Um estudo teórico relativo à não-linearidade da ligação de hidrogênio em sistemas heterocíclicos C2H4O-C2H2 e C2H4S-C2H2

B3LYP/6-31G(d,p) calculations were used to determine the optimized geometries of the C2H4O-C2H2 and C2H4S-C2H2 heterocyclic hydrogen-bonded complexes. Results of structural, rotational, electronic and vibrational parameters indicate that the hydrogen bonding is non-linear due to the pi bond of the acetylene interacting with the hydrogen atoms of the methyl groups of the three-membered rings. Moreover, the theoretical investigation showed that the non-linearity is much more intriguing, since there is a structural disjunction on the acetylene within the heterocyclic system.

Efeito das interações hiperconjugativas na constante de acoplamento ¹J CH da hexametilenotetramina e do adamantano: estudo teórico e experimental

The objective of this work was to determine the influence of hyperconjugative interactions on the ¹J CH coupling constant for hexamethylenetetramine (1) and adamantane (2). For this end, theoretical and experimental ¹J CH were obtained and hyperconjugative interactions were investigated using NBO. It was observed, theoretically and experimentally, that ¹J CH in 1 is 20 Hz larger than in 2, mainly due to the nN®s*C-H hyperconjugative interaction. This interaction occurs only in 1, with an energy of 9.30 kcal mol-1. It increases the s-character of the carbon atom in the C-H bond and the occupancy of the sigma*C-H orbital in (1).

Determinação da diferença entre o valor real e o teórico do triglicerídeo ECN 42 para a detecção de adulteração em azeites de oliva comercializados no Brasil

The difference between the actual ECN 42 triacylglyceride content in vegetable oils, obtained by HPLC analysis, and the theoretical value calculated from the fatty acid composition was applied to detect the addition of seed oils with high contents of linoleic acid to olive oils commercialized in Brazil. The results indicate that samples analyzed were probably adulterated with low commercial value seed oils, rich in linoleic acid, like soybean, sunflower or corn.

Um estudo teórico de propriedades moleculares em complexos de hidrogênio trimoleculares C2H4···2HF, C2H2···2HF e C3h6···2HF

We present a theoretical study of molecular properties in C2H4···2HF, C2H2···2HF and C3H6···2HF trimolecular hydrogen-bonded complexes. From B3LYP/6-311++G(d,p) calculations, the most important structural deformations are related to the C=C (C2H4), C≡C (C2H2), C-C (C3H6) and HF bond lengths. According to the Bader's atoms in molecules and CHELPG calculations, it was identified a tertiary interaction between the fluorine atom of the second hydrofluoric acid molecule and hydrogen atoms of the ethylene and acetylene within the C2H4···2HF and C2H2···2HF complexes, respectively. Additionally, the evaluation of the infrared spectrum characterized the new vibrational modes and bathochromic effect of the HF molecules.

Estudo teórico de propriedades ópticas não-lineares de nanotubos de carbono de parede única quimicamente modificados

Structure and first hyperpolarizability for a series of armchair a(5,5) chemically modified carbon nanotubes (CNT) were calculated at semiempirical and density functional levels of theory. The 4,4´-substituted stilbenes were selected as chromophore with substituents at position 4´ set to X=NO2, H, Cl, OH and NH2. The calculated values for static first hyperpolarizability (β) were almost linearly dependent on the electronic effect of the group X, increasing from NO2 to NH2. At DFT level the effect of inserting the chromophore in the CNT surface was to enhance the β value up to 70% relative to the free 4,4´-substituted stilbene.

Sistemas tampão: uma estrutura didática teórico-prática

Courses with practical and theoretical classes are potentially didactic structures for the development of motor and complex cognitive skills when operated in an integrated manner. When worked aligned, theory and practice enable a clearer view of the issue, opening scope for introducing concepts from other disciplines and for the development of lab skills. This paper presents a methodology for biochemistry labwork that promotes the teaching of the buffering systems contents together with to the development of scientific research practice concepts in an interdisciplinary perspective that integrates theory and practice.

Estudio teórico de la isomerización del ácido maleico en ácido fumárico: un enfoque basado en el concepto de superficie de energía potencial

A comparative study based on potential energy surfaces (PES) of 2-butanedioic and hypothetic 2-butanedioic/HCl acids is useful for understanding the maleic acid isomerization. The PES enables locating conformers of minimum energy, intermediates of reactions and transition states. From contour diagrams, a set of possible reaction paths are depicted interconnecting the proposed structures. The study was carried out in absentia and in the presence of the catalyst (HCl), using an solvatation model provided by the Gaussian software package. Clearly, the effect of HCl is given by new reaction paths with lower energetic barriers in relation to the reaction without catalyzing.

Abordagem teórico-experimental da teoria do campo cristalino na disciplina de síntese inorgânica

We describe herein the synthesis and characterization of the complexes KNiF3, [Ni(en)3]I2, [Ni(en)3]Cl2, [Ni(acac)2(H2O)2], [Ni(en)2(H2O)2]Cl2 and [Ni(NH3)6](BF4)2 (en = ethylenediamine, acac- = acetylacetonate) performed in the inorganic synthesis major course at the Chemistry Institute of UFRGS (Universidade Federal do Rio Grande do Sul). The compounds were characterized by infrared and electronic spectroscopy and the electrolytic conductivity was measured. The parameters 10Dq and B were obtained from the electronic spectra and the nefelauxetic and spectrochemical series were determined. The obtained spectrochemical series was F- < acac- < NH3 < en and the nefeulaxetic series was en < NH3 < acac- < F-.

Estudo teórico e experimental de espectros infravermelho de ésteres de ácido graxo presentes na composição do biodiesel de soja

In this work, theoretical and experimental infrared spectra of fatty acid methyl esters (FAME) contained in soybean biodiesel were analyzed seeking the assignments of the relevant vibrational modes to characterize crude soybean oil and soybean biodiesel. The results showed the usefulness of infrared spectra for monitoring saturated and unsaturated compounds as well as impurities (mainly glycerol) in raw samples. This is the first step toward proposing an efficient molecular spectroscopy routine to certify biodiesel fuel.

Estudo teórico da estrutura eletrônica e da dinâmica induzida por lasers da molécula de HCl

Potential energy and dipole moment curves for the HCl molecule were computed. Calculations were performed at different levels of theory (DFT, MRCI). Spectroscopic properties are reported and compared with experimental data, for validating the theoretical approaches. Interaction of infrared radiation with HCl is simulated using the wave packet formalism. The quantum control model for population dynamics of the vibrational levels, based on pi-pulse theory, is applied. The results demonstrate that wavepackets with specific composition can be built with short infrared laser pulses and provide the basis for studies of H + HCl collision dynamics with infrared laser excitation.

Estudo teórico das transições eletrônicas usando métodos simples e sofisticados

In this paper, the use of both simple and sophisticated models in the study of electronic transitions was explored for a set of molecular systems: C2H4, C4H4, C4H6, C6H6, C6H8, "C8", C60, and [H2NCHCH(CHCH)kCHNH2]+, where k = 0 to 4. The simple model of the free particle (1D, 2D, and 3D boxes, rings or spherical surfaces), considering the boundary conditions, was found to yield similar results to the sophisticated theoretical methods such as EOM-CCSD/6-311++G** or TD(NStates=5,Root=1)-M06-2X/6-311++G**.

A teoria de pearson para a disciplina de química orgânica: um exercício prático e teórico aplicado em sala de aula

We report a didactic experience in teaching Pearson's theory (HSAB) to graduate students in organic chemistry. This approach was based on teaching students how to use computer programs to calculate frontier orbitals (HOMO-LUMO). The suggested level of calculation was a semi-empiric PM3, proving to be efficient for obtaining robust and fast numerical results that can be performed easily in the classroom. We described a practical computational exercise and asked students to compare these numerical data with qualitative analysis using valence bond theory. A comprehensive solution of this exercise is presented, aiming to support teachers in their lessons.

Uso de diagrama V modificado como relatório em aulas teórico-práticas de química geral

In this article, we present data from a study in practical classes for General Chemistry. To this end, it was proposed to use a modified V diagram to replace traditional reporting. These reports consist of material commonly prepared in the subject, including introduction, materials and methods, results and discussion and conclusions. From the preparation of the modified V, the students were able to establish relationships between the theoretical and methodological aspects necessary for understanding the objects and events studied. Thus, student learning can be evaluated in light of the Theory of Meaningful Learning.

ESTUDIO TEÓRICO DE LA REACTIVIDAD QUÍMICA DEL CARBÓN ACTIVO

We used conceptual DFT to study global and local reactivity of both nonfunctionalized and functionalized activated carbons, with groups -OH,-CHO, -NH2, -COOH, and -CONH2. Electron-withdrawing groups were observed to increase the reactive surface, while electro-donating groups increase stability as reactivity of the activated carbon decreases. Descriptor groups were used to study the reactivity of structural fragments of activated carbons. The electrophilic and nucleophilic sites indicate that the carbon surface has an amphiphilic behavior that allows it to be used as an adsorbent material for a variety of molecules.

Esfera pública e democracia deliberativa em Habermas: modelo teórico e discursos críticos

Os argumentos a favor da concepção deliberativa de esfera pública e democracia têm sido alvos de muitas críticas. Muitos teóricos que se ocupam com teorias democráticas têm questionado as assunções básicas da teoria política deliberativa que resulta da obra sobre Faktizität und Geltung (1992), apontando pontos frágeis, sobre as implicações práticas, possibilidades de efetividade, entre outros. Embora não seja possível acompanhar em toda sua amplitude a bibliografia crítica sobre o tema, para nossos propósitos, vamos aqui nos limitar a apresentar alguns comentários acerca das controvérsias envolvendo as concepções de esfera pública e democracia deliberativa que resultam da obra sobre direito e democracia; questões que se tornaram problemáticas para a literatura e que poderiam ser melhor investigadas.