Variação do equilíbrio muscular durante uma temporada em jogadores de futebol categoria sub-20

O objetivo deste estudo foi analisar o equilíbrio muscular dos flexores e extensores (RFE) de joelho ao longo de uma temporada de treinamento em jogadores de futebol categoria sub-20. Fizeram parte da amostra 15 sujeitos pertencentes à equipe sub-20 da Associação Atlética Ponte Preta de Campinas. Os atletas participaram de um macrociclo de preparação (MP) de 29 semanas, composto por período preparatório e competitivo que foram divididos em quatro mesociclos: etapa geral (M1), etapa especial (M2), etapa pré-competitiva (M3) e etapa competitiva (M4). A RFE de ambos os membros foi determinada em dinamômetro isocinético utilizando o pico de torque (PT) obtido em três séries consecutivas de cinco repetições com velocidade de 60º/s. Avaliação isocinética foi realizada em quatro momentos ao longo do MP, sempre ao final de cada mesociclo (M1, M2, M3 e M4). Para análise estatística, foi empregado teste Friedman de medidas repetidas, seguida do teste de Wilcoxon e teste U de Mann-Whitney, com nível de significância de p<0,05. O PT nos músculos flexores de joelho, em ambos os membros, no M2 e M3 foram superiores aos observados em M1 e M4. O PT dos extensores de joelho em M1 foi significantemente inferior aos demais momentos do estudo (M2, M3 e M4), em ambos os membros. A RFE, em ambos os membros, foi inferior em M1 quando comparado a M2 e M3. A comparação da RFE entre os membros não revelou diferenças significantes em nenhum dos momentos do estudo (M1, M2, M3 e M4). Os resultados encontrados na presente investigação indicaram existência de alterações na magnitude da RFE, porém dentro da normalidade, e, manutenção da proporcionalidade entre os membros ao longo do MP. Esses resultados sugerem que não existem períodos sensíveis para a ocorrência de lesões em virtude de desequilíbrios musculares ao longo do MP em jogadores de futebol da categoria sub-20.

Cyclooligomerisation of azido-alkyne-functionalised sugars: synthesis of 1,6-linked cyclic pseudo-galactooligosaccharides and assessment of their sialylation by Trypanosoma cruzi trans-sialidase

Cyclic pseudo-galactooligosaccharides were synthesized by cyclooligomerisation of isomeric azido-alkyne derivatives of beta-D-galactopyranose under Cu(I)-catalysed azide-alkyne 1,3-dipolar cycloaddition reaction conditions. The principal products isolated were cyclic dimers and trimers, with lower amounts of cyclic tetramer and pentamer also evident in some cases. Molecular mechanics calculations suggest very compact but flexible structures for the cyclic trimers, with secondary OH groups exposed outside the macrocycle and available for enzymatic glycosylation. The cyclic dimers and trimers represent a new type of acceptor substrate for Trypanosoma cruzi trans-sialidase, giving rise to doubly and triply sialylated glycomacrocycles, respectively.

Photophysical properties of a photocytotoxic fluorinated chlorin conjugated to four beta-cyclodextrins

A meso-tetrakis(pentafluorophenyl)-chlorin with the reduced pyrrole ring linked to an isoxazolidine ring (FC) has been conjugated to four beta-cyclodextrins (CDFC). The CDFC exhibits excellent water solubility and is a potent photosensitizer towards proliferating NCTC 2544 human keratinocytes. The study by conventional steady state absorption and fluorescence spectroscopies and by time-resolved femto- and nanosecond laser flash spectroscopies suggests that in ethanol and pH 7 buffer the beta-cyclodextrins embed the highly hydrophobic tetrakis(pentafluorophenyl)-chlorin macrocycle and strongly interact with the chlorin rings in the singlet and triplet manifolds. In these solvents, femtosecond spectroscopy suggests that the conjugate undergoes a rapid relaxation in the upper excited singlet states induced by photochemical and/or conformation change(s) at a rate of about 5 ps(-1) to fluorescent states whose lifetime is similar to 8 ns. This interaction is destroyed upon addition of Triton X100 to buffer. Both FC and CDFC strongly fluoresce (Phi(F) similar to 0.5) in micelles. Similar behavior is observed at the triplet level. In ethanol and water, the initial transient triplet state absorbance decays within 1-3 mu s yielding a longer lived triplet with spectral properties indistinguishable from that of original difference absorbance spectra. The determination of the molar absorbance in the 440-460 nm region (similar to 35 000 M(-1) cm(-1)) leads to an estimate of similar to 0.2 for the triplet formation quantum yield of FC in toluene and of FC and CDFC in Triton X100 micelles. Quenching of the CDFC triplets by dioxygen in buffer produces (1)O(2) in a good yield consistent with the effective photocytotoxicity of the chlorin-cyclodextrins conjugate towards cultured NCTC 2544 human keratinocytes. By contrast, FC which aggregates in buffer produces little if any (1)O(2).

A new oxovanadium(IV)-cucurbit[6]uril complex: Properties and potential for confined heterogeneous catalytic oxidation reactions

This work presents a new oxovanadium(IV)-cucurbit[6]uril complex, which combines the catalytic properties of the metal ion with the size-excluding properties of the macrocycle cavity. In this coordination compound, the VO(2-) ions are coordinated to the oxygen atoms located at the rim of the macrocycle in slightly distorted square-pyramidal configurations, which are in fact C(2v) symmetries. This combination results in a size-selective heterogeneous catalyst, which is able to oxidize linear alkanes like n-pentane at room temperature, but not styrene, cyclohexane or z-cyclooctene, which are too big to enter the cucurbit[6]uril cavity. The results presented here contribute to understanding the mechanism of alkane catalytic oxidation by oxovanadium(IV) complexes. (C) 2010 Elsevier Ltd. All rights reserved.

Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.