O trabalho se propõe a fazer uma análise da Provedoria da Fazenda do Continente do Rio de Grande de São Pedro a partir de um estudo prosopográfico dos principais funcionários que compunham o órgão fazendário. O recorte temporal se fará da criação da Provedoria da Fazenda, em 1748, até a sua extinção definitiva, em 1802. A partir disso, verificamos como as práticas individuais desses oficiais régios podem revelar aspectos importantes da trama social, contribuindo para entendermos como esses sujeitos foram tecendo suas relações sociais, em constantes negociações - com as elites locais e seus subalternos - para viabilizar sua governabilidade. Nessa perspectiva, buscamos evidenciar comportamentos à margem da lei, percebendo o que era, de fato, transgressão às normas e quais práticas políticas consideradas comuns na lógica da sociedade de Antigo Regime. Dessa forma, procuramos perceber como a corrupção permitiu aos sujeitos formar cadeias informais de mando, influência e poder na Colônia Nesse sentido, encontramos na provedoria da Fazenda Real uma instituição permeada por práticas ditas ilegais, que têm sua própria lógica de existência em redes de poder, legitimadas pela monarquia corporativa em uma concepção de ilegalidade tolerada. Por fim, mediante essas biografias coletivas, buscaremos perceber suas experiências em um campo de interesses múltiplos, bem como pensar as transformações em curso no Império Ultramarino Português na segunda metade do século XVIII, com as reformulações das instituições administrativas da Fazenda. / The paper aims to make an analysis of the Provedoria da Fazenda (Crown Purveyor) of the Continent of Rio de Grande de São Pedro from a prosopographical study of different employees who formed this Treasury agency. The time frame will be from the creation of the Crown Purveyor, in 1748, until its final closure, in 1802. From this, we investigate how the individual practices of this royal officials may reveal important aspects of the social fabric, contributing to understand how these subjects were weaving their social relations, in constant negotiations – with local elites and their subalterns – to enable their governance. In this perspective, we seek to show behaviors outside the law, realizing what it was, in fact, transgression of rules and what political practices was considered common in the logic of Old Regime society. In this way, we seek to understand how corruption allowed people to form informal chains of command, influence and power in Cologne. In this sense, in the Crown Purveyor we find an institution permeated by practices considered illegal, which have their own logic of existence in networks of power, legitimized by corporate monarchy in a conception of tolerated illegality. Finally, we will seek to understand the experiences of these individuals in a field of multiple interests, as well as to think the changes taking place in the core of the Portuguese Overseas Empire in the second half of the eighteenth century, with the reformulation of the administrative institutions of Finance.

This dissertation is the result of a study of power relations between the crown and the church in Sweden during the 17th century. The study is focused on the Swedish Parliament and how the Estate of the Clergy responded to royal pretensions. The Swedish Clerical Estate is viewed as essential for the Swedish state formation process. The argument in the study is inspired by theories suggesting that state building and state formation were outcomes of a bargaining process between rulers and local power holders. The perspective presented by the historian Jan Glete is of great importance. He defines the early modern state as a complex organization providing protection and violence control. He emphasizes that the power of the state and the state’s character were dependent upon how the state could assert power. In order to do this, the rulers bartered with their subjects using protection as a commodity while in return the subjects paid required taxes. This bargaining process is interpreted as interactive. The rulers linked various local interests to the state and in doing so gained control of the society and the use of violence. The Swedish Clerical Estate played an important role in this process. Due in part to this fact, the clergy differed from the other subjects of the realm such as the nobility or the peasants. The clergy did not own any sizeable amount of property and did not exert any economical influence. Instead the Clerical Estate negotiated using their ideological, cultural and political resources. These commodities became essential in how the king organized the state. In exchange for royal protection, the clergy were given the task of supporting and explaining the crown’s economical and military needs. By doing so, the Clerical Estate legitimated the royal power in the parliament and in the society as a whole. At the same time, this negotiation signified a definition of the role of the clergyman within the state. Though the Clerical Estate sometimes tried to reject royal claims, it was the king who decided the conditions of negotiation. The parliament as a political field was created by the king and for the king. From a political point of view, religion and a theological framework became of great importance and were adopted by the crown in order to exploit resources. Taking this into consideration, the 17th century Swedish state seems to be more effective than other European early modern states.

This thesis deals with the design and syntheses of chiral,enantiopure pyridinecontaining ligands and their applicationsin asymmetric catalyis. Chiral pyridyl pyrrolidine ligands and pyridyl oxazolineligands were synthesized and employed in thepalladium-catalysed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. Theinfluence of the steric properties of the ligands wereinvestigated. Ditopic ligands, containing crown ether units as structuralelements, were synthesized and some of the ligands were used asligands in the palladiumcatalysed allylic alkylation of1,3-diphenyl-2-propenyl acetate with dimethyl malonate. A smallrate enhancement was observed, compared with analogous ligandslacking the crown ether unit, when these ditopic ligands wereused in dilute systems. A modular approach was used to synthesize chiralenantiomerically pure pyridyl alcohols and C2-symmetric2,2’-bipyridines, with the chirality originating from thechiral pool. Electronic and steric properties of the compoundswere varied and they were used as ligands in theenantioselective addition of diethylzinc to benzaldehyde. Thesense of asymmetric induction was found to be determined by theabsolute configuration of the carbinol carbon atom. Theelectronic properties of the ligands had a minor influence onthe levels of enantioselectivity induced by the ligands. Chiral pyridyl phosphinite ligands and pyridyl phosphiteligands were synthesized from the pyridyl alcohols andevaluated as ligands in palladiumcatalysed allylic alkylations.With the phosphinite ligands, the sense of chiral induction wasfound to be determined by the absolute configuration of theformer carbinol carbon atom. A kinetic resolution of theracemic starting material was observed with one of thephosphite ligands. Moderate enantioselectivities wereachieved. <b>Kewords:</b>asymmetric catalysis, chiral ligand, chiralpool, oxazoline, crownether, ditopic receptor, bipyridine,pyridyl alcohol, modular approach, P,Nligand, diethylzinc,allylic alkylation.

The existing rights paradigm in Aboriginal law accepts Crown sovereignty claims grounded in ethnocentric conceptions of terra nullius and discovery, and views Aboriginal rights as arising out of prior occupation. The Supreme Court of Canada has shaken this paradigm by characterizing Crown sovereignty as merely de facto until reconciled with Aboriginal sovereignty and legitimated by a treaty, by developing the duty to consult, and by characterizing reconciliation as a process that is part of a generative constitutional order. The moves the Court toward a new paradigm rooted in the principle of the equality of peoples in which treaties provide a framework for sharing sovereignty. As part of the Canadian federation, Aboriginal sovereignty can strengthen Canadas territorial integrity and contribute to Canadas economic development.<p> In the past, courts allowed the act of state doctrine to shield Crown assertions of sovereignty from scrutiny. This doctrine protects Canadas territorial integrity, but does not shield the Crowns actions from legal and constitutional scrutiny. The fundamental constitutional principle of rule of law and the de facto doctrine will protect interests that relied on assumptions of Crown sovereignty that lacked constitutional legitimacy.<p> The transformation in the fundamental principles of Aboriginal law has parallels to Thomas Kuhns description of a paradigm shift in the natural sciences. The rights paradigm is in a crisis with moral and practical dimensions. It is incommensurable with the equality paradigm, and therefore the choice of paradigms will depend on normative criteria. Fundamental principles of the Canadian constitution, international standards of human rights and the perspectives of growing numbers of practitioners in the field that are of Aboriginal ancestry are all forces that will complete the shift to the equality paradigm.<p> An equality paradigm will result in the abandonment of some Aboriginal law doctrines, and the modification of others. Aboriginal title is inconsistent with an equality paradigm because it assumes the legitimacy of the Crowns claims to sovereignty, gives the Crown a superior title, and limits Aboriginal nations to a burden of only limited and subordinate rights. The fiduciary relationship rooted in the honour of the Crown will grow into a non-hierarchical relationship with reciprocal obligations.<p> Decisions of courts can play a supporting role, but only negotiations and treaties can build a genuine partnership, effective and equitable sharing of sovereignty and ultimately reconciliation between Aboriginal and non-Aboriginal peoples in Canada.

The existing rights paradigm in Aboriginal law accepts Crown sovereignty claims grounded in ethnocentric conceptions of terra nullius and discovery, and views Aboriginal rights as arising out of prior occupation. The Supreme Court of Canada has shaken this paradigm by characterizing Crown sovereignty as merely de facto until reconciled with Aboriginal sovereignty and legitimated by a treaty, by developing the duty to consult, and by characterizing reconciliation as a process that is part of a generative constitutional order. The moves the Court toward a new paradigm rooted in the principle of the equality of peoples in which treaties provide a framework for sharing sovereignty. As part of the Canadian federation, Aboriginal sovereignty can strengthen Canadas territorial integrity and contribute to Canadas economic development.<p> In the past, courts allowed the act of state doctrine to shield Crown assertions of sovereignty from scrutiny. This doctrine protects Canadas territorial integrity, but does not shield the Crowns actions from legal and constitutional scrutiny. The fundamental constitutional principle of rule of law and the de facto doctrine will protect interests that relied on assumptions of Crown sovereignty that lacked constitutional legitimacy.<p> The transformation in the fundamental principles of Aboriginal law has parallels to Thomas Kuhns description of a paradigm shift in the natural sciences. The rights paradigm is in a crisis with moral and practical dimensions. It is incommensurable with the equality paradigm, and therefore the choice of paradigms will depend on normative criteria. Fundamental principles of the Canadian constitution, international standards of human rights and the perspectives of growing numbers of practitioners in the field that are of Aboriginal ancestry are all forces that will complete the shift to the equality paradigm.<p> An equality paradigm will result in the abandonment of some Aboriginal law doctrines, and the modification of others. Aboriginal title is inconsistent with an equality paradigm because it assumes the legitimacy of the Crowns claims to sovereignty, gives the Crown a superior title, and limits Aboriginal nations to a burden of only limited and subordinate rights. The fiduciary relationship rooted in the honour of the Crown will grow into a non-hierarchical relationship with reciprocal obligations.<p> Decisions of courts can play a supporting role, but only negotiations and treaties can build a genuine partnership, effective and equitable sharing of sovereignty and ultimately reconciliation between Aboriginal and non-Aboriginal peoples in Canada.

A new class of &pi / -conjugated monomers was synthesized with combination of electron donating and electron-withdrawing heterocyclics to understand the effects of structural differences on electrochemical and optoelectronic properties of the resulting polymers. Electron deficient benzotriazole, substititued with benzyl from two available sites, coupled with stannylated electron donating groups, ethylenedioxythiophene (EDOT) and thiophene (Th), to yield four different monomers / 1-benzyl-4,7-di(thiophen-2-yl))-2H-benzo[d][1,2,3] triazole (BBTA), 2-benzyl-4,7-di(thiophen-2-yl))-2H-benzo[d][1,2,3] triazole (BBTS), 1-benzyl-4,7-bis(2,3-dihydrothieno[3,4-b]dioxin-5-yl)-2H-benzo [d][1,2,3]triazole (BBTEA), 2-benzyl-4,7-bis(2,3-dihydrothieno[3,4-b]dioxin-5-yl)-2H-benzo [d][1,2,3]triazole (BBTES). Furthermore, EDOT and thiophene terminated napthalene-2,3-crown ether containing monomers, 14,19-di(thiophen-2-yl)-naphtho[2,3-b][1,4,7,10,13] pentaoxacyclo pentadecane (TNCT), 14,19-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-naphtho[2,3-b][1,4,7,10,13]pentaoxacyclopenta decane (ENCE), were synthesized to observe the effect crown ether moiety on the final electrochemical and optoelectronic properties of resultant polymers. Cyclic voltammetry, UV-Vis-NIR spectroscopy and colorimetry techniques were employed to examine electrochemical and optoelectronic properties of all monomers and polymers. Experimental results showed that alteration of substituent, substitution position and donor groups&rsquo / strength lead to obtain polymers with different redox behaviors, optical band gaps and different number of achievable colored states.

Thio metallates are known for many years for their utility in many processes. They have been established as versatile reagents in organic synthesis. However the heavier metal chalcogenides, though known for many years, have been ignored for a long time. In this thesis the results of the development of tetraethylammonium tetraselenotungstate [EttN]2Wse4 1 as a new class of selenium transfer reagent have been described. The thesis also deals with the chemistry of benzyltriethylammonium tetrathiomolybdate, [BnEt3N]2MoS4,2 in the synthesis of diselenides and thio esters. The thesis entitled "Chemistry of Thio and Seleno Metallates in Organic Synthesis" is divided into four Chapters. Chapter 1 In this chapter a detailed studies of alkylation of tetraethylammonium tetraselenotungstate (EuN)2WSe4,1 with a variety of alkyl halides, benzylic halides and acyl halides to yield the corresponding diselenides in excellent yields are described. (structural Formula) Scheme 1 Various carbohydrate-derived diselenides were also prepared by treating the sugar bromides with tetraethylammonium tetraselenotungstate 1 (Scheme 2). An attempt was made to synthesize seleno lactones from co- bromo acyl halides. This reaction mainly furnished the corresponding diacyl diselenides (Scheme 3). The reaction of 1 with aryldiazonium tetrafluoroborates led to the formation of corresponding diselenides or mono selenides depending on the substitution on the aromatic ring (Scheme 4). (structural formula) Scheme 2 (structural formula) Scheme 3 (structural formula) Scheme 4 Chapter 2 In this chapter a general methodology for the formation of the diselenide bond has been extended to the synthesis of a number of redox- switched crown ethers of various ring size using the reagents tetraethylammonium tetraselenotungstate (Et4N)2WSe4 t 1 and benzyltriethylammonium tetrathiomolybdate, [BnEt3NJ2MoS4,2 (Scheme 5). (structural formula) Scheme 5 The association constants for the binding of silver and potassium ions with the diselena crown ethers were determined. This methodology is very useful for obtaining selenacrown ethers under very mild conditions and also without using high dilution conditions. Chapter 3 In this chapter a general methodology for the facile conversion of amides and lactams to the corresponding seleno amides and selenolactams is described. A number of amides and lactams were converted into their selenocarbonyl derivatives in excellent yield via the formation of Vilsmeier intermediates followed by treatment with tetraethylammonium tetraselenotungstate (EuN^WSe4,1 (Scheme .6). (structural formula( Scheme 6 Chapter 4 In this chapter, a general method for the synthesis of thioesters is described. The reaction of p- nitrophenyl esters and disulfides with benzyltriethylammonium tetrathiomolybdate (PhCH2NEt3)2MoS4,2 furnished the corresponding thio esters in good yield (Scheme (7). The intramolecular version of this reaction furnished dimeric thiolactones as the major product (Scheme 8) (structural formula) Scheme 7 (structural formula) Scheme 8 (for structural formula pl see the original document)

<p>This thesis deals with the design and syntheses of chiral,enantiopure pyridinecontaining ligands and their applicationsin asymmetric catalyis.</p><p>Chiral pyridyl pyrrolidine ligands and pyridyl oxazolineligands were synthesized and employed in thepalladium-catalysed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. Theinfluence of the steric properties of the ligands wereinvestigated.</p><p>Ditopic ligands, containing crown ether units as structuralelements, were synthesized and some of the ligands were used asligands in the palladiumcatalysed allylic alkylation of1,3-diphenyl-2-propenyl acetate with dimethyl malonate. A smallrate enhancement was observed, compared with analogous ligandslacking the crown ether unit, when these ditopic ligands wereused in dilute systems.</p><p>A modular approach was used to synthesize chiralenantiomerically pure pyridyl alcohols and C2-symmetric2,2’-bipyridines, with the chirality originating from thechiral pool. Electronic and steric properties of the compoundswere varied and they were used as ligands in theenantioselective addition of diethylzinc to benzaldehyde. Thesense of asymmetric induction was found to be determined by theabsolute configuration of the carbinol carbon atom. Theelectronic properties of the ligands had a minor influence onthe levels of enantioselectivity induced by the ligands.</p><p>Chiral pyridyl phosphinite ligands and pyridyl phosphiteligands were synthesized from the pyridyl alcohols andevaluated as ligands in palladiumcatalysed allylic alkylations.With the phosphinite ligands, the sense of chiral induction wasfound to be determined by the absolute configuration of theformer carbinol carbon atom. A kinetic resolution of theracemic starting material was observed with one of thephosphite ligands. Moderate enantioselectivities wereachieved.</p><p><b>Kewords:</b>asymmetric catalysis, chiral ligand, chiralpool, oxazoline, crownether, ditopic receptor, bipyridine,pyridyl alcohol, modular approach, P,Nligand, diethylzinc,allylic alkylation.</p>

No description available.

Magistro darbe tiriama paliktų biologinei įvairovei medžių Prienų miškų urėdijoje plyno kirtimo biržėse būklė. Darbo objektas – Prienų miškų urėdijos plyno kirtimo birž��s ir jose biologinei įvairovei palikti medžiai. Darbo tikslas – Įvertinti 2002-2006 matų laikotarpyje biologinei įvairovei paliktų medžių Prienų miškų urėdijos plyno kirtimo biržėse būklę. Darbo metodika – surinkta informacija apie Prienų miškų urėdijoje plynų kirtimų biržes ir jose biologinei įvairovei paliktus medžius. Iš kiekvienų 2002 – 2006 metais plynais kirtimais kirstų biržių buvo pasirinkta po 10 biržių. Pasirinktose plyno kirtimo biržėse buvo įvertinti biologinei įvairovei paliktų medžių būklė pagal šiuos rodiklius: medžių būklė, lajos defoliacija ir medžių pažeidimai. Darbo rezultatai – Nuo 2002 iki 2006 metų vidutinis paliktų medžių skaičius plyno kirtimo biržėse viename hektare išaugo 1,5 karto, bet jų vidutinis skersmuo sumažėjo. Vadinasi su kiekvienais metais buvo paliekama vis daugiau, bet smulkesnių medžių. Medžių lajų vertinimo duomenimis, medžių būklė yra nepatenkinama, o to priežastis gali būti staigus pavienių medžių augusių medyne atidengimas, dėl ko neprisiteikę augti atviroje vietoje medžiai nusilpo. Tyrimo metu nustatyta, kad apie ketvirtadalį medžių iš biologinei įvairovei paliktų medžių galima vertinti, kaip potencialų negyvos medienos šaltinį plynose biržėse. Artimoje ateityje šie medžiai pasitarnaus daugeliui miško ekosistemos organizmų egzistavimui. / The master thesis presents evaluation of the condition of the trees, left fot biological diversity in clear cutting areas of Prienai forestry region. Object of the work – trees left for biological diversity in clear cutting areas of Prienai forestry region. Aim of the work – to evaluate the condition of the trees, left fot biological diversity in clear cutting areas of Prienai forestry region in the period of 2002-2006. Methods of the work – 10 clear cutting areas from each of smooth wood areas, felt in Prienai forestry region of the period of 2002-2006, were selected for investigation. Each of the left trees was estimated according to the following indicates: condition of trees, crow defoliation and injuries of trees Results of the work – In 2002-2006 period mean number of trees decreased, but mean diameter of trees increased. Almost ¼ of trees died in offer the first year. Left trees for biological diversity had higher defoliation of crowns.