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排序方式: 共有181条查询结果,搜索用时 15 毫秒
1.
Xilin Ren Chingkuang Tu Deepa Bhatt J. Jefferson P. Perry John A. Tainer Diane E. Cabelli David N. Silverman 《Journal of Molecular Structure》2006,790(1-3):168-173
Incorporation of 3-fluorotyrosine and site-specific mutagenesis have been used with stopped-flow spectrophotometry and pulse radiolysis to investigate the catalytic properties of human manganese superoxide dismutase (MnSOD). All of the nine tyrosine residues in each of the four subunits of the homotetramer of human MnSOD were replaced with 3-fluorotyrosine. Previous studies showed that the crystal structures of the unfluorinated and fluorinated human MnSOD are nearly superimposable with the root-mean-square deviation for 198 -carbon atoms at 0.3 Å. However, the catalytic activity kcat/Km of the fluorinated MnSOD at 30 μM−1 s−1 was less than unfluorinated wild type at 800 μM−1 s−1. Comparison of the values of kcat/Km for fluorinated and unfluorinated wild-type andY34F MnSOD showed that this decrease for the fluorinated enzyme was in significant part due to 3-fluorotyrosine residues distant (>7 Å) from the active-site metal, not to 3-fluorotyrosine at position 34 close (5 Å) to the metal. Although many rate constants for the catalysis are decreased by this fluorination, the rate of dissociation of the product-inhibited complex appears unchanged by the presence of fluorinated tyrosines. These results suggest that Tyr34 is not a proton donor in the release of the product-inhibited complex, which involves protonation of a peroxo complex of the metal with release of hydrogen peroxide. 相似文献
2.
The action of ultra violet rays of 260 nm on aqueous solutions of bases, nucleosides and nucleotides of DNA at 77°K is studied by electron spin resonance. It is shown that the free radicals observed are similar, with a few noteworthy exceptions to those induced by X-rays, under the same conditions of temperature, in the solid state. Contrary to what might be excepted on the basis of the results obtained by X-rays, the variation in the yield in paramagnetic centres in each sequence studied does not seem to be important. 相似文献
3.
ALBERT VAN DE VORST 《Photochemistry and photobiology》1971,13(4):321-336
Abstract— –The photosensitization of amino acids by proflavine is studied using the technique of electron spin resonance spectroscopy. The analysis of the line shape as a function of the incident microwave power (both in the presence and absence of oxygen) and the dependence of the numbers of free radicals on the intensity of the incident light allow one to suggest that two types of radicals are formed. One is formed by a biphotonic process, the nature of the radicals being the same as in the case of ionising radiation, while the other is probably the RO2 radical formed as a result of photodynamic action. 相似文献
4.
BARB FLORIN DAN; IONESCU VLAD; KONING WILLEM DE 《IMA Journal of Mathematical Control and Information》1994,11(4):277-309
In this paper, we deal with the digital output-measurement-feedbackH control problem for Pritchard-Salamon infinite-dimensionalsystems with unbounded input and output operators. A discretePopov-theory-based solution is given in terms of the solvabilityof Kalman-Szegö-Popov-Yakubovitch systems associated withthe equivalent discrete-time time-invariant system obtainedby lifting the T-periodic continuous-time system. 相似文献
5.
The rate constants at which oxidizing and reducing radicals react with the dinuclear iron(III) complex Fe2O(ttha)2− were measured in neutral aqueous solution. The rate constants for reduction of the complex by ·CO2.− CH3.CHOH and O2.− were found to be comparable with rate constants previously measured in mononuclear iron(III) polyaminocarboxylate systems. Fe2O(ttha)2− reacts slowly with O2.− (k8 = (1.2 ± 0.2) × 104 dm3 mol−1 s−1) and, hence, is a relatively poor catalyst for the dismutation of superoxide radical. The hydrated electron reduces the complex at a diffusion-controlled rate in a process which consumes one proton: eaq− + Fe2O(ttha)2− → Fe2III,IIO(ttha)3− The reduction by carbon-centered radicals produces a (III,II) mixed-valence complex with an absorption spectrum different from that of the Fe2(II,III) species produced from reduction by the hydrated electron. The oxidizing radicals .OH and ·CO3− appear to act as reductants of the complex via ligand oxidation rather than by oxidation of the Fe2IIIO core to Fe2III,IVO. In the former case ligand attack appears to occur mainly at the methylene carbon of a glycinate group. The decarboxylation product, CO2, was detected by its aquation reaction in the presence of a pH sensitive dye, bromthymol blue. 相似文献
6.
Abstract— Ellipsometric angles and reflectivity of black lipid membranes containing either egg lecithin or chloroplast extracts were measured at a wavelength of 6328 Å. Evidence was found for positive uniaxial anisotropy in membranes of lecithin. If the thickness of those films is assumed to be 62 Å, the refractive index normal to the film surface is 1.471 ± 0.004, and the refractive index parallel to the film surface is 1.454 ± 0.003. The results for membranes of chloroplast extracts also indicate a positive anisotropy in the indices of absorption. 相似文献
7.
ELISABETH TAFFIN DE GIVENCHY FREDERIC GUITTARD FREDERIC BRACON AIME CAMBON 《Liquid crystals》2013,40(9):1371-1377
In order to determine the influence of 'sulphur-containing' spacers on the formation of mesophases in low molecular mass compounds, we have examined the mesomorphic behaviour of molecules which consists of a 4-biphenyl unit linked to an unbranched fluorinated chain via a short spacer including at least a sulphur atom. The synthesis of these compounds has been carried out from 2-F-butylethyl iodide or from the 2-F-alkylethyl mercaptans in the case of the F-hexyl and F-octyl tails. The mesomorphic properties have been characterized by polarized light microscopy and by differential thermal analysis showing the peculiar contribution of each of the spacers. The influence of the fluorinated chain and the shape of the connector on the stability of the mesophases has been investigated. The compounds with a thioether or a hemithioacetal spacer showed no mesomorphic properties, whereas the structures with a thioester spacer showed a very interesting enantiotropic behaviour of the smectic A type over a wide temperature range. Furthermore from the series exhibiting liquid crystalline behaviour, increasing the number of fluoromethylene units simultaneously increases both the melting and the clearing temperature. These mesomorphic properties within the fluorinated series are compared with those of their monocatenar hydrocarbon homologues. 相似文献
8.
We attempt to resolve the discrepancy between the Buckingham—Longuet-Higgins (BLH) and Imrie—Raab (IR) theories of linear birefringence induced in a gas of dipolar molecules by an electric field gradient. To this end we present a new calculation of the effect, based on forward scattering of a light beam incident on a thin lamina of gas molecules. We work to electric quadrupole—magnetic dipole order. The beam undergoes a time delay which is proportional to the thickness of the lamina and the electric field gradient, and can therefore be interpreted in terms of a contribution to the refractive index of the gas due to the field gradient. The birefringence is obtained by considering appropriate polarizations of the incident beam. To avoid the occurrence of a divergent quantity, such as appears in the BLH theory, it is essential to take account of the finite beam width. Calculations are performed using both primitive (traced) and traceless molecular quadrupole moments; as required on basic grounds, these results are equivalent. They are also identical to the BLH result. By contrast, the IR result is physically unacceptable because it is not invariant with respect to the use of traced and traceless moments. The source of error in the IR theory remains unclear. 相似文献
9.
O. L. DE Lange 《Molecular physics》2013,111(4):607-611
We apply general arguments (based on spatial transformation properties, intrinsic symmetry and dimensional analysis) to the theory of the Buckingham effect (electric-field–gradient-induced birefringence in a gas). These yield, in a simple manner, the temperature-dependent and temperature-independent terms in the birefringence (each to within a numerical factor), and also the expression, derived by Buckingham and Longuet-Higgins, for the effective quadrupole centre of a molecule. We show in addition how the calculation of the two numerical factors can be simplified in our approach. 相似文献
10.