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Caldeira J Figueirinhas JL Santos C Godinho MH 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,170(2):213-219
Correlation of the g-tensor of a paramagnetic active center of a protein with its structure provides a unique experimental information on the electronic structure of the metal site. To address this problem, we made solid films containing metalloprotein (Desulfovibrio gigas cytochrome c(3)) microcrystals. The microcrystals in a liquid crystalline polymer medium (water/hydroxypropylcellulose) were partially aligned by a shear flow. A strong orientation effect of the metalloprotein was observed by EPR spectroscopy and polarizing optical microscopy. The EPR spectra of partially oriented samples were simulated, allowing for molecular orientation distribution function determination. The observed effect results in enhanced sensitivity and resolution of the EPR spectra and provides a new approach towards the correlation of spectroscopic data, obtained by EPR or some other technique, with the three-dimensional structure of a protein or a model compound. 相似文献
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Elasticity of various poly(hydroxybutyrate) (PHB) molecules of regular and irregular conformational structure was examined by the molecular mechanics (MM) calculations. Force - distance functions and the Young's moduli E were computed by stretching of PHB molecules. Unwinding of the 2(1) helical conformation H is characterized at small deformations by the Young's modulus E = 1.8 GPa. The H form is transformed on stretching into the highly extended twisted form E, similar to the beta-structure observed earlier by X-ray fiber diffraction. The computations revealed that in contrast to paraffins, the planar all-trans structure of undeformed PHB is bent. Hence, a PHB molecule attains the maximum contour length in highly straightened, but slightly twisted conformations. A dependence of the single-chain moduli of regular and disordered conformations on the chain extension ratio x was found. The computed data were used to analyze elastic response of tie (bridging) molecules in the interlamellar (IL) region of a semi-crystalline PHB. A modification of the chain length distribution function of tie molecules tau(N) due to secondary crystallization of PHB was conjectured. The resulting narrow distribution tau(N) comprises the taut tie molecules of higher chain moduli prone to overstressing. The molecular model outlined is in line with the macroscopically observed increase in the modulus and brittleness of PHB with storage time. 相似文献