943 resultados para leave to proceed
Resumo:
This pro gradu –thesis discusses generating competitive advantage through competitor information systems. The structure of this thesis follows the structure of the WCA model by Alter (1996). In the WCA model, business process is influenced by three separate but connected elements: information, technology, and process participants. The main research question is how competitor information can be incorporated into or made into a tool creating competitive advantage. Research subquestions are: How does competitor information act as a part of the business process creating competitive advantage? How is a good competitor information system situated and structured in an organisation? How can management help information generate competitive advantage in the business process with participants, information, and technology? This thesis discusses each of the elements separate, but the elements are connected to each other and to competitive advantage. Information is discussed by delving into competitor information and competitor analysis. Competitive intelligence and competitor analysis requires commitment throughout the organisation, including top management, the desire to perform competitive intelligence and the desire to use the end products of that competitive intelligence. In order to be successful, systematic competitive intelligence and competitor analysis require vision, willingness to strive for the goals set, and clear strategies to proceed. Technology is discussed by taking a look into the function of the competitor information systems play and the place they occupy within an organization. In addition, there is discussion about the basic infrastructure of competitor information systems, and the problems competitor information systems can have plaguing them. In order for competitor information systems to be useful and worthy of the resources it takes to develop and maintain them, competitor information systems require on-going resource allocation and high quality information. In order for competitor information systems justify their existence business process participants need to maintain and utilize competitor information systems on all levels. Business process participants are discussed through management practices. This thesis discusses way to manage information, technology, and process participants, when the goal is to generate competitive advantage through competitor information systems. This is possible when information is treated as a resource with value, technology requires strategy in order to be successful within an organization, and process participants are an important resource. Generating competitive advantage through competitor information systems is possible when the elements of information, technology, and business process participants all align advantageously.
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Pelastuslaitosten liiketoimintatiedonhallinnalla, tietoperusteisuudella ja tietojohtamisella on tulevaisuudessa merkittävä rooli päätettäessä palveluista. Julkisen pelastustoimen kuntien liikelaitoksina ja eriytettyinä taseyksiköinä toimivien pelastuslaitosten haasteet tulevat olemaan jatkossa tehokkaiden ja vaikuttavien palveluiden strategisessa johtamisessa ja suunnittelussa. Näistä asioista päättäminen on kriittinen vaihe onnistumisen kannalta. Päätöksenteko eri tasoilla tarvitsee tuekseen toiminnasta ja palveluista kanavoitua analysoitua tietoa. Asiakastarpeesta lähtevä vaikuttavuus ja laatu korostuvat. Liiketoimintatiedonhallinta ja tietoperusteisuus haastavat pelastuslaitoksen johtamisjärjestelmän. Johtamisen kyvykkyys ja henkilöstön osaaminen ovat tietoperusteisuuden ja tiedonhallinnan keskiössä. Systemaattisen liiketoimintatiedonhallinnan ja tietoperusteisuuden erottaa perinteisestä virkamiehen tietojen hyväksikäytöstä käsitteen kokonaisvaltaisuus ja järjestelmällisyys kaikessa tiedollisessa toiminnassa. Tämä kattaa tietojärjestelmät, mittarit, prosessit, strategian suunnitelmat, asiakirjat, raportoinnin, kehittämisen ja tutkimuksen. Liiketoimin-tatiedonhallinta ja tietojohtaminen linkittävät kaiken toisiinsa muodostaen keskinäisriippuvaisen yhtenäisen järjestelmän ja kokonaisvaltaisen ymmärryksen. Tutkimukseni on laadullinen tutkimus jossa tiedon keruu ja analysointi on toteutettu toisiaan tukevilla tutkimusotteilla. Metodologia nojaa teorialähtöiseen systemaattiseen analyysiin, jossa on valikoituja osia sisällön analyysistä. Tutkimuksessa on käytetty aineisto- ja menetelmätriangulaatioita. Tutkimuksen aineisto on kerätty teemahaastatteluilla valittujen kohde pelastuslaitosten asiantuntijoilta palveluiden päätös- ja suunnittelutasolta, johtoryhmistä ja joh-tokunnista. Haastatteluja varten tutkija on tutustunut kohdepelastuslaitosten palveluita mää-rittävään tiedolliseen dokumentaatioon kuten palvelutasopäätöksiin ja riskianalyyseihin. Ai-neisto keruun kohteiksi valikoitui pääkaupunkiseudun alueen pelastuslaitokset: Helsingin kaupungin pelastuslaitos sekä Itä-, Keski- ja Länsi-Uudenmaan pelastuslaitokset. Tulosten mukaan pelastuslaitosten keskeiset liiketoimintatiedonhallinnan esteet muodostuvat johtamisen ongelmista, organisaation muutosvastarinnasta ja päätöksenteon tietoperusteen puutteesta. Nämä ilmenevät strategisen johtamisen puutteina, vaikuttavuuden mittaamisen sekä tiedon jalostamisen ongelmina. Keskeistä tiedollista yhdistävää ja linkittävää tekijää ei tunnisteta ja löydetä. Tiedollisessa liiketoimintatiedonhallinnan prosessityössä voisi olla tulos-ten mukaan mahdollisuuksia tämän tyhjiön täyttämiseen. Pelastuslaitoksille jää tulevaisuudessa valinta suunnasta johon ne haluavat edetä tiedonhal-linnan, tietojohtamisen ja tietoperusteisuuden kanssa. Tämä vaikuttaa kehitykseen ja tavoitteeseen keskeisistä palveluiden päätöksentekoa tukevista johtamis- ja tietojärjestelmistä, tietoa kokoavista ja luovista dokumenteista sekä organisaation joustavasta rakenteesta. Tietoprosessiin, tiedon prosessimaiseen johtamiseen ja systemaattiseen tiedonhallintaan meneminen vaikuttaa tutkimuksen tulosten mukaan lupaavalta mahdollisuudelta. Samalla se haastaa pelauslaitokset suureen kulttuuriseen muutokseen ja asettaa uusien vaikuttavuusmittareiden tuottaman tiedon ennakoivan hyväksynnän vaateen strategiselle suunnittelulle. Tämä vaatii pelastuslaitosten johdolta ja henkilöstöltä osaamista, yhteisymmärrystä, muutostarpeiden hyväksyntää sekä asiakkaan asettamista vaikuttavuuden keskiöön.
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This paper reviews the use of confocal microscopy as it pertains to the identification of G-protein coupled receptors and the study of their dynamic properties in cell cultures and in mammalian brain following their tagging with specific fluorescent ligands. Principles that should guide the choice of suitable ligands and fluorophores are discussed. Examples are provided from the work carried out in the authors' laboratory using custom synthetized fluoresceinylated or BODIPY-tagged bioactive peptides. The results show that confocal microscopic detection of specifically bound fluorescent ligands permits high resolution appraisal of neuropeptide receptor distribution both in cell culture and in brain sections. Within the framework of time course experiments, it also allows for a dynamic assessment of the internalization and subsequent intracellular trafficking of bound fluorescent molecules. Thus, it was found that neurotensin, somatostatin and mu- and delta-selective opioid peptides are internalized in a receptor-dependent fashion and according to receptor-specific patterns into their target cells. In the case of neurotensin, this internalization process was found to be clathrin-mediated, to proceed through classical endosomal pathways and, in neurons, to result in a mobilization of newly formed endosomes from neural processes to nerve cell bodies and from the periphery of cell bodies towards the perinuclear zone. These mechanisms are likely to play an important role for ligand inactivation, receptor regulation and perhaps also transmembrane signaling.
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The aim of the present set of longitudinal studies was to explore 3-7-year-old children.s Spontaneous FOcusing on Numerosity (SFON) and its relation to early mathematical development. The specific goals were to capture in method and theory the distinct process by which children focus on numerosity as a part of their activities involving exact number recognition, and individual differences in this process that may be informative in the development of more complex number skills. Over the course of conducting the five studies, fifteen novel tasks were progressively developed for the SFON assessments. In the tasks, confounding effects of insufficient number recognition, verbal comprehension, other procedural skills as well as working memory capacity were aimed to be controlled. Furthermore, how children.s individual differences in SFON are related to their development of number sequence, subitizing-based enumeration, object counting and basic arithmetic skills was explored. The effect of social interaction on SFON was tested. Study I captured the first phase of the 3-year longitudinal study with 39 children. It was investigated whether there were differences in 3-year-old children.s tendency to focus on numerosity, and whether these differences were related to the children.s development of cardinality recognition skills from the age of 3 to 4 years. It was found that the two groups of children formed on the basis of their amount of SFON tendency at the age of 3 years differed in their development of recognising and producing small numbers. The children whose SFON tendency was very predominant developed faster in cardinality related skills from the age of 3 to 4 years than the children whose SFON tendency was not as predominant. Thus, children.s development in cardinality recognition skills is related to their SFON tendency. Studies II and III were conducted to investigate, firstly, children.s individual differences in SFON, and, secondly, whether children.s SFON is related to their counting development. Altogether nine tasks were designed for the assessments of spontaneous and guided focusing on numerosity. The longitudinal data of 39 children in Study II from the age of 3.5 to 6 years showed individual differences in SFON at the ages of 4, 5 and 6 years, as well as stability in children.s SFON across tasks used at different ages. The counting skills were assessed at the ages of 3.5, 5 and 6 years. Path analyses indicated a reciprocal tendency in the relationship between SFON and counting development. In Study III, these results on the individual differences in SFON tendency, the stability of SFON across different tasks and the relationship of SFON and mathematical skills were confirmed by a larger-scale cross-sectional study of 183 on average 6.5-year-old children (range 6;0-7;0 years). The significant amount of unique variance that SFON accounted for number sequence elaboration, object counting and basic arithmetic skills stayed statistically significant (partial correlations varying from .27 to .37) when the effects of non-verbal IQ and verbal comprehension were controlled. In addition, to confirm that the SFON tasks assess SFON tendency independently from enumeration skills, guided focusing tasks were used for children who had failed in SFON tasks. It was explored whether these children were able to proceed in similar tasks to SFON tasks once they were guided to focus on number. The results showed that these children.s poor performance in the SFON tasks was not caused by their deficiency in executing the tasks but on lacking focusing on numerosity. The longitudinal Study IV of 39 children aimed at increasing the knowledge of associations between children.s long-term SFON tendency, subitizing-based enumeration and verbal counting skills. Children were tested twice at the age of 4-5 years on their SFON, and once at the age of 5 on their subitizing-based enumeration, number sequence production, as well as on their skills for counting of objects. Results showed considerable stability in SFON tendency measured at different ages, and that there is a positive direct association between SFON and number sequence production. The association between SFON and object counting skills was significantly mediated by subitizing-based enumeration. These results indicate that the associations between the child.s SFON and sub-skills of verbal counting may differ on the basis of how significant a role understanding the cardinal meanings of number words plays in learning these skills. The specific goal of Study V was to investigate whether it is possible to enhance 3-year old children.s SFON tendency, and thus start children.s deliberate practice in early mathematical skills. Participants were 3-year-old children in Finnish day care. The SFON scores and cardinality-related skills of the experimental group of 17 children were compared to the corresponding results of the 17 children in the control group. The results show an experimental effect on SFON tendency and subsequent development in cardinality-related skills during the 6-month period from pretest to delayed posttest in the children with some initial SFON tendency in the experimental group. Social interaction has an effect on children.s SFON tendency. The results of the five studies assert that within a child.s existing mathematical competence, it is possible to distinguish a separate process, which refers to the child.s tendency to spontaneously focus on numerosity. Moreover, there are significant individual differences in children.s SFON at the age of 3-7 years. Moderate stability was found in this tendency across different tasks assessed both at the same and at different ages. Furthermore, SFON tendency is related to the development of early mathematical skills. Educational implications of the findings emphasise, first, the importance of regarding focusing on numerosity as a separate, essential process in the assessments of young children.s mathematical skills. Second, the substantial individual differences in SFON tendency during the childhood years suggest that uncovering and modeling this kind of mathematically meaningful perceiving of the surroundings and tasks could be an efficient tool for promoting young children.s mathematical development, and thus prevent later failures in learning mathematical skills. It is proposed to consider focusing on numerosity as one potential sub-process of activities involving exact number recognition in future studies.
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Joidenkin tutkimusten mukaan naisten vähäinen määrä johdossa voi olla uhka organisaatiolle. Lasikattoilmiöllä tarkoitetaan naisten urakehityksen katkeamista tietylle tasolle ylimmän johdon alapuolelle ikään kuin naisten ja tuon ylimmän tason välissä olisi lasinen, näkymätön katto, sukupuolistereotypioiden muodostama este. Yksi yleinen lasikaton selitysten kolmijako on henkilökohtaiset, organisatoriset ja yhteiskunnalliset tekijät. (Lämsä & Hautala 2004, 252). Hoyt (2007, 270-278) tekee kolmijaon seuraavasti: inhimillinen pääoma, sukupuolierot ja ennakkoluulot. Yritys X:n keskijohdossa työskentelee yksi nainen, ylimmässä johdossa ei yhtäkään. Tutkimuksessa halu-taan selvittää miesjohtajien ja ei-johtavassa asemassa olevien naisten käsitystä siitä, onko yritys x:ssä lasi-kattoa, miksi naisjohtajia on niin vähän ja "mitä siitä" ts. onko mitään ongelmaa olemassakaan. Tässä tutkimuksessa pohditaan diskurssianalyysin keinoin, miten yritys X:ssä puhutaan naisjohtajuusaiheesta, millai-seksi sukupuolen merkitys työelämässä määritellään ja mitä ajatellaan naisten kykenevyydestä johtajiksi. Naturalisoiva diskurssi oli vahva niin miesjohtajien ja ei-johtavassa asemassa olevien naisten puheessa. Sen lisäksi hahmotellaan familistista, empiiristä, humanistista ja historiallista diskurssia naisjohtajuuspuheesta. Diskurssien yhteenkietominen hegemonisoimisstrategiana kuvaa tapaa, jolla palasia muista diskursseista käytetään tukemaan tiettyä toista diskurssia (Jokinen et al. 1993c, 95) Miesjohtajien puheessa naisten keskeiset, ominaisuudet - liiallinen tarkkuus ja huolellisuus yhdistettynä epävarmuuteen - ovat ongelmallisia johtajanuran kannalta. Jos näistä johtajuuden kannalta negatiivisista ominaisuuksista ei jostain syystä kuitenkaan muodostuisi uralla etenemisen estettä, äitiys ja perheellisyys "luonnollisesti" tekee tämän. Aiheet myös kietoutuvat yhteen: äitiys ja vastuu perheestä lisäävät naisten huolellisuutta, tarkkuutta ja epävarmuutta entisestään. Lisäksi äitiyslomat ja työhön käytettävissä oleva aika ja puut-tuva halu käyttää elämästä iso osa uranluomiseen ovat johtajaksi etenemisen esteitä. Miesjohtajien mukaan tämä on jossain määrin ongelma, kun heterogeenisyyttä johtamiseen kuitenkin tarvittaisiin, mutta loppujen lopuksi kuitenkin melko epäkiinnostava ja pieni ongelma; ongelma ei miesten mielestä johdu miesten tai yhteiskunnallisista asenteista, vaan naisista itsestään ja he tarvitsevat uralla edetäkseen tukea, rohkaisua ja henkilöstöpankkeja, joita miesjohtajat voivat tuottaa. Johtaminen ylipäänsä ei ole miesjohtajien mielestä hirveän kiinnostavaa. Jos naiset (kaikesta edellä sanotusta huolimatta) etenevät yritysten johtoon, eivät he tule siellä toimeen keskenään. Kaiken kaikkiaan koko naisjohtajuusaihe ei ole kovin kiinnostava ja naisjohtajuuden vähäisyyden (mahdollisen) ongelman ratkaisee aika uuden, tasa-arvoisemman sukupolven myötä. Naishaastateltujen näkökulmasta sen sijaan naisilla on pyrkyä johtotehtäviin - joskaan ei samassa määrin kuin miehillä. Naishaastateltujen mukaan miehet suosivat toisiaan työelämässä ja naiset kohtaavat asenteita, joita vastaan joutuvat taistelemaan ja tästä syystä johtajien joukossa on niin vähän naisia. Historialliset tekijät pitävät asenteita yllä. Perheellisyys on naisille suurempi uraeste kuin miehille, "luonnollisesti". Naishaastateltujen mielestä naisten vähäisyys johdossa on merkittävä ongelma, koska naisilla on erityislaatuisia ominaisuuksia, joista olisi hyötyä tehtävässä. Naishaastateltujen puheessa miesten ominaisuuksia vastaavasti vähäteltiin. Naisjohtajien vähäisyyden ongelmalle ei naishaastateltujen mielestä kuitenkaan ole tehtävissä paljonkaan: miesten ja yhteiskunnan asenteiden pitäisi muuttua, mutta keinoja tähän ei esitetä, sen sijaan naisten itsensä pitäisi vain "yrittää vielä kovemmin".
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The purpose of this thesis is to explore a different kind of digital content management model and to propose a process in order to manage properly the content on an organization’s website. This process also defines briefly the roles and responsibilities of the different actors implicated. In order to create this process, the thesis has been divided into two parts. First, the theoretical analysis helps to find the two main different content management models, content management adaptation and content management localization model. Each of these models, have been analyzed through a SWOT model in order to identify their particularities and which of them is the best option according to particular organizational objectives. In the empirical part, this thesis has measured the organizational website performance comparing two main data. On one hand, the international website is analyzed in order to identify the results of the content management standardization. On the other hand, content management adaptation, also called content management localization model, is analyzed by looking through the key measure of the Dutch page from the same organization. The resulted output is a process model for localization as well as recommendations on how to proceed when creating a digital content management strategy. However, more research is recommended to provide more comprehensive managerial solutions.
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Julkisen sektorin raportointi toimintansa yhteiskunnallisista vaikutuksista on yleisesti vielä vähäistä verrattuna yritysmaailmaan. Liikenneviraston tavoitteena on julkaista ensimmäinen vastuullisuusraportti vuodesta 2015. Työ on tehty Liikennevirastolle tavoitteena kehittää vastuullisuustoimintaa tunnistamalla Liikenneviraston prosesseihin liittyvät vastuullisuusnäkökohdat ja kytkemällä ne osaksi Liikenneviraston strategiaa, toimintoja ja päätöksentekoa sekä soveltaa Liikenneviraston toimintaympäristöön sopivat vastuullisuusraportointityökalut. Työssä tarkastellaan liikennesektorin yhteiskunnallisia ja ympäristöllisiä vaikutuksia, yhteiskuntavastuun merkitystä ja erityispiirteitä julkisella sektorilla, vastuullisuustoiminnan kehittämistä ja yhteyttä laatujärjestelmään sekä erilaisia raportointityökaluja. Vertailuanalyysillä tunnistetaan vastuullisuusraportin laadunvarmistuksen kannalta tärkeät toiminnot. Laatujärjestelmän prosessilähtöistä tarkastelua sovelletaan vastuullisuustoiminnan kehittämisessä, jonka pohjalta laaditaan tarkistuslista apuvälineeksi kokonaisuuksien hahmottamiseen ja toimintojen kehittämiseen sekä yhteisten käytäntöjen luomiseen ja juurtumiseen. Tuloksena esitetään toimintamalli Liikenneviraston vastuullisuustoiminnan kehittämisestä, joka perustuu vastuullisuusnäkökohtien systemaattiseen tunnistamiseen toimintaprosesseista, toiminnan vaikuttavuuden ja vaikutusten arvioimiseen sekä sidosryhmien sitouttamiseen vastuullisuustoiminnan tavoitteisiin. Lisäksi annetaan suosituksia jatkotoimenpiteistä.
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Tavoite on selvittää hinnoittelupäätöksien noudattamista ohjelmistoliiketoimintaa harjoittavassa yrityksessä. Lisäksi syitä noudattamiseen ja noudattamatta jättämiseen sekä asiakkaiden hinnoittelutoiveisiin selvitettiin. Teoriassa esitellään kolmea hinnoittelumallia, kuinka näitä malleja käytetään käytännössä? Teoriaosuudessa käsitellään hintaa, hinnoittelua, hinnoittelumalleja ja ohjelmistoliiketoiminnan piirteitä. Empiirisessä osassa tehdään laadullista tutkimusta henkilökohtaisilla puolistrukturoiduilla haastatteluilla, joista kerätään tarjousten kanssa tutkimuksen aineisto. Tutkimusmateriaalin pohjalta vastataan tutkimuskysymyksiin. Vaikka käytännöt olisivat valideja, mutta mikäli hintoja ei nähdä järkevinä, käytännöistä on joustettava. Kohdetuotteilla pitäisi myös olla yhtäläiset hinnoittelumallit. Pääsyyksi käytännöistä joustamiseen nähtiin kohdeasiakkaan olevan avainasiakas tai kilpailijan tarjouksen voittaminen.
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Modifications to the commercial hydride generator, manufactured by Spectrametrics, resulted in improved operating procedure and enhancement of the arsenic and germanium signals. Experiments with arsenic(III) and arsenic(V) showed that identical reiults could be produced from both oxidation states. However, since arsenic(V) is reduced more slowly than arsenic(III), peak areas and not peak heights must be measured when the arsine is immediately stripped from the system (approximately 5 seconds reaction). When the reduction is allowed to proceed for 20 seconds before the arsine is stripped, peak heights may be used. For a 200 ng/mL solution, the relative standard deviation is 2.8% for As(III) and 3.8% for As(V). The detection limit for arsenic using the modified system is 0.50 ng/mL. Studies performed on As(V) standards show that the interferences from 1000 mg/L of nickel(II), cobalt(II), iron(III), copper(II), cadmium(II), and zinc(II) can be eliminated with the aid of 5 M Hel and 3% L-cystine. Conditions for the reduction of germanium to the corresponding hydride were investigated. The effect of different concentrations of HCl on the reduction of germanium to the covalent hydride in aqueous media by means of NaBH 4 solutions was assessed. Results show that the best response is accomplished at a pH of 1.7. The use of buffer solutions was similarly characterized. In both cases, results showed that the element is best reduced when the final pH of the solution after reaction is almost neutral. In addition, a more sensitive method, which includes the use of (NH4)2S208' has been developed. A 20% increase in the germanium signal is registered when compared to the signal achieved with Hel alone. Moreover, under these conditions, reduction of germanium could be accomplished, even when the solution's pH is neutral. For a 100 ng/mL germanium standard the rsd is 3%. The detection limit for germanium in 0.05 M Hel medium (pH 1.7) is 0.10 ng/mL and 0.09 ng/mL when ammonium persulphate is used in conjunction with Hel. Interferences from 1000 mg/L of iron(III), copper(II), cobalt(II), nickel(II), cadmium(II), lead(II), mercury(II), aluminum(III), tin(IV), arsenic(III), arsenic(V) and zinc(II) were studied and characterized. In this regard, the use of (NH4)ZS20S and Hel at a pH of 1.7 proved to be a successful mixture in the sbppression of the interferences caused by iron, copper, aluminum, tin, lead, and arsenic. The method was applied to the determination of germanium in cherts and iron ores. In addition, experiments with tin(IV) showed that a 15% increase in the tin signal can be accomplished in the presence of 1 mL of (NH4)2S20S 10% (m/V).
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The lower Silurian Whirlpool Sandstone is composed of two main units: a fluvial unit and an estuarine to transitional marine unit. The lowermost unit is made up of sandy braided fluvial deposits, in shallow valleys, that flowed towards the northwest. The fluvial channels are largely filled by cross-bedded, well sorted, quartzose sands, with little ripple crosslaminated or overbank shales. Erosionally overlying this lower unit are brackish water to marine deposits. In the east, this unit consists of estuarine channels and tidal flat deposits. The channels consist of fluvial sands at the base, changing upwards into brackish and tidally influenced channelized sandstones and shales. The estuarine channels flowed to the southwest. Westwards, the unit contains backbarrier facies with extensive washover deposits. Separating the backbarrier facies from shoreface sandstone facies to the west, are barrier island sands represented by barrier-foreshore facies. The barrier islands are dissected by tidal inlets characterized by fining upward abandonment sequences. Inlet deposits are also present west of the barrier island, abandoned by transgression on the shoreface. The sandy marine deposits are replaced to the west by carbonates of the Manitoulin Limestone. During the latest Ordovician, a hiatus in crustal loading during the Taconic Orogeny led to erosional offloading and crustal rebound, the eroded material distributed towards the west, northwest and north as the terrestrial deposits of the fluvial Whirlpool. The "anti-peripheral bulge" of the rebound interfered with the peripheral bulge of the Michigan Basin, nulling the Algonquin Arch, and allowing the detritus of the fluvial Whirlpool to spread onto the Algonquin Arch. The Taconic Orogeny resumed in the earliest Silurian with crustal loading to the south and southeast, and causing tilting of the surface slope in subsurface Lake Erie towards the ii southwest. Lowstand terrestrial deposits were scoured into the new slope. The new crustal loading also reactivated the peripheral bulge of the Appalachian Basin, allowing it to interact with the bulge of the Michigan Basin, raising the Algonquin Arch. The crustal loading depressed the Appalachian basin and allowed transgression to occur. The renewed Algonquin Arch allowed the early Silurian transgression to proceed up two slopes, one to the east and one to the west. The transgression to the east entered the lowstand valleys and created the estuarine Whirlpool. The rising arch caused progradation of the Manitoulin carbonates upon shoreface facies of the Whirlpool Sandstone and upon offshore facies of the Cabot Head Formation. Further crustal loading caused basin subsidence and rapid transgression, abandoning the Whirlpool estuary in an offshore setting.
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The phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) has been employed as an efficient reusable media for the palladium catalyzed Suzuki cross-coupling reaction of aryl halides, including aryl chlorides, under mild conditions. The cross-coupling reactions were found to proceed in THPC containing small amounts ofwater and toluene (single phase) using potassium phosphate and 1% Pd2(dba)3'CHCI3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and were all complete within 1 hour at 50°C. The corresponding aryl bromides also reacted under these conditions with the addition of a catalytic amount of triphenylphosphine that allowed for complete conversion and high isolated yields. The reactions involving aryl chlorides were considerably slower, although the addition of triphenylphosphine and heating at 70°C allowed high conversion of electron deficient derivatives. Addition of water and hexane to the reaction products results in a triphasic system, from which the catalyst was then recycled by removing the top (hexanes) and bottom (aqueous) layers and adding the reagents to the ionic liquid which was heated again at 50°C; resulting in complete turnover of iodobenzene. Repetition of this procedure gave the biphenyl product in 82-97% yield (repeated five times) for both the initial and recycled reaction sequences. IL ESTERIFICATIONREACTION A new class oftrialkylphosphorane has been prepared through reaction of a trialkylphosphine with 2-chlorodimethylmalonate in the presence oftriethylamine. These new reagents promote the condensation reaction of carboxylic acids with alcohols to provide esters along with trialkylphosphine oxide and dimethylmalonate. The condensation reaction of chiral secondary alcohols can be controlled to give either high levels of inversion or retention through a subtle interplay involving basicity of the reaction media, solvent, and tuning the electronic and steric nature of the carboxylic acid and stenc nature of the phosphorane employed. A coherent mechanism is postulated to explain these observations involving reaction via an initial acyloxyphosphonium ion.
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This thesis describes the synthesis, structural studies, and stoichiometric and catalytic reactivity of novel Mo(IV) imido silylamide (R'N)Mo(R2)(173_RIN-SiR32-H)(PMe3)n (1: Rl = tBu, Ar', Ar; R2 = Cl; R32 = Me2, MePh, MeCl, Ph2, HPh; n = 2; 2: R' = Ar, R2 = SiH2Ph, n = 1) and hydride complexes (ArN)Mo(H)(R)(PMe3)3 (R = Cl (3), SiH2Ph (4». Compounds of type 1 were generated from (R'N)Mo(PMe3)n(L) (5: R' = tBu, Ar', Ar; L = PMe3, r/- C2H4) and chlorohydrosilanes by the imido/silane coupling approach, recently discovered in our group. The mechanism of the reaction of 5 with HSiCh to give (ArN)MoClz(PMe3)3 (8) was studied by VT NMR, which revealed the intermediacy of (ArN)MCh(172 -ArN=SiHCl)(PMe3)z (9). The imido/silyl coupling methodology was transferred to the reactions of 5 with chlorine-free hydrosilanes. This approach allowed for the isolation of a novel ,B-agostic compound (ArN)Mo(SiHzPh)(173 -NAr-SiHPhH)(PMe3) (10). The latter was found to be active in a variety of hydrosilation processes, including the rare monoaddition of PhSiH3 to benzonitrile. Stoichiometric reactions of 11 with unsaturated compounds appear to proceed via the silanimine intermediate (ArN)M(17z-ArN=SiHPh)(PMe3) (12) and, in the case of olefins and nitriles, give products of Si-C coupling, such as (ArN)Mo(R)(173 -NAr-SiHPh-CH=CHR')(PMe3) (13: R = Et, R' = H; 14: R = H, R' = Ph) and (ArN)Mo(172-NAr-SiHPh-CHR=N)(PMe3) (15). Compound 13 was also subjected to catalysis showing much improved activity in the hydrosilation of carbonyls and alkenes. Hydride complexes 3 and 4 were prepared starting from (ArN)MoCh(PMe3)3 (8). Both hydride species catalyze a diversity of hydrosilation processes that proceed via initial substrate activation but not silane addition. The proposed mechanism is supported by stoichiometric reactions of 3 and 4, kinetic NMR studies, and DFf calculations for the hydrosilation of benzaldehyde and acetone mediated by 4.
Resumo:
Letter (unsigned) from the Welland Canal Office regarding a quantity of wood felled upon the bank of the feeder. It is laid too near the back ditch. The recipient of the letter is instructed to proceed with the removal of the wood so that the excavation of the ditch might proceed, Aug. 7, 1858.
Resumo:
- The first part of the document traces Mr. Haile’s lineage. His father, James Haile was a farmer. His grandfather, Amos Haile was a sailor for the early part of his life. He was placed on a British man-of- war in about 1758. He escaped and settled in Putney. (p.1) - His father’s mother’s maiden name was Parker. His mother’s maiden name was Campbell. Her father was a captain in the Revolutionary Army. (p.2) - His earliest memories revolve around the death of his aunt and the funeral of General Washington (although he did not witness this). At the time, his father was a Lieutenant in a regiment militia of Light Dragoons who wore red coats. (p.3) - In 1804, an addition was added to the Haile house which necessitated that William was to stay home to help with the building. He continued to study and read on his own. He was particularly interested in Napoleon Bonaparte’s victories. In that same year he was sent to Fairfield Academy where Reverend Caleb Alexander was the principal. (p.4) - On June 1, 1812, William was appointed as an Ensign in the Infantry of the Army of the United States. He was put into the recruiting service at Nassau (20 miles east of Albany) where he remained until September. (p.4) - He was assigned to the 11th Regiment of the W.S. Infantry and directed to proceed to Plattsburgh to report to Colonel Isaac Clark. (p.7) - He was assigned to the company commanded by Captain Samuel H. Halley who was not in the best of health and often absent. For a good part of the time William was in charge of the company. (p.8) - The 11th Regiment was encamped beside the 15th Regiment commanded by Col. Zebulon Montgomery Pike [Pike’s Peak was named after him]. Col. Pike generously drilled and disciplined the 11th Regiment since their officers didn’t seem capable of doing so. (p.8) - The first brigade to which William’s regiment was attached to was commanded by Brigadier General Bloomfield of New Jersey. Brigadier Chandler of Maine commanded the second brigade. (p.9) - At the beginning of November, Major General Dearborn took command of the army. He had been a good officer in his time, but William refers to him as “old and inefficient” earning him the nickname “Granny Dearborn” (p.9) - On November 17th, 1812, General Dearborn moved north with his army. The troops ended up in Champlain. There was no fighting, only a skirmish between a party of men under Colonel Pike and a few British troops who he succeeded in capturing. (p.10) - The troops were moved to barracks for the winter. Colonel Pike’s troops were put into suitable barracks and kept healthy but another part of the army (including the 11th Regiment) were sent to a barracks of green lumber north of Burlington. Disease soon broke out in the damp barracks and the hundreds of deaths soon followed. One morning, William counted 22 bodies who had died the previous night. He puts a lot of this down to an inexperienced commanding officer, General Chandler. (p.11) - At the beginning of 1813, William was stationed as a recruiter on the shore of Shoreham across from Fort Ticonderoga. In February, he returned to Burlington with his recruits. In March he received an order from General Chandler to proceed to Whitehall and take charge of the stores and provisions. In April and May it was decided that his half of the regiment (the First Battalion) should march to Sackett’s Harbour, Lake Ontario. They arrived at Sackett’s Harbour about the 10th of June, a few days after the Battle of Sackett’s Harbour. (p.12) - He was camped near the site of Fort Oswego and got word to head back to Sackett’s Harbour. A storm overtook the schooner that he was on. (p.14) - William was involved in the Battle of Williamsburg (or Chrysler’s Farm) which he calls a “stupid and bungling affair on the part of our generals”.(p. 18) - General Covington was wounded and died a few days after the battle. (p.19) - William speaks of being ill. The troops were ordered to march to Buffalo, but he is able to go to his father’s house in Fairfield where his mother nursed him back to health (p.23) - Upon arrival at Buffalo, the “old fogy Generals” were replaced with younger, more efficient men. (p.25) - On page 27 he sums up a few facts: In 1812, the army was assembled on Lake Champlain with the intention of capturing Montreal, and then Quebec. That year, under General Dearborn the army marched as far as Champlain, then turned back and went into winter quarters. In 1813, the army was assembled at Sackett’s Harbour and that year the campaign ended at French Mills which was 70 or 80 miles from Montreal. In 1814, the army at Buffalo were some 400 miles from Montreal with still the same object in view. - He says that these facts make “a riddle – difficult to explain”. (p.27) - On the evening of July 2nd they embarked on the boats with the objective of capturing Fort Erie. The enemy were all made prisoners of war (p.27) - On July 4th they went to Street’s Creek, 2 miles above the Chippewa [Chippawa] River (p.28) - Page 29 is titled The Battle of Chippewa [Chippawa] - He speaks of 2 drummers who were fighting over the possession of a drum when a cannonball came along and took of both of their heads (p.29) - He proclaims that this was one of the “most brilliant battles of the war”. The battle was fought and won in less than an hour after they left their tents. He credits General Scott with this success and states that was due to his rapid orders and movements. (p.30) - The dead of the battle remained on the field during the night. He describes this as quite gloomy seeing friend and foe lying side by side. At daybreak they set to work digging trenches to bury the dead. (p.31) - Colonel Campbell was wounded and advised to have his leg amputated. He refused, and subsequently died. (p.32) - It is said that the British threw several of their dead into the river and they went over the Falls. (p.32) - His troops repaired the bridge over Chippawa which the enemy had partially destroyed and then pursued the British as far as Queenston Heights. (p.32) - On pages 33 and 34 he speaks about meeting an old friend of his, Philip Harter. - The account ends at Queenston Heights
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This paper is an examination of the Supreme Court of Canada's interpretation of federalism since constitutional repatriation in 1982. It argues that the lure of centralist efficiency is overpowering a fundamentally important part of our federal order: regionalism. The author contends that changes made by the Court to certain fundamental concepts of Canadian constitutional law now provide Parliament with greater latitude than before in the exercise of its legislative powers. According to the author, these changes are disturbing because they are structured so as to preclude consideration of the legitimate concerns of regional polities. Furthermore, he argues that the Court has reinforced the central government's power to regulate the economy, including intraprovincial matters affecting trade, by resorting to highly functional tests that emphasize economic efficiency over other criteria. This, he claims, makes it more difficult to invoke legitimate regional interests that would lead to duplication, overlapping and even, in the eyes of some, inefficiency. The author the focuses on the Court's treatment of environmental protection in an attempt to show the tension between the Court's desire to use a functional approach and the need to recognize regional interests. Finally, through an examination of recent case law, he attemps to demonstrate that the Court's dominant perspective remains functional despite its endorsement of a more community-oriented undestanding of federalism in Secession Reference. If the Court chooses to proceed in this manner, it will alienate regional polities and may encourage them to choose more radical means of asserting their differences. Further, the author argues that strict adherence to the functional effectiveness approach will undermine the very values that federalism is meant to promote.