajaa perspektiiviä ja toiminnan vaikutusten suhteuttamista mittakaavaan, ajalliseen ulottuvuuteen, interventioon ja sosiaalisiin kysymyksiin. Teolliseen ekologiaan perustuva kierrätysliiketoiminta luo mahdollisuuksia edistää kestävyyttä, joten tällä perusteella kierrätystä ja uudelleenvalmistusta voidaan pitää kestävänä liiketoimintamahdollisuutena. Avainsanat: kierrätysliiketoiminta, kierrätys, uudelleenvalmistus, systeemiajattelu, teollinen ekologia, ekoteollinen kehitys, kierrätystalous, win-win-ajattelu, kestävyys One company's waste is another's raw material –Recycling and remanufacturing as an economically and environmentally sustainable business opportunity The thesis investigates whether product recycling and remanufacturing can serve as a business opportunity that is economically and ecologically sustaina- ble. In this effort, my idea is to contribute to solving the waste issue in a manner that makes it possible to strive toward sustainable societal develop- ment. The economic and ecological questions associated with waste flows are a significant challenge. The complexity of the issue requires a multidimen- sional approach in which the operation of an individual company is viewed in the context of the larger societal system. In this thesis waste utilization as a resource with value is considered both from an empirical perspective on the firm as well as from a more general viewpoint offered by systems analysis. The objective of the thesis is to under- stand recycling and remanufacturing as a business opportunity. The thesis considers the meaning of recycling and remanufacturing for a single company, for the region the company is located and for the recycling economy. The objective of this study is important for it enhances the understanding of the product recycling and remanufacturing processes that take place within busi- ness organizations and how these processes affect societal sustainable development. The theoretical basis arises from industrial ecology and from the literature on eco-industrial development. The business-economic win-win situation and this vision serve as the basic position from which recycling business is inves- tigated in the thesis. In the theoretical discussion, key elements are recycling economy model, regional and local industrial ecosystems, eco-industrial networks and the role of a company as an actor that applies industrial ecology in practice. The main contribution of this study lies in integrating the company perspective more strongly into the industrial ecology discourses. The recycling business has been studied by conducting interviews in companies and by secondary analysis of an existing interview material. During 2007 and 2008 I made 10 interviews in companies that are active in recycling business. In addition, I used interview material gathered for the project “Recycling business and resource efficiency as the strength of Southwest Finland” (RESU) by Turku University of Applied Sciences and Turku Science Park during the period 2013–2014. This data covers altogether 25 businesses that either utilize and/or produce waste materials. The data has been analyzed using the content analysis method. This process led to the development of 5 main themes and 12 sub-themes. These themes describe the recycling business multi-dimensionally and thus understanding of the phenomenon and its role in building a sustainable society are substantially deepened in this research. In the field of industrial ecology qualitative studies are relatively rare and therefore the qualitative research approach is an evident strength of the thesis. The results show that the recycling business activity supporting recycling economy has diverse dimensions including various business opportunities and diverse value chains. The results show that for waste producers it is important to know the local situational factors and to have a central geographical location. Waste materials are, however, transported over long distances as well. The study indicates that local waste flow utilization can support regional sustainability, while occasionally a more centralized utilization can be sustain- able. Collaboration networks are important to secure the quality and availabil- ity of utilizable waste materials. The thesis demonstrates that the companies practicing recycling business serve simultaneously as actors that implement recycling economy and enhance a new operation culture within the business community. The overall conclusion of the thesis argues that recycling business is a business opportunity that can support both an economically and environmen- tally viable business operation. However, win-win solutions do not secure the sustainability of recycling business. The sustainability evaluation of recycling business requires a holistic systems perspective. The actions undertaken need to be considered with changing spatial and temporal system boundaries, societal intervention and placed in the context of relevant societal issues. Industrial ecology -based recycling business creates opportunities for sustain- ability and thus recycling and remanufacturing present an opportunity for sustainable business. Keywords: Recycling business; Recycling; Remanufacturing, Systems thinking; Industrial ecology; Eco-industrial development; Recycling Economy; Win-Win thinking; Sustainability

As definições teóricas de direitos humanos de Jürgen Habermas: o princípio legal e as correções morais[ign] [title language="en"]The theoretical definitions of human rights of Jürgen Habermas[ign]: [subtitle]legal principle and moral corrections

No entendimento de Habermas, "direito", na expressão "direitos humanos", é um conceito jurídico, donde direitos humanos, para ele, serem direitos jurídicos, normas legais declaradas em atos de fundações do Estado ou anunciadas em convenções do direito internacional e/ou constituições estatais. Ao conceber assim os direitos e tematizar os direitos humanos numa abordagem tríplice (focando-os entre moral, direito e política), ele fornece diferentes definições teóricas dos direitos humanos. O texto apresenta uma exposição sistemática dessas definições e focaliza os diferentes problemas que motivaram Habermas a alterar e ampliar suas concepções de direitos humanos.

Foraging ecology and parental behaviour in the common tern (Sterna hirundo)

One component of successful parenting is related to efficiency in foraging behaviour. The relationships among chick feeding, the size and type of food package, and length of parental foraging trips has not been well studied in seabirds. In addition, relatively few data have been collected on the activities of seabirds when foraging away from the nest site. The objectives of this study were: (1) to contrast productivity, feeding rate, and attendance patterns of individuals carrying a novel transmitter with a control group of birds; (2) to use radio-telemetry to assess the variability in foraging locations within and between individual male Common Terns; (3) to determine the seasonal variation in chick diet; (4) to determine for each transmittered bird, the relationships among the foraging patterns, parental behaviour, and seasonal reproductive success. The study took place over two years (1990-91) on a concrete breakwater 1 km offshore on Lake Erie near Port Colbome, Ontario. Ten pairs of terns in 1990 and 12 pairs in 1991 were radio-tracked by boat or car during the chick rearing stage. Concurrent behavioural observations documented the time each sex spent foraging or at the nest. The frequency and prey species composition of feeds to chicks were also recorded. The transmitters had negligible effects on the feeding frequency and brood attendance patterns of transmitter carrying birds. Peak nesting transmittered birds in 1990 and 1991 exhibited some inter-individual variability in foraging locations, however intraindividual variability was low. Birds foraged primarily to the west and northwest of the colony. Late nesters exhibited greater inter-individual variability, however intra-individual variability remained low for most birds. Neither group demonstrated sufficient variability to support the regular use of this colony as an "information centre". Individual transmittered birds had unique and predictable foraging patterns, and corresponding differences in feeding frequencies and brood attendance patterns, yet productivity was essentially equal between nests due to the impact and importance of stochastic events. Individuals that were recaptured in 1991 exhibited very similar foraging patterns to 1990, suggesting littie variability between years. Conservation of foraging patterns between years may have potential implications for mate choice decisions in future breeding seasons. Prey species delivered to chicks differed between morning and evening for peak and late nesters in 1990, but not 1991. Peak nesters in 1990 fed significantiy more Rainbow Smelt fOsmerus mordM) than Emerald Shiner (Notropis atherinoidesV this trend was reversed for late nesters who also fed large numbers of unidentified larval fish. No significant differences were found in 1991. Seasonal changes in prey species delivered to chicks is believed to be attributable to the temperature tolerances of the smelt and shiners, and the presence of large schools of larval fish during the late nesting season.

The backwoods of our backyards : Ontario pioneers and the crisis of ecology /

Early in his landmark ecocritical book The Comedy of Survival, Joseph Meeker develops an intriguing hypothesis about human behaviour. He remarks the species Homo sapiens tend to behave like an invasive or pioneering organism, entering a bio-geographical region and aggressively outcompeting all other species for space and resources. Moreover, he suggests, human cultural traditions, at least in the West, have reinforced such behaviour, continually insisting that the impulses he describes are both necessary and right. While Meeker's work goes on to assess a number of literary works in both the tragic and comic modes, his work never fully explores this hypothesis in the context of human pioneers; that is, there is no ~xploration o( how these themes manifest themselves within our culture and what role they might play in the culture of specific pioneering groups. This project is an attempt at just such an analysis, examining the validity of Meeker's hypothesis through a case study of settler literature in Upper Canada/Ontario between the . years 1800-1867. It explores Meeker's work within three main areas: first, Chapter Two situates his book historically within the field of ecocriticism, showing what came before and the explosion of ecocritical inquiry that followed its release. This chapter also delves into the rift between the natural sciences and humanities, arguing that a move towards deeper interdisciplinarity is r:tecessary for the future. Chapter Three examines the biological and ecological ground on which Meeker rests his hypothesis through exploring evolutionary biology as well as invasive and pioneer species behaviour. Lastly, Chapter Four examines how these ecological principles are manifested in the writings of early Canadian settlers, suggesting that Meeker's hypothesis indeed finds itself on stable footing.

Fluorescence spectra and ab initio theoretical studies of HCOOH /

A fluorescence excitation spectrum of formic acid monomer (HCOOH) , has been recorded in the 278-246 nm region and has been attributed to an n >7r* electron promotion in the anti conformer. The S^< S^ electronic origins of the HCOOH/HCOOD/DCOOH/DCOOD isotopomers were assigned to weak bands observed at 37431.5/37461.5/37445.5/37479.3 cm'''. From a band contour analysis of the 0°^ band of HCOOH, the rotational constants for the excited state were estimated: A'=1.8619, B'=0.4073, and C'=0.3730 cm'\ Four vibrational modes, 1/3(0=0), j/^(0-C=0) , J/g(C-H^^^) and i/,(0-H^yJ were observed in the spectrum. The activity of the antisymmetric aldehyde wagging and hydroxyl torsional modes in forming progressions is central to the analysis, leading to the conclusion that the two hydrogens are distorted from the molecular plane, 0-C=0, in the upper S. state. Ab initio calculations were performed at the 6-3 IG* SCF level using the Gaussian 86 system of programs to aid in the vibrational assignments. The computations show that the potential surface which describes the low frequency OH torsion (twisting motion) and the CH wagging (molecular inversion) motions is complex in the S^ excited electronic state. The OH and CH bonds were calculated to be twisted with respect to the 0-C=0 molecular frame by 63.66 and 4 5.76 degrees, respectively. The calculations predicted the existence of the second (syn) rotamer which is 338 cm'^ above the equilibrium configuration with OH and CH angles displaced from the plane by 47.91 and 41.32 degrees.

The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halide molecules /

TITLE: The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halides. AUTHOR: J. L. Brema SUPERVISOR: Dr. D. C. Moule NUMBER OF PAGES: 89 ABSTRACT: The vibrational assignment of the five-in-plane fundamental modes of CSClBr has been made on the basis of infrared gas phase and liquid Raman spectral analyses to supplement our earlier vibrational studies. Even though the one out-of-plane fundamental was not observed spectroscopically an attempt has been made to predict its frequency. The vibrational spectra contained impurity bands and the CSClBr assignment was made only after a thorough analysis of the impurities themselves. A normal co-ordinate analysis calculation was performed assuming a Urey-Bradley force field. This calculation yielded the fundamental frequencies in good agreement with those observed after refinement of the originally transferred force constants. The theoretical frequencies are the eigenvalues of the secular equation and the calculation also gave the corresponding eigenvectors in the form of the very important LLj matrix. The [l] matrix is the transfoirmation between internal co-ordinates and normal co-ordinates and it is essential for Franck-Condon calculations on electronically excited molecules and for infrared Integrated band intensity studies. Using a self-consistent molecular orbital calculation termed "complete neglect of differential overlap" (CNDO/2) , theoretical values of equilibrium bond lengths and angleswere calcuted for a series of carbonyl and thlocarbonyl molecules. From these calculations valence force field force constants were also determined but with limited success. With the CNIX)/2 method theoretical dipole moment derivatives with respect to symmetrized internal co-ordinates were calculated and the results should be useful in a correlation with experimentally determined values.

Quantum Monte Carlo : some theoretical and numerical studies

In Part I, theoretical derivations for Variational Monte Carlo calculations are compared with results from a numerical calculation of He; both indicate that minimization of the ratio estimate of Evar , denoted EMC ' provides different optimal variational parameters than does minimization of the variance of E MC • Similar derivations for Diffusion Monte Carlo calculations provide a theoretical justification for empirical observations made by other workers. In Part II, Importance sampling in prolate spheroidal coordinates allows Monte Carlo calculations to be made of E for the vdW molecule var He2' using a simplifying partitioning of the Hamiltonian and both an HF-SCF and an explicitly correlated wavefunction. Improvements are suggested which would permit the extension of the computational precision to the point where an estimate of the interaction energy could be made~

A microanalysis of EMG and EEG changes during the sleep onset period (SOP) : a theoretical investigation with practical applications /

The present study has both theoretical and practical aspects. The theoretical intent of the study was to closely examine the relationship between muscle activity (EMG) and EEG state during the process of falling asleep. Sleep stages during sleep onset (SO) have been generally defined with regards to brain wave activity (Recht schaff en & Kales (1968); and more precisely by Hori, Hayashi, & Morikawa (1994)). However, no previous study has attempted to quantify the changes in muscle activity during this same process. The practical aspect of the study examined the reliability ofa commercially developed wrist-worn alerting device (NovAlert™) that utilizes changes in muscle activity/tension in order to alert its user in the event that he/she experiences reduced wakefulness that may result in dangerous consequences. Twelve female participants (aged 18-42) sp-ent three consecutive nights in the sleep lab ("Adaptation", "EMG", and "NOVA" nights). Each night participants were given 5, twenty-minute nap opportunities. On the EMG night, participants were allowed to fall asleep freely. On the NOV A night, participants wore the Nov Alert™ wrist device that administered a Psychomotor Vigilance Test (PVT) when it detected that muscle activity levels had dropped below baseline. Nap sessions were scored using Hori's 9-stage scoring system (Hori et aI, 1994). Power spectral analyses (FFT) were also performed. Effects ofthe PVT administration on EMG and EEG frequencies were also examined. Both chin and wrist EMG activity showed reliable and significant decline during the early stages ofHori staging (stages HO to H3 characterized by decreases in alpha activity). All frequency bands studied went through significant changes as the participants progressed through each ofHori's 9 SO stages. Delta, theta, and sigma activity increased later in the SO continuum while a clear alpha dominance shift was noted as alpha activity shifted from the posterior regions of the brain (during Hori stages HO to H3) to the anterior portions (during Hori stages H7 to H9). Administration of the PVT produced significant increases in EMG activity and was effective in reversing subjective drowsiness experienced during the later stages of sleep onset. Limitations of the alerting effects of the PVTs were evident following 60 to 75 minutes of use in that PVTs delivered afterwards were no longer able to significantly increase EMG levels. The present study provides a clearer picture of the changes in EMG and EEG during the sleep onset period while testing the efficacy of a commercially developed alerting device. EMG decreases were found to begin during Hori stage 0 when EEG was - dominated by alpha wave activity and were maximal as Hori stages 2 to 5 were traversed (coincident with alpha and beta activity). This signifies that EMG decrements and the loss of resting alpha activity are closely related. Since decreased alpha has long been associated with drowsiness and impending sleep, this investigation links drops in muscle tone with sleepiness more directly than in previous investigations. The EMG changes were reliably demonstrated across participants and the NovAlert™ detected the EMG decrements when Hori stage 3 was entered. The alerting vibrations produced by the NovAlert™ occurred early enough in the SO process to be of practical importance as a sleepiness monitoring and alerting device.

Foraging ecology and parental care of common terns (Sterna hirundo) nesting in Windermere Basin, Lake Ontario

The relationships among chick feeding, size and type of prey item, and foraging time away from the brood have not been well studied in seabirds. This study investigated spatial and temporal patterns of foraging and chick-provisioning among 23 radio-tagged male common terns nesting at Hamilton Harbour, Lake Ontario during 1991 and 1992. Telemetry data were collected concurrently with behavioural observations from an elevated blind. Terns fitted with transmitters did not differ from controls with respect to either brood attendance, patterns of chick mortality, species and size distributions of prey delivered to offspring, or chick-provisioning rates. There was a clear separation of parental roles: males were primarily responsible for feeding chicks while females allocated more time to brood attendance. The prey species most commonly delivered to chicks by adults were rainbow smelt (Osmerus mordax) and alewife (A/osa pseudoharengus), followed in importance by larval fish, emerald shiner (Notropis antherinoides), salmonids, and fathead minnows (Pimepha/es prome/as). The relative proportions of various fish speCies delivered to chicks by males differed over the course of each breeding season, and there was also much variability in species composition of prey between years. Sizes of prey delivered to chicks also differed between sampling periods. The modal size of fish brought to chicks during Peak 1991 was 1.5 bill lengths, while the majority of prey in Late 1991 were small larval fish. The reverse trend occurred in 1992 when small fish were delivered to chicks predominantly during the Peak nesting period. During periods when predominantly small fish were delivered to chicks, the foraging activity of radio-tagged males was concentrated within a two kilometer radius of the colony. The observed variation in prey composition and foraging locations during the study likely reflects temporal variation in the availability of prey in the vicinity of the colony. Males delivered fish to chicks at a constant rate, while females 4 increased their feeding frequency over the first six to ten brood days. The mean length of fish delivered to chicks by adults increased significantly with increasing chick age. As a group, within each nesting period, transmittered males either foraged predominantly in the same directional bearing (north during Peak 1991, south during Late 1992), or concentrated foraging activity in the immediate vicinity of the colony (Late 1991, Peak 1992). However, individual radio-tagged males exhibited unique and predictable foraging patterns, often favouring specific locations within these areas and differing in their secondary foraging patterns. Overall, the Lake Ontario shoreline between NCB Bay" (3.5 km south of colony) and the lift bridge canal (4 km north of colony) was the foraging area used most frequently by radiotagged males during the chick-rearing period. Foraging patterns of transmittered males at Windermere Basin are similar to patterns of peak-nesting common terns, but differ from those of late-nesters, at a nearby colony (Port Colborne, Lake Erie). Differences between the foraging patterns of late-nesting terns at these colonies likely reflect differences in annual patterns of fish availability between the two locations. No relationship was found between foraging proficiency of adults and survival of offspring. Stochastic factors, such as predation by black-crowned nightherons (Nycticorax nycticorax) and adverse weather conditions during the early stages of chick rearing, may be more important determinants of common tern breeding success than parental quality or fish availability.

Aspects of spatial and habitat ecology of multiple Anopheles species (Diptera: Culicidae): malaria vectors in the highlands and foothills of Ecuador

The resurgence of malaria in highland regions of Africa, Oceania and recently in South America underlines the importance of the study of the ecology of highland mosquito vectors of malaria. Since the incidence of malaria is limited by the distribution of its vectors, the purpose of this PhD thesis was to examine aspects of the ecology of Anopheles mosquitoes in the Andes of Ecuador, South America. A historical literature and archival data review (Chapter 2) indicated that Anopheles pseudopunctipennis transmitted malaria in highland valleys of Ecuador prior to 1950, although it was eliminated through habitat removal and the use of chemical insecticides. Other anopheline species were previously limited to low-altitude regions, except in a few unconfirmed cases. A thorough larval collection effort (n=438 attempted collection sites) in all road-accessible parts of Ecuador except for the lowland Amazon basin was undertaken between 2008 - 2010 (Chapter 3). Larvae were identified morphologically and using molecular techniques (mitochondrial COl gene), and distribution maps indicated that all five species collected (Anopheles albimanus, An. pseudopunctipennis, Anopheles punctimacula, Anopheles oswaldoi s.l. and Anopheles eiseni) were more widespread throughout highland regions than previously recorded during the 1940s, with higher maximum altitudes for all except An. pseudopunctipennis (1541 m, 1930 m, 1906 m, 1233 m and 1873 m, respectively). During larval collections, to characterize species-specific larval habitat, a variety of abiotic and biotic habitat parameters were measured and compared between species-present and species-absent sites using chi-square tests and stepwise binary logistic regression analyses (Chapter 4). An. albimanus was significantly associated with permanent pools with sand substrates and An. pseudopunctipennis with gravel and boulder substrates. Both species were significantly associated with floating cyanobacterial mats and warmer temperatures, which may limit their presence in cooler highland regions. Anopheles punctimacula was collected more often than expected from algae-free, shaded pools with higher-than-average calculated dissolved oxygen. Anopheles oswaldoi s.l., the species occurring on the Amazonian side of the Andes, was associated with permanent, anthropogenic habitats such as roadside ditches and ponds. To address the hypothesis that human land use change is responsible for the emergence of multiple highland Anopheles species by creating larval habitat, common land uses in the western Andes were surveyed for standing water and potential larval habitat suitability (Chapter 5). Rivers and road edges provided large amounts of potentially suitable anopheline habitat in the western Andes, while cattle pasture also created potentially suitable habitat in irrigation canals and watering ponds. Other common land uses surveyed (banana farms, sugarcane plantations, mixed tree plantations, and empty lots) were usually established on steep slopes and had very little standing water present. Using distribution and larval habitat data, a GIS-based larval habitat distribution model for the common western species was constructed in ArcGIS v.l 0 (ESRI 2010) using derived data layers from field measurements and other sources (Chapter 6). The additive model predicted 76.4 - 97.9% of the field-observed collection localities of An. albimanus, An. pseudopunctipennis and An. punctimacula, although it could not accurately distinguish between species-absent and speciespresent sites due to its coarse scale. The model predicted distributional expansion and/or shift of one or more anopheline species into the following highland valleys with climate warming: Mira/Chota, Imbabura province, Tumbaco, Pichincha province, Pallatanga and Sibambe, Chimborazo province, and Yungilla, Azuay province. These valleys may serve as targeted sites of future monitoring to prevent highland epidemics of malaria. The human perceptions of malaria and mosquitoes in relation to land management practices were assessed through an interview-based survey (n=262) in both highlands and lowlands, of male and female land owners and managers of five property types (Chapter 7). Although respondents had a strong understanding of where the disease occurs in their own country and of the basic relationship among standing water, mosquitoes and malaria, about half of respondents in potential risk areas denied the current possibility of malaria infection on their own property. As well, about half of respondents with potential anopheline larval habitat did not report its presence, likely due to a highly specific definition of suitable mosquito habitat. Most respondents who are considered at risk of malaria currently use at least one type of mosquito bite prevention, most commonly bed nets. In conclusion, this interdisciplinary thesis examines the occurrence of Anopheles species in the lowland transition area and highlands in Ecuador, from a historic, geographic, ecological and sociological perspective.

Understanding the Origin of Selectivity in the Asymmetric Lithiation Reaction of N-Heterocycles: A Theoretical Study

The natural abundance of the N-heterocycle containing compounds has pushed the synthetic community toward the invention of new synthetic methods that result in the structural diversity of N-heterocycles. Among this, is the efficient and highly selective diamine mediated asymmetric lithiation process. Amongst the diamine chiral ligands, (-)-sparterine, which is a naturally occurring alkaloid proved to be an efficient one. Many successful, good yielding and highly selective lithiation reactions have been accomplished with the mediation by this chiral diamine base. Although, there are some examples of experimental and theoretical mechanistic studies in the literature, there is a lack of detailed understanding as to how it exactly induces the chirality. In this thesis is described a systematic investigation of how (-)-sparteine influences the stereoselectivity in the course of asymmetric lithiation reaction. This led us to the establishment of the function of A-ring’s β-CH2 effect and D-ring effect. Consequently, the importance of the A-ring and D-ring portions of (-)-sparteine in the stereoselectivity is unraveled. Another part of this thesis deals with the asymmetric lithiation of BF3-activated N,N- dimethylaminoferrocene in the presence of (1R, 2R)-N1,N2-bis(3,3-dimethylbutyl)-N1,N2-dimethylcyclohexane-1,2-diamine ( a (R,R)-TMCDA surrogate) with i-PrLi. Computational findings were in full accord with the experimental observations. Subsequently, the theoretically provided insights into the mechanism of the reaction were exploited in computational design of a new ligand. Unfortunately, the outcome of this design was not experimentally robust and an updated approach towards a successful design was explained.

Spectroscopic and theoretical considerations of cyclopropenone

Please consult the paper edition of this thesis to read. It is available on the 5th Floor of the Library at Call Number: Z 9999 P65 D53 2007