Estudo teórico QTAIM e DFT dos compostos de coordenação: efeito quelato, titanocenos e ligação química

This work is a study of coordination compounds by quantum theory of atoms in molecules (QTAIM), based on the topological analysis of the electron density of molecular systems, both theoretically and experimentally obtained. The coordination chemistry topics which were studied are the chelate effect, bent titanocene and chemical bond in coordination complexes. The chelate effect was investigated according to topological and thermodynamic parameters. The exchange of monodentate ligands on polydentate ligands from same transition metal increases the stability of the complex both from entropy and enthalpy contributions. In some cases, the latter had a higher contribution to the stability of the complex in comparison with entropy. This enthalpic contribution is explained according to topological analysis of the M-ligand bonds where polidentate complex had higher values of electron density of bond critical point, Laplacian of electron density of bond critical point and delocalization index (number of shared electrons between two atoms). In the second chapter, was studied bent titanocenes with bulky cyclopentadienyl derivative π-ligand. The topological study showed the presence of secondary interactions between the atoms of π-ligands or between atoms of π-ligand and -ligand. It was found that, in the case of titanocenes with small difference in point group symmetry and with bulky ligands, there was an nearly linear relationship between stability and delocalization index involving the ring carbon atoms (Cp) and the titanium. However, the titanocene stability is not only related to the interaction between Ti and C atoms of Cp ring, but secondary interactions also play important role on the stability of voluminous titanocenes. The third chapter deals with the chemical bond in coordination compounds by means of QTAIM. The quantum theory of atoms in molecules so far classifies bonds and chemical interactions in two categories: closed shell interaction (ionic bond, hydrogen bond, van der Waals interaction, etc) and shared interaction (covalent bond). Based on topological parameters such as electron density, Laplacian of electron density, delocalization index, among others, was classified the chemical bond in coordination compounds as an intermediate between closed shell and shared interactions

Teoria do déficit de autocuidado análise da sua importância e aplicabilidade na prática de enfermagem

submeter a teoria do déficit de autocuidado de Orem a uma reflexão crítica. Metodologia: estudo teórico sobre os aspectos Importância e Aplicabilidade contidos no Modelo de Análise Crítica de Chinn e Kramer para análise crítica da teoria do déficit de autocuidado. Desenvolvido no período de outubro a dezembro de 2008. Resultados: o posicionamento da teoria do déficit de autocuidado está essencialmente relacionado à filosofia da enfermagem e demonstra potencial para influenciar ações de enfermagem, em especial relativas à educação para o autocuidado em pacientes portadores de cardiopatia isquêmica. Conclusões: a enfermagem, mediante a teoria do déficit de autocuidado, pode oferecer condições mais saudáveis e de maior autonomia ao indivíduo portador de cardiopatia isquêmica

A teoria de Callista Roy, a nanda-i e o cuidado ao paciente prostatectomizado

Trata-se de um estudo descritivo de caso clínico, com abordagem qualitativa, o qual possui como objetivo estabelecer relações entre os diagnósticos de enfermagem da NANDA-I e os problemas de adaptação segundo o Modelo Teórico de Roy em um paciente prostatectomizado. A coleta de dados ocorreu em um hospital universitário localizado na cidade de Natal-RN, no mês de janeiro de 2011, por meio de um roteiro de entrevista e exame físico. Os diagnósticos que apresentaram relações entre a NANDA-I e o Modelo de Roy foram: dor, ansiedade, constipação, sono, atividade, volume de líquido e infecção. Conclui-se que grande parte dos problemas adaptativos segundo o Modelo de Roy, manifestados pelos pacientes no pós-operatório de prostatectomia, possuem semelhança com os diagnósticos da NANDA-I

Justiça juvenil: teoria e prática no sistema socioeducativo

Em um momento histórico de violações e ameaças aos direitos fundamentais de crianças e adolescentes, é preciso somar esforços na luta pela transformação das políticas voltadas para esses sujeitos. A ideologia que fundamenta a criminalização de adolescentes pobres e da periferia é a mesma que impõe a redução da idade penal e que autoriza e legitima as violências institucionais cometidas no sistema socioeducativo. “Justiça juvenil: teoria e prática no sistema socioeducativo” vem apresentar fundamentos teóricos e experiências práticas com vistas à desconstrução desses processos ideológicos e à defesa intransigente da proteção integral

Recursos intangíveis de um destino turístico: um estudo de desempenho da cidade de Natal tendo como base a teoria das capacidades dinâmicas

O objetivo desta tese foi analisar os recursos intangíveis de um destino turístico. Foi feito um estudo de desempenho da cidade de Natal tendo como base a teoria das capacidades dinâmicas. Inicialmente, foi desenvolvido um instrumento de pesquisa para oportunizar a construção de um modelo de medida com vistas à captação de variáveis latentes para os recursos intangíveis existentes no setor do turismo em Natal-RN. Em seguida, foi realizada uma análise dos recursos intangíveis que são evidenciados pelos turistas acerca da cidade. Finalmente, foi feita a investigação de um modelo de estrutura que estabeleceu as relações entre as variáveis latentes dos recursos intangíveis e a percepção de desempenho do turismo na cidade de Natal. Procedeu-se uma revisão de literatura para construção de um modelo inicial acerca dos ativos intangíveis dentro da teoria das capacidades e foram relacionados dez recursos, quais sejam: recursos humanos prestadores de serviços; recursos humanos como gestores; cultura local; conservação do meio ambiente; know-how empresarial; inovação empresarial; tecnologia; marca; preço; e promoção. Estes dez recursos, em conjunto, seriam responsáveis pelo desempenho do destino turístico. Após ser realizada uma análise de equações estruturais, apenas quatro recursos manifestaram relações com o desempenho: marca; cultura; conservação do meio ambiente; e preço. Análisando dos dados, verificou-se que a variável desempenho positivo da cidade na ótica do turista se manifestou fortemente e foi influenciada de forma forte pela cultura local, marca e conservação do meio ambiente em conjunto. O preço foi influenciado pelo desempenho positivo mostrando que o turista sente que o preço pago foi satisfatório diante dos atributos do destino Provavelmente, isso seja um ponto positivo muito forte para o destino turístico de Natal, pois, em termos de recursos intangíveis e de juntos formarem capacidades, eles são inimitáveis, raros e são capazes de se ajustarem às mudanças organizacionais e ambientais, para reconfigurar os ativos e as estruturas de um destino, corroborando, assim, com a teoria das capacidades dinâmicas. Esses recursos da cidade de Natal, como destino turístico, são únicos e provavelmente têm um peso muito maior para o desempenho da cidade do que problemas existentes na localidade. Logo, esses atributos devem ser estimulados a continuar crescendo e se modificando de acordo com as exigências atuais e futuras de consumo

Teoria de carteiras e a alocação de parques eólicos offshore

The consumption of energy on the planet is currently based on fossil fuels. They are responsible for adverse effects on the environment. Renewables propose solutions for this scenario, but must face issues related to the capacity of the power supply. Wind energy offshore emerging as a promising alternative. The speed and stability are greater winds over oceans, but the variability of these may cause inconvenience to the generation of electric power fluctuations. To reduce this, a combination of wind farms geographically distributed was proposed. The greater the distance between them, the lower the correlation between the wind velocity, increasing the likelihood that together achieve more stable power system with less fluctuations in power generation. The efficient use of production capacity of the wind park however, depends on their distribution in marine environments. The objective of this research was to analyze the optimal allocation of wind farms offshore on the east coast of the U.S. by Modern Portfolio Theory. The Modern Portfolio Theory was used so that the process of building portfolios of wind energy offshore contemplate the particularity of intermittency of wind, through calculations of return and risk of the production of wind farms. The research was conducted with 25.934 observations of energy produced by wind farms 11 hypothetical offshore, from the installation of 01 simulated ocean turbine with a capacity of 5 MW. The data show hourly time resolution and covers the period between January 1, 1998 until December 31, 2002. Through the Matlab R software, six were calculated minimum variance portfolios, each for a period of time distinct. Given the inequality of the variability of wind over time, set up four strategies rebalancing to evaluate the performance of the related portfolios, which enabled us to identify the most beneficial to the stability of the wind energy production offshore. The results showed that the production of wind energy for 1998, 1999, 2000 and 2001 should be considered by the portfolio weights calculated for the same periods, respectively. Energy data for 2002 should use the weights derived from the portfolio calculated in the previous time period. Finally, the production of wind energy in the period 1998-2002 should also be weighted by 1/11. It follows therefore that the portfolios found failed to show reduced levels of variability when compared to the individual production of wind farms hypothetical offshore

Processo de implantação de um sistema integrado de gestão em uma organização pública à luz da teoria da hospitalidade :um estudo de caso

In the present time, public organizations are employing more and more solutions that uses information technology in order to ofer more transparency and better services for all citizens. Integrated Systems are IT which carry in their kernel features of integration and the use of a unique database. These systems bring several benefits and face some obstacles that make their adoption difficult. The conversion to a integrated system may take years and, thus, the study of the adoption of this IT in public sector organizations become very stimulant due to some peculiarities of this sector and the features of this technology. First of all, information about the particular integrated system in study and about its process of conversion are offered. Then, the researcher designs the configuration of the conversion process aim of this study the agents envolved and the moments and the tools used to support the process in order to elaborate the methodology of the conversion process understood as the set of procedures and tools used during all the conversion process. After this, the researcher points out, together with all the members of the conversion team, the negative and positive factors during the project. Finally, these factors were analysed through the Hospitality Theory lens which, in the researcher opinion, was very useful to understand the elements, events and moments that interfered in the project. The results consolidated empirically the Hospitality Theory presumptions, showing yet a limitation of this theory in the case in study

Determinação de motivos de ligação à quitina em vicilinas de Canavalia ensiformis e Vigna unguiculata através de métodos in silico e relação com suas toxicidades para o bruquídeo Callosobruchus maculatus (Coleoptera:Bruchidae)

Chitin is an important structural component of the cellular wall of fungi and exoskeleton of many invertebrate plagues, such as insects and nematodes. In digestory systems of insects it forms a named matrix of peritrophic membrane. One of the most studied interaction models protein-carbohydrate is the model that involves chitin-binding proteins. Among the involved characterized domains already in this interaction if they detach the hevein domain (HD), from of Hevea brasiliensis (Rubber tree), the R&R consensus domain (R&R), found in cuticular proteins of insects, and the motif called in this study as conglicinin motif (CD), found in the cristallography structure of the β-conglicinin bounded with GlcNac. These three chitin-binding domains had been used to determine which of them could be involved in silico in the interaction of Canavalia ensiformis and Vigna unguiculata vicilins with chitin, as well as associate these results with the WD50 of these vicilins for Callosobruchus maculatus larvae. The technique of comparative modeling was used for construction of the model 3D of the vicilin of V. unguiculata, that was not found in the data bases. Using the ClustalW program it was gotten localization of these domains in the vicilins primary structure. The domains R&R and CD had been found with bigger homology in the vicilins primary sequences and had been target of interaction studies. Through program GRAMM models of interaction ( dockings ) of the vicilins with GlcNac had been gotten. The results had shown that, through analysis in silico, HD is not part of the vicilins structures, proving the result gotten with the alignment of the primary sequences; the R&R domain, although not to have structural similarity in the vicilins, probably it has a participation in the activity of interaction of these with GlcNac; whereas the CD domain participates directly in the interaction of the vicilins with GlcNac. These results in silico show that the amino acid number, the types and the amount of binding made for the CD motif with GlcNac seem to be directly associates to the deleterious power that these vicilins show for C. maculatus larvae. This can give an initial step in the briefing of as the vicilins interact with alive chitin in and exert its toxic power for insects that possess peritrophic membrane

Modelagem molecular na caracterização eletrônica de oligopeptídeos e na descrição quântica da interação fármaco-receptor

In this dissertation, the theoretical principles governing the molecular modeling were applied for electronic characterization of oligopeptide α3 and its variants (5Q, 7Q)-α3, as well as in the quantum description of the interaction of the aminoglycoside hygromycin B and the 30S subunit of bacterial ribosome. In the first study, the linear and neutral dipeptides which make up the mentioned oligopeptides were modeled and then optimized for a structure of lower potential energy and appropriate dihedral angles. In this case, three subsequent geometric optimization processes, based on classical Newtonian theory, the semi-empirical and density functional theory (DFT), explore the energy landscape of each dipeptide during the search of ideal minimum energy structures. Finally, great conformers were described about its electrostatic potential, ionization energy (amino acids), and frontier molecular orbitals and hopping term. From the hopping terms described in this study, it was possible in subsequent studies to characterize the charge transport propertie of these peptides models. It envisioned a new biosensor technology capable of diagnosing amyloid diseases, related to an accumulation of misshapen proteins, based on the conductivity displayed by proteins of the patient. In a second step of this dissertation, a study carried out by quantum molecular modeling of the interaction energy of an antibiotic ribosomal aminoglicosídico on your receiver. It is known that the hygromycin B (hygB) is an aminoglycoside antibiotic that affects ribosomal translocation by direct interaction with the small subunit of the bacterial ribosome (30S), specifically with nucleotides in helix 44 of the 16S ribosomal RNA (16S rRNA). Due to strong electrostatic character of this connection, it was proposed an energetic investigation of the binding mechanism of this complex using different values of dielectric constants (ε = 0, 4, 10, 20 and 40), which have been widely used to study the electrostatic properties of biomolecules. For this, increasing radii centered on the hygB centroid were measured from the 30S-hygB crystal structure (1HNZ.pdb), and only the individual interaction energy of each enclosed nucleotide was determined for quantum calculations using molecular fractionation with conjugate caps (MFCC) strategy. It was noticed that the dielectric constants underestimated the energies of individual interactions, allowing the convergence state is achieved quickly. But only for ε = 40, the total binding energy of drug-receptor interaction is stabilized at r = 18A, which provided an appropriate binding pocket because it encompassed the main residues that interact more strongly with the hygB - C1403, C1404, G1405, A1493, G1494, U1495, U1498 and C1496. Thus, the dielectric constant ≈ 40 is ideal for the treatment of systems with many electrical charges. By comparing the individual binding energies of 16S rRNA nucleotides with the experimental tests that determine the minimum inhibitory concentration (MIC) of hygB, it is believed that those residues with high binding values generated bacterial resistance to the drug when mutated. With the same reasoning, since those with low interaction energy do not influence effectively the affinity of the hygB in its binding site, there is no loss of effectiveness if they were replaced.

Estudo in silico da interação da albumina de soro humano com o ibuprofeno

Currently, computational methods have been increasingly used to aid in the characterization of molecular biological systems, especially when they relevant to human health. Ibuprofen is a nonsteroidal antiinflammatory or broadband use in the clinic. Once in the bloodstream, most of ibuprofen is linked to human serum albumin, the major protein of blood plasma, decreasing its bioavailability and requiring larger doses to produce its antiinflamatory action. This study aimes to characterize, through the interaction energy, how is the binding of ibuprofen to albumin and to establish what are the main amino acids and molecular interactions involved in the process. For this purpouse, it was conducted an in silico study, by using quantum mechanical calculations based on Density Functional Theory (DFT), with Generalized Gradient approximation (GGA) to describe the effects of exchange and correlation. The interaction energy of each amino acid belonging to the binding site to the ligand was calculated the using the method of molecular fragmentation with conjugated caps (MFCC). Besides energy, we calculated the distances, types of molecular interactions and atomic groups involved. The theoretical models used were satisfactory and show a more accurate description when the dielectric constant ε = 40 was used. The findings corroborate the literature in which the Sudlow site I (I-FA3) is the primary binding site and the site I-FA6 as secondary site. However, it differs in identifying the most important amino acids, which by interaction energy, in order of decreasing energy, are: Arg410, Lys414, Ser 489, Leu453 and Tyr411 to the I-Site FA3 and Leu481, Ser480, Lys351, Val482 and Arg209 to the site I-FA6. The quantification of interaction energy and description of the most important amino acids opens new avenues for studies aiming at manipulating the structure of ibuprofen, in order to decrease its interaction with albumin, and consequently increase its distribution

A teoria democrática e a participação popular : as trajetórias participativas no Recife e em Módena

This work basically achieve three goals. Critically investigate the liberal democratic regime and its historical reformulation, rejecting the popular power and popular self-organization, limiting the entry of normal citizen in decision-making, believing in the market as a mediating body in regulating of the different life spheres of social. Starting from the critical liberal democracy, it discussed the concept of popular participation in the democracy, searching new democratically horizons, where the masses could have the opportunity to make decisions about their own destiny. On the basis of theoretical discussion on participation, we discuss a concrete instrument of participation, the Participatory Budgeting, comparing two participatory experiences in North and South

A Eficácia dos direitos fundamentais nos contratos civis e de consumo: uma teoria contratual baseada na colisão dos direitos ou bens constitucionalmente protegidos

The apparent virtuosity that if could wait of the globalization and the neoliberalism has given signals of deterioration in the contractual relations, especially in contracts of mass consumption, generating innumerable offensive situations to the basic rights and the goods constitutionally protected of the contractors. In the world of today, still that it does not reveal any desire, the individual practically is compelled to contract, for force of necessities and customs completely imposed, mainly in face of the essentiality of the services or agreed to goods. Ahead of as much and unexpected changes in the civil liames and of consumption, dictated for the globalization, it comes to surface the reflection if the private law e, more specifically, the civil law, meet prepared adequately to deal with these new parameters of the economy. The present dissertation has the intention to investigate if the globalization and the consequent neoliberalism, in this beginning of third millennium, will imply to revive of the principles and the basics paradigms of the contracts that consolidated and had kept, for more than two centuries, the liberal State. One notices that the study of this phenomenon it gains importance to the measure where if it aggravates the decline of the social State (Welfare State), with the embrittlement and the loss of the autonomy of the state authority, over all in countries of delayed modernity, as it is the case of Brazil, that presents deep deficiencies to give or to promote, with a minimum of quality and efficiency, essential considered public services to the collective and that if they find consecrated in the Federal Constitution, as basic rights or as goods constitutionally protecting, the example of the health, the education, the housing, the security, the providence, the insurance, the protection the maternity, the infancy and of aged and deficient. To the end, the incidence of constant basic rights of the man in the Constitution is concluded that, in the process of interpretation of the right contractual conflicts that have as object rights or goods constitutionally proteges, in the universe of the globalized perhaps economy and of the neoliberalismo, it consists in one of the few ways - unless the only one - that still they remain to over all deal with more adequately the contractual relations, exactly that if considers the presence of clauses generalities in the scope of the legislation infraconstitutional civil and of consumption, front the private detainers of social-economic power. To be able that it matters necessarily in disequilibrium between the parts, whose realignment depends on the effect and the graduation that if it intends to confer to the basic right in game in the private relation. The Constitution, when allowing the entailing of the basic rights in the privates relations, would be assuming contours of a statute basic of all the collective, giving protection to the man against the power, if public or independently private

Teoria da despesa pública: uma leitura ético-constitucional em busca do possível da reserva

Brazilian law passes through a crisis of effectiveness commonly attributed to the extravagance of fundamental rights and public shortage. However, public finances are not dogmatically structured to solve the conflicts around the limitations of public spending. There are ethical conditioning factors, like morality, proportionality and impartiality, however, these principles act separately, while the problem of public shortage is holistic. Also, the subjectivity of politics discretionary in the definition of public spending, which is supported in an indeterminate concept of public interest, needs material orientation about the destination of public funds, making it vulnerable to ideological manipulation, resulting in real process of catching rights. Not even the judicial activism (such as influx of constitutionalism) is shown legally appropriate. The Reserve of Possible, also presents basic ethical failure. Understanding the formation of public shortage is therefore essential for understanding the crisis of effectiveness of state responsibilities, given the significant expansion of the state duty of protection, which does not find legal technique of defense of the established interests. The premise of argument, then, part of the possibility of deducting minimal model ethical of desire to spend (public interest) according to objective parameters of the normative system. Public spending has always been treated disdainfully by the Brazilian doctrine, according to the legal character accessory assigned to the monetary cost. Nonetheless, it is the meeting point between economics and law, or is in the marrow of the problem of public shortage. Expensive Subjects to modernity, as the effectiveness of fundamental rights, pass necessarily an ethical legal system of public spending. From the ethical principles deducted from the planning, only the democratic principle guides the public spending through the approval of public spending in the complex budget process. In other words, there is an ethical distancing of economic reality in relation to state responsibilities. From the dogmatic belief of insufficiency, public spending is evaluated ethically, according to the foundations of modern constitutionalism, in search of possible of the financial reserve, certain that the ethics of public economy is a sine qua non condition for legal ethics.

Saída compulsória do estrangeiro do território nacional à luz dos direitos humanos: análise de casos

This paper aims to review traditional concepts inherent to the general theory of the state and human rights, relating to the legal situation of foreign, understood as the subject of rights, especially when the is case of compulsory legal imposition of exit from national territory. After the serious violations during the Second World War and the importance acquired by the International Law of Human Rights, values as dignity, justice and equality are enshrined in the legal system and its respect required beyond the boundaries of any country. The creation of an international community, which is governed by rules that its members are subordinated, without distinction, as well as state - based on volunteerism, become inspired by one principled nature of these new concepts required of Global Society, as well as the adoption, influenced by neoconstitutionalism, to the model of State Constitutional rule of law, are opposed to the idea of state sovereignty connected to a superiority, absolute and unlimited power which recognizes no other above it, not even the basic principles or axioms that must govern the relationships internally. So looks for a concept of state that includes all the requirements of a democratic society, that have the people as the power holder, understanding that state element has undergone a relativization, because had to adapt to the contemporary values applicable to the individual, inserting in its concept, the indispensable obligation to protect the inalienable rights of citizens, regardless of with whom he have legal and political bond of nationality. It happens that, to consecrate these privileges to individuals, which, because they contain reference to values with supranational characteristics, are very abstract and are in constant collision course with internal rules, making it difficult to reconcile, it will use hermeneutics of human rights, due mainly to international courts, correlated with constitutional exegesis, in particular, legal principiologia, using, among others, the principles of reasonableness and proportionality, the systematic interpretation of the Constitution and international legal standards. Thus, it seek to enshrine the common foundation of all law , the link between the systems, namely, the dignity of human beings. Finally, it will see if Brazilian jurisdiction, through case studies, is tuned in line with these new paradigms, and in line with the International Bill of Human Rights, the Federal Constitution, the values and principles she hired

O direito fundamental contra a autoincriminação: a análise a partir de uma teoria do Processo Penal Constitucional

The right against self-incrimination is a fundamental right that works in the criminal prosecution, and therefore deserves a study supported by the general theory of criminal procedure. The right has a vague origin, and despite the various historical accounts only arises when there is a criminal procedure structured that aims to limit the State´s duty-power to punish. The only system of criminal procedure experienced that reconciles with seal self-incrimination is the accusatory model. The inquisitorial model is based on the construction of a truth and obtaining the confession at any cost, and is therefore incompatible with the right in study. The consecration of the right arises with the importance that fundamental rights have come to occupy in the Democratic Constitutional States. In the Brazilian experience before 1988 was only possible to recognize that self-incrimination represented a procedural burden for accused persons. Despite thorough debate in the Constituent Assembly, the right remains consecrated in a textual formula that´s closer to the implementation made by the Supreme Court of the United States, known as "Miranda warnings", than the text of the Fifth Amendment to the U.S. Constitution that established originally the right against self-incrimination with a constitutional status. However, the imprecise text does not prevent the consecration of the principle as a fundamental right in Brazilian law. The right against self-incrimination is a right that should be observed in the Criminal Procedure and relates to several of his canons, such as the the presumption of not guilty, the accusatory model, the distribution of the burden of proof, and especially the right of defense. Because it a fundamental right, the prohibition of self-incrimination deserves a proper study to her constitutional nature. For the definition of protected persons is important to build a material concept of accused, which is different of the formal concept over who is denounced on the prosecution. In the objective area of protection, there are two objects of protection of the norm: the instinct of self-preservation of the subject and the ability to self-determination. Configuring essentially a evidence rule in criminal procedure, the analysis of the case should be based on standards set previously to indicate respect for the right. These standard include the right to information of the accused, the right to counsel and respect the voluntary participation. The study of violations cases, concentrated on the element of voluntariness, starting from the definition of what is or is not a coercion violative of self-determination. The right faces new challenges that deserve attention, especially the fight against terrorism and organized crime that force the development of tools, resources and technologies about proves, methods increasingly invasive and hidden, and allow the use of information not only for criminal prosecution, but also for the establishment of an intelligence strategy in the development of national and public security