Índice de aromaticidade baseado na deslocalização, degenerescência e densidade (D3BIA) para acenos e moléculas homoaromáticas

The aromaticity index is an important tool for the investigation of aromatic molecules. This work consists on new applications of the aromaticity index developed by teacher Caio Lima Firme, so-called D3BIA (density, delocalization, degeneracy-based index of aromaticity). It was investigated its correlation with other well-known aromaticity indexes, such as HOMA (harmonic oscillator model of aromaticity), NICS (nucleus independent chemical shielding), PDI (para-delocalization index), magnetic susceptibility (), and energetic factor in the study of aromaticity of acenes and homoaromatic species based on bisnoradamantanyl cage. The density functional theory (DFT) was used for optimization calculations and for obtaining energetic factors associated with aromaticity and indexes HOMA and NICS. From quantum theory of atoms in molecules (QTAIM) it was obtained the indexes D3BIA, PDI and . For acenes, when the over-mentioned indexes were applied it was observed no correlation except for D3BIA and HOMA (R2=0.752). For bisnoradamantenyl dication and its derivatives, it was obtained a good correlation between D3BIA and NICS. Moreover, it was evaluated solely one of the factors used on D3BIA calculation, the delocalization index uniformity (DIU), so as to investigate its possible influence on stability of chemical species. Then, the DIU was compared with the formation Gibbs free energy of some pairs of carbocations, isomers or not, which each pair had small difference in point group symmetry and no difference among other well-known stability factors. The obtained results indicate that DIU is a new stability factor related to carbocations, that is, the more uniform the electron density delocalization, the more stable the is carbocation. The results of this work validate D3BIA and show its importance on the concept of aromaticity, indicating that it can be understood from degeneracy of atoms belonging the aromatic site, the electronic density in the aromatic site and the degree of uniformity of electron delocalization

Novos protocolos teóricos utilizados nos estudos das ligações hidrogênio-hidrogênio, na estabilidade do tetraedrano, seus derivados e das reações de diels-alder e na quantificação da afinidade de fármacos

This thesis was performed in four chapters, at the theoretical level, focused mainly on electronic density. In the first chapter, we have applied an undergraduate minicourse of Diels-Alder reaction in Federal University of Rio Grande do Norte. By using computational chemistry tools students could build the knowledge by themselves and they could associate important aspects of physical-chemistry with Organic Chemistry. In the second chapter, we studied a new type of chemical bond between a pair of identical or similar hydrogen atoms that are close to electrical neutrality, known as hydrogen-hydrogen (H-H) bond. In this study performed with complexed alkanes, provides new and important information about their stability involving this type of interaction. We show that the H-H bond playing a secondary role in the stability of branched alkanes in comparison with linear or less branched isomers. In the third chapter, we study the electronic structure and the stability of tetrahedrane, substituted tetrahedranes and silicon and germanium parents, it was evaluated the substituent effect on the carbon cage in the tetrahedrane derivatives and the results indicate that stronger electron withdrawing groups (EWG) makes the tetrahedrane cage slightly unstable while slight EWG causes a greater instability in the tetrahedrane cage. We showed that the sigma aromaticity EWG and electron donating groups (EDG) results in decrease and increase, respectively, of NICS and D3BIA aromaticity indices. In addition, another factor can be utilized to explain the stability of tetra-tert-butyltetrahedrane as well as HH bond. GVB and ADMP were also used to explain the stability effect of the substituents bonded to the carbon of the tetrahedrane cage. In the fourth chapter, we performed a theoretical investigation of the inhibitory effect of the drug abiraterone (ABE), used in the prostate cancer treatment as CYP17 inhibitor, comparing the interaction energies and electron density of the ABE with the natural substrate, pregnenolone (PREG). Molecular dynamics and docking were used to obtain the CYP1ABE and CYP17-PREG complexes. From molecular dynamics was obtained that the ABE has higher diffusion trend water CYP17 binding site compared to the PREG. With the ONIOM (B3LYP:AMBER) method, we find that the interaction electronic energy of ABE is 21.38 kcal mol-1 more stable than PREG. The results obtained by QTAIM indicate that such stability is due a higher electronic density of interactions between ABE and CYP17

Uma Estranha Forma de DIU - a Propósito de um Caso Clínico

A propósito de um caso clínico de corpo estranho intra-uterino diagnosticado em ecografia como D.I.U., os autores fazem uma revisão da literatura sobre esta patologia. O papel da histeroscopia é discutido em relação ao diagnóstico e à terapêutica desta situação.

El culte al cos: què sap la ciència que la publicitat no diu?

Treball de recerca realitzat per una alumna d’ensenyament secundari i guardonat amb un Premi CIRIT per fomentar l'esperit científic del Jovent l’any 2008. La pressió social viscuda actualment imposa insistentment un model únic de cos ideal prim, amb el conseqüent rebuig de l’obesitat. Maldar per aconseguir aquest ideal és el que s’anomena “culte al cos”, qualificat per molts especialistes d’epidèmia que afecta totes les capes socials. Els objectius del treball han estat: saber quines són les dificultats que hi ha per a moltes persones per arribar o mantenir l’ideal; corroborar el model d’imatge corporal que transmeten les revistes femenines; i demostrar que la informació dels anuncis publicitaris relacionats amb els productes de bellesa ometen informació imprescindible per a la salut o falsegen l’eficàcia dels productes en qüestió.

The nature of the Cr-C bond: direct estimation of aromaticity in Fischer carbenes

Report for the scientific sojourn at the the Philipps-Universität Marburg, Germany, from september to december 2007. For the first, we employed the Energy-Decomposition Analysis (EDA) to investigate aromaticity on Fischer carbenes as it is related through all the reaction mechanisms studied in my PhD thesis. This powerful tool, compared with other well-known aromaticity indices in the literature like NICS, is useful not only for quantitative results but also to measure the degree of conjugation or hyperconjugation in molecules. Our results showed for the annelated benzenoid systems studied here, that electron density is more concentrated on the outer rings than in the central one. The strain-induced bond localization plays a major role as a driven force to keep the more substituted ring as the less aromatic. The discussion presented in this work was contrasted at different levels of theory to calibrate the method and ensure the consistency of our results. We think these conclusions can also be extended to arene chemistry for explaining aromaticity and regioselectivity reactions found in those systems.In the second work, we have employed the Turbomole program package and density-functionals of the best performance in the state of art, to explore reaction mechanisms in the noble gas chemistry. Particularly, we were interested in compounds of the form H--Ng--Ng--F (where Ng (Noble Gas) = Ar, Kr and Xe) and we investigated the relative stability of these species. Our quantum chemical calculations predict that the dixenon compound HXeXeF has an activation barrier for decomposition of 11 kcal/mol which should be large enough to identify the molecule in a low-temperature matrix. The other noble gases present lower activation barriers and therefore are more labile and difficult to be observable systems experimentally.

Reliure de : Achillis (Bocchi), Bononiensis, apologia in Plautum. Vita Ciceronis, auctore Plutarcho nuper inventa ac diu desiderata. - "A la fin" : Apologiam Philer. unaque M. Tulli vitam ex Plutarcho Joannes Anto. Pla. promulgavit Juli Liguris Pont. Max. Bonon. Soteris aureo saeculo M D VIII, nonis april

Comprend : Marci Tullii Ciceronis vita...

The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes

The encapsulation of metal clusters in endohedral metallofullerenes (EMFs) takes place in cages that in most cases are far from being the most stable isomer in the corresponding hollow fullerenes. There exist several possible explanations for the choice of the hosting cages in EMFs, although the final reasons are actually not totally well understood. Moreover, the reactivity and regioselectivity of (endohedral metallo)fullerenes have in the past decade been shown to be generally dependent on a number of factors, such as the size of the fullerene cage, the type of cluster that is being encapsulated, and the number of electrons that are transferred formally from the cluster to the fullerene cage. Different rationalizations of the observed trends had been proposed, based on bond lengths, pyramidalization angles, shape and energies of (un)occupied orbitals, deformation energies of the cages, or separation distances between the pentagon rings. Recently, in our group we proposed that the quest for the maximum aromaticity (maximum aromaticity criterion) determines the most suitable hosting carbon cage for a given metallic cluster (i.e. EMF stabilization), including those cases where the IPR rule is not fulfilled. Moreover, we suggested that local aromaticity plays a determining role in the reactivity of EMFs, which can be used as a criterion for understanding and predicting the regioselectivity of different reactions such as Diels-Alder cycloadditions or Bingel-Hirsch reactions. This review highlights different aspects of the aromaticity of fullerenes and EMFs, starting from how this can be measured and ending by how it can be used to rationalize and predict their molecular structure and reactivity

A topologia molecular QTAIM e a descrição mecânico-quântica de ligações de hidrogênio e ligações de di-hidrogênio

Hydrogen bonds formed through the interaction between a high electronic density center (lone electron pairs, π or pseudo-π bonds) and proton donors cause important electronic and vibrational phenomena in many systems. However, it was demonstrated that proton donors interact with hydrides, such as alkali and alkaline earth metals (BeH2, MgH2, LiH and NaH), what yields a new type of interaction so-called dihydrogen bonds. The characterization of these interactions has been performed at light of the Quantum Theory of Atoms in Molecules (QTAIM), by which the electronic densities ρ are quantified and the intermolecular regions are characterized as closed-shell interactions through the analysis of the Laplacian field ∇2ρ.

Estudo dopplerfluxométrico das artérias uterinas antes e após inserção do DIU

OBJETIVO: averiguar se ocorrem alterações nos parâmetros da dopplervelocimetria em usuárias do dispositivo intra-uterino (DIU) T cobre 380, por meio do estudo das artérias uterinas antes e depois da inserção do DIU em mulheres lactantes e não lactantes. MÉTODOS: ensaio clínico prospectivo, analítico, com 100 pacientes, em que avaliamos à dopplervelocimetria: índice de resistência (IR), índice de pulsatilidade (IP) e relação sístole/diástole (SD). As pacientes selecionadas foram submetidas à avaliação pré-inserção do DIU e a novos exames pós-inserção, realizados com 30 dias (um ciclo) e com 90 dias (três ciclos). RESULTADOS: os valores obtidos nas artérias uterinas no grupo antes da inserção do DIU foram de 0,9 para o IR, de 2,4 para o IP e de 10,0 para a relação SD. Os valores 30 dias após a inserção do DIU foram de 0,9 para o IR, de 2,5 para o IP e de 10,7 para a relação SD. Após três ciclos aferimos um valor de 0,9 para o IR, de 2,5 para o IP e de 10,7 para a relação SD. A comparação dos resultados obtidos antes e depois da inserção do DIU mostrou valor p de 0,51 para o IR, de 0,37 para o IP e de 0,51 para a relação SD, demonstrando que após a inserção, não houve modificações significativas na dopplervelocimetria. CONCLUSÕES: o uso do DIU T cobre 380 não tem efeito nos índices de dopplervelocimetria das artérias uterinas tanto em pacientes amamentando ou não.

Gu??a did??utica del v??diu : T??mulos ya d??lmenes d'Asturies. 'Gu??a did??ctica del v??deo : T??mulos y d??lmenes de Asturias'

Se trata de una gu??a para explotar did??cticamente en el aula partiendo de unas actividades propuestas que puedan adaptarse seg??n con quien se empleen estos materiales. Se estudian las manifestaciones megal??ticas, necr??polis, ritos funerarios, t??mulos y d??lmenes que hay por toda Asturias. El objetivo es crear valores y respetar el patrimonio cultural, art??stico e hist??rico, estimarlo; apreciar y valorar con actitud cr??tica la forma de recibir informaciones y su contenido. La metodolog??a es activa e investigadora para potenciar en el alumno la capacidad de descubrir, etc. Se relacionan una serie de actividades, y posteriormente un vocabulario y dos textos sobre el tema, uno de Alberto ??lvarez Pe??a y el otro de Daniel Garc??a de la Cuesta.

Què hi diu aquí? : procés evolutiu de la lectura. '¿Qué dice aquí? : proceso evolutivo de la lectura'.

Resumen de las autoras en catalán

Que diu la crítica? Tres opinions sobre el mateix llibre. '¿Que dice la crítica? Tres opiniones sobre el mismo libro'.

Resumen en catalán

Mitjans de comunicació i escola: Qui diu què? Què diu qui? : conversa entre una periodista i una mestra. 'Medios de comunicación y escuela : ¿Quién dice qué? ¿Qué dice quién? : conversación entre una periodista y una maestra'.

Se abordan las dificultades encontradas en la relación entre los medios de comunicación y los diferentes agentes sociales y políticos, teniendo en cuenta la independencia del país y de la época. El desconocimiento que existe entre los profesionales de las dos partes crea una profunda sensación de decepción, contrariedad y malestar que provoca fuegos entrecruzados de palabras y de relaciones complicadas. El trato entre periodistas y profesores, medios de comunicación y sistema educativo, no parece una excepción.