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Xiao-Yuan Liu Kazuo O. Cottrell Thomas M. Nordlund 《Photochemistry and photobiology》1989,50(6):721-731
The effects of citrate ion concentration and pH on the optical spectra and fluorescence decay have been measured for several tyrosine model compounds and lima bean trypsin/chymotrypsin inhibitor, a protein containing one tyrosine at position 69 and seven disulfides but no tryptophan, in order to determine the location and environment of Tyr 69. Tyrosine in the protein is protected from citrate collisional quenching, as indicated by the dynamic quenching constant 9 to 15 times smaller than those for the model peptides. Static quenching remains, with a Stern-Volmer constant of about 1.0 M-1, somewhat smaller than those of L-tyrosine, tyrosine-glutamate, and leucine-tyrosine-leucine. The elevated pKa of Tyr 69, greater than or equal to 11.6, also indicates protein protection from solvent ions. Though Coulomb repulsion of the Glu 70/citrate pair may play a role in the shielding of Tyr 69 from citrate, our measurements indicate that steric effects of the protein structure are more important. Tyrosinate emission in the protein at neutral pH is minimal. 相似文献
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A. H. Cottrell 《Contemporary Physics》2013,54(6):417-432
Metals contain free electrons. Various theoretical and practical implications of this characteristic feature of the metallic state are discussed. Recent views which emphasize ease of ionization, unsaturated metallic bonds, and screening of electrical charges by free electrons, as the basis for distinguishing between metals, semi-conductors, and insulators, are described. The importance of the free electron bond for the crystal structures, cohesive properties, and alloy behaviour of metals is emphasized, and the principles underlying the engineering strength properties of matter and the design of creep-resistant alloys are briefly discussed in terms of free electrons and dislocations in solids. 相似文献
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An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol?1)·T?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. 相似文献
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Abstract Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood. 相似文献
8.
Probability-based protein identification by searching sequence databases using mass spectrometry data 总被引:96,自引:0,他引:96
Several algorithms have been described in the literature for protein identification by searching a sequence database using mass spectrometry data. In some approaches, the experimental data are peptide molecular weights from the digestion of a protein by an enzyme. Other approaches use tandem mass spectrometry (MS/MS) data from one or more peptides. Still others combine mass data with amino acid sequence data. We present results from a new computer program, Mascot, which integrates all three types of search. The scoring algorithm is probability based, which has a number of advantages: (i) A simple rule can be used to judge whether a result is significant or not. This is particularly useful in guarding against false positives. (ii) Scores can be compared with those from other types of search, such as sequence homology. (iii) Search parameters can be readily optimised by iteration. The strengths and limitations of probability-based scoring are discussed, particularly in the context of high throughput, fully automated protein identification. 相似文献
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W.B. Atwood E.D. Bloom R.L.A. Cottrell H. DeStaebler M. Mestayer C.Y. Prescott L.S. Rochester S. Stein R.E. Taylor D. Trines 《Physics letters. [Part B]》1976,64(4):479-482
Inelastic electron scattering cross sections have been measured for four-momentum transfers between 4.1 GeV2 and 30.5 GeV2. At the large scattering angles of this experiment, the dominant contribution to the cross section comes from the W1 structure function. In the conventional scaling variables, x and x′, this structure function does not exhibit scaling behavior, and at fixed x or x′ it is found to decrease with increasing four-momentum transfer. 相似文献
10.
C.R.A. Catlow M. Cherry K.H. Chow S.P. Cottrell S.F.J. Cox E.A. Davis K.V. Wright 《Hyperfine Interactions》1997,106(1-4):119-122
The expectation that the hydroxyl analogue state of positive muons implanted in quartz should be stabilized by a suitable
charge compensation centre is supported by preliminary data. The diamagnetic fraction correlates with aluminium content over
the narrow range investigated.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献