Análise de glicocorticosteróides por CG-EM: uma nova abordagem de derivatização para o controle de dopagem no esporte

Glucocorticosteroids (CT) show a powerful anti-inflammatory effect. In view of this, they are extensively used in sports medicine, but their misuse (systemic administration) can lead to severe injuries on athletes and has been restricted by the IOC in recent years. For GC-MS analysis, a derivatization step is necessary in order to convert them to a stable form, thus preventing thermal breakdown with the loss of the ketone side chain. Derivatization of CT is reviewed and a new approach of silylation is presented for screening of CT in urine.

Estudo da estrutura e da solvatação do HNP-3, um antibiótico natural, por dinâmica molecular

The structure and hydration of the HNP-3 have been derived from molecular dynamics data using root mean square deviation, radial and energy distributions. Three antiparallel beta sheets were found to be preserved. 15 intramolecular hydrogen bonds were identified together with 36 hydrogen bonds on the backbone and 35 on the side chain atoms. From the point of view of the hydration dynamics, the analysis shows a high solvent accessibility of the monomer and attractive interactions with water molecules.

O uso de pseudopotenciais e modelos HF/MP2/DFT na previsão de freqüências vibracionais em complexos metálicos

Four different pseudopotentials and three methodologies were employed in the calculation of the geometry and the frequencies of metal complexes like [M(NH3)2X2] [X=halogen, M=Zn, Cd], and [Hg(NH3)2]Cl2. The vibrational assignments were carefully checked and compared to the theoretically calculated ones. Graphical procedures were employed to estimate family errors and their average behavior. The calculated results show the SBK-X basis set with the best results for the geometries and calculated frequencies, for individual species and statistical results. Its use is recommend, mainly if the neighborhood atoms are described with similar pseudopotentials. Excellent results were also obtained with the Hay and Wadt pseudopotential.

Propriedades eletrônicas e estruturais do PbTiO3: teoria do funcional de densidade aplicada a modelos periódicos

Calculations based on density functional theory at the B3LYP hybrid functional level applied to periodic models have been performed to characterize the structural and electronic properties of PbTiO3. Two different slab terminations (PbO and TiO2) have been considered to obtain and discuss the results of band structure, density of states, charge distribution on bulk and surface relaxation. It is observed that the relaxation processes are most prominent for the Ti and Pb surface atoms. The electron density maps confirm the partial covalent character of the Ti-O bonds. The calculated optical band gap and other results are in agreement with experimental data.

Interações hiperfinas em catalisadores metálicos

Heterogeneous catalysts are of fundamental importance in several modern chemical processes. The characterization of catalysts is an issue of very present interest as it can provide a better understanding of the fundamental aspects of the catalytic phenomena, thus helping in the development of more efficient catalysts. In order to extend and improve the characterization of catalysts, new and less conventional methods are being applied, such as nuclear spectroscopies. In this paper we focus on the application of angular correlation, with can be used to resolve different local environments of probe atoms in solids and can be applied, as shown here, in the characterization of heterogeneous catalysts. A brief theoretical introduction is given and experimental results related to catalytic systems of alumina and niobia-supported Pt-In and Pd-In catalysts are presented.

Interfaces e organização da pesquisa no Brasil: da Química à Nanotecnologia

Nanotechnology can be viewed as a powerful tool, capable of shaping the chemistry of atoms and molecules, converting them into exciting nanosized and nanostructured materials, devices and machines. However, in pursuing this task, an exceptional ability is required to deal with complex inter- and multidisciplinary approaches, as imposed by the nanoscale. A new research organization framework, capable of promoting cooperative interactions in many complementary areas, including the industries, is demanded. In this sense, an interesting example are the nanotechnology networks and millenium institutes recently created in Brazil. The highlights and weakness of such cooperative research networks are discussed, in addition to relevant nanotechnology themes focusing on the special needs and resources from the developing nations.

Cloreto isocianúrico e cloreto cianúrico: aspectos gerais e aplicações em síntese orgânica

The aromatic six-membered heterocycles having three nitrogen atoms are denominated triazines. Among these heterocycles, isocyanuric chloride and cyanuric chloride are inexpensive and readily available 1,3,5-triazine derivatives, which have been attracting significant attention of organic chemists due to their different kinds of applications, which vary from pharmaceuticals to explosives. This short overview explores their uses in synthetic methods, as chlorinating and oxidating agents and some procedures for their preparation.

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.

Funcionalização de nanotubos de Carbono

Carbon nanotubes are very stable systems having considerable chemical inertness due to the strong covalent bonds of the carbon atoms on the nanotube surface. Many applications of carbon nanotubes require their chemical modification in order to tune/control their physico-chemical properties. One way of achieving this control is carrying out functionalization processes where atoms and molecules interact (covalent or non-covalent) with the nanotubes. We review some of the progress that has been made in chemical functionalization of carbon nanotubes. Emphasis is given to chemical strategies, the most used techniques, and applications.

O enfoque da metrologia química em análises toxicológicas na atividade turfística: validação de método analítico para determinação de cafeína em matrizes biológicas

This paper proposes an alternate method to detect forbidden doping substances present in biological matrices of horseracing. The method was fully validated for caffeine, identified as the most frequent forbidden substance in the analysis conducted by the Antidoping Laboratory of the Brazilian Jockey Club, which adopts a zero threshold limit according to national and international horseracing practices. The metrological reliability of the method applied to toxicological analysis in biological matrices is discussed. Although the analytical method proposed for detection of a zero threshold level of the doping substance is qualitative, it was validated for the determination of the limiting value (also known as quantification limit value) introducing a criterion that prevents the issuing of incorrect results ("false-positives" and "false-negatives").

Efeito da presença e concentração de compostos carbonílicos na qualidade de vinhos

Studies on identification of compounds that make up the aroma and flavor in wines involve research evaluating mainly the influence of terpenes, esters, lactones and alcohols upon these sensory characteristics. However, carbonylic compounds (CC) play an important role concerning the substances that impact aroma to these drinks. Their origin is reported to be linked to the grape's chemical composition, must fermentation or micro-oxidation occurring during storage in barrels. Some CCs, like E-ionone, E-damascenone, siryngaldehyde, can contribute a pleasant aroma and improve the wine quality whereas others are responsible for unpleasant characteristics (acetaldehyde, furfural, 5-hydroxy-methyl furfural, diacetil, E-non-2-enal, etc). A fraction of CCs present is associated with bisulfite ions in the form of hydroxyalkylsulfonic acids. Some of them are stable and play an important role in determining wine quality. The reaction involving the formation of this aduct commonly occurs with CCs of low molar mass, such as formaldehyde and acetaldehyde. The reaction involving CCs with more than three carbon atoms demands further studies.

Nanocompósitos cerâmicos a partir do processo de moagem mecânica de alta energia

Pb/Ti, Sn and Mg-based nanocomposite materials were prepared by the high-energy mechanical milling of commercial powders. The surface of these ceramic compounds was strongly influenced by the doping, diameter of the milling spheres and time of the mechanical milling (amorphization process). Such milling leads to the formation of nanocrystalline materials. The mechanical processing parameters of these compounds were investigated through Brunauer, Emmett and Teller isotherms, wide angle X-ray diffraction, transmission electron microscopy and CO2 adsorption.

Estudo da eletrocristalização de Ni e Ni-P sobre ultramicroeletrodo de platina

This work describes a comparative study of the electrocrystallization of Ni and Ni-P on Pt ultramicroelectrodes using chronoamperometric measurements. It was possible to confirm that in all cases a progressive nucleation was the predominant mechanism. Moreover, the application of the Atomistic Theory to the experimental rate of nuclei formation showed that the number of atoms in the critical nucleus was zero, except for Ni-P on Pt at low overpotentials were a value of one was observed. Furthermore, the physical characterisation of the different deposits on Pt by atomic force microscopy allowed observing the coalescence of the hemispherical nuclei of Ni and Ni-P at t max thus confirming the results obtained from the current-time analysis.

Synthesis, structure and physicochemical properties of zinc and copper complexes based on sulfonamides containing 8-aminoquinoline ligands

Sulfonamides obtained by reaction of 8-aminoquinoline with 4-nitrobenzenesulfonylchloride and 2,4,6-triisopropylbenzenesulfonyl chloride were used to synthesize coordination compounds with CuII and ZnII with a ML2 composition. Determination of the crystal structures of the resulting zinc and copper complexes by X-ray diffraction show a distorted tetrahedral environment for the [Cu(qnbsa)2], [Cu(qibsa)2] and [Zn(qibsa)2] complexes in which the sulfonamide group acts as a bidentate ligand through the nitrogen atoms from the sulfonamidate and quinoline groups. The complex [Zn(qnbsa)2] crystallizes with a water molecule from the solvent and the Zn is five-coordinated and shows a bipyramidal-trigonal geometry. The electrochemical and electronic spectroscopy properties of the copper complexes are also discussed.

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.