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41.
Peggy S. Eis Józef Kuśba Michael L. Johnson Joseph R. Lakowicz 《Journal of fluorescence》1993,3(1):23-31
Time-resolved fluorescence resonance energy transfer (FRET) measurements were used to measure distance distributions and intramolecular dynamics (site-to-site diffusion) of a 28-residue single-domain zinc finger peptide in the absence and presence of zinc ion. Energy transfer was measured between TRP14 and a N-terminal DNS group. As expected, the TRP-to-DNS distance distribution for zinc-bound peptide is shorter and narrower (R
av=11.2 Å,hw=2.8 Å) than the metal-free peptide (R
av=20.1 Å,hw=14.5 Å). The degree of mutual donor-to-acceptor diffusion (D) was also determined for these distributions. For zinc-bound peptide there is no detectible diffusion (D0.2 Å2/ns), whereas for metal-free peptide a considerable amount of motion is occurring between the donor and the acceptor (D=12 Å2/ns). These results indicate that the zinc-bound peptide folds into a unique, well-defined conformation, whereas the metal-free conformation is flexible and rapidly changing. The absence of detectible mutual site-to-site diffusion between the donor and the acceptor in the metal-bound zinc finger peptide indicates that intramolecular motion is essentially frozen out, on the FRET time scale, as a consequence of zinc coordination.Dedicated to the memory of Barbara D. Wells. 相似文献
42.
Sharon E. Navard John W. Seaman Jr. Dean M. Young 《Annals of the Institute of Statistical Mathematics》1993,45(4):603-614
Bertin and Theodorescu (1984,Statist. Probab. Lett.,2, 23–30) developed a characterization of discrete unimodality based on convexity properties of a discretization of distribution functions. We offer a new characterization of discrete unimodality based on convexity properties of a piecewise linear extension of distribution functions. This reliance on functional convexity, as in Khintchine's classic definition, leads to variance dilations and upper bounds on variance for a large class of discrete unimodal distributions. These bounds are compared to existing inequalities due to Muilwijk (1966,Sankhy, Ser. B,28, p. 183), Moors and Muilwijk (1971,Sankhy, Ser. B,33, 385–388), and Rayner (1975,Sankhy, Ser. B,37, 135–138), and are found to be generally tighter, thus illustrating the power of unimodality assumptions. 相似文献
43.
M. A. Eyler 《Journal of Optimization Theory and Applications》1985,45(1):159-163
The effect of small changes in parameter values on the sample values is investigated further. The concept of linearity with respect to parameters is introduced, and the linear and the nonlinear cases are treated separately. The relation with the sample-path analysis is discussed. 相似文献
44.
Summary We present a molecular theory of the energy distributions for the internal quantum states of a solute in a liquid or glassy solvent. We show that the energy distributions for different states are correlated in a way that depends on the solute-solvent interactions. We show how the theory can be modified easily to describe the transition-energy distributions for different pairs of states, which are of course related to inhomogeneously broadened absorption spectra. We also show that the distributions for different transitions are correlated, and describe how this correlation is measured by nonresonant fluorescence- and phosphorescence-line-narrowing and hole-burning experiments. The theory provides a microscopic framework within which to interpret different phenomenological models. For the case of a Lennard-Jones solute in a Lennard-Jones liquid solvent, we compare our theory to Monte Carlo simulation. 相似文献
45.
A combination of "black box" and "calendar-time" methods for the determination of calibration intervals of an analytical
measuring instrument is discussed. Since the methods require information on the distributions of the calibration parameters,
such information is described for an atomic absorption spectrophotometer, as an example. The hypotheses on the normal distribution
of the calibration parameters are tested using the ω2-criterion and accepted at 0.90–0.95 levels of confidence. Corresponding control charts are designed for indication of warning
and action limits of the calibration parameters, and diagnoses of outliers in further calibrations. Control charts indicate
also when the calibration should be done according to the full program of the equipment manufacturer.
Received: 15 April 2000 / Accepted: 24 July 2000 相似文献
46.
An extended bubble point method has been used to examine the porous morphology of several track-etched microporous polycarbonate membranes with nominal pore sizes ranging from 0.1 to 5.0 μm. The technique has been carefully analyzed and corrected to take into account the diverse non-ideal factors in flow along with the prevalence of Knudsen flow over the Hagen-Poiseuille one in the smaller pores. 相似文献
47.
Electron diffraction and lattice dynamical calculations are used to investigate the unit cells, space group symmetries and inherent displacive flexibility of the room-temperature average structures of AlPO4-8, AlPO4-16 and AlPO4-tridymite. The zero-frequency rigid unit modes (RUMs) of the idealized high-symmetry polymorphs thereof are also investigated along with their relationship to the lower-temperature polymorphism of these zeotypic aluminophosphates. The clear presence of satellite reflections in addition to the Bragg reflections (G) of the underlying Cmc21 parent structure in the case of AlPO4-8 shows that the true unit cell of the room-temperature polymorph has a doubled c-axis due to a condensed RUM mode. Structured diffuse scattering is also observed which can be related to the thermal excitation of RUM modes. In the case of AlPO4-tridymite, a complex F1 triclinic polymorph is observed and related to soft RUM modes while, in the case of AlPO4-16, a soft q=0 RUM mode is shown to be responsible for an observed phase transition in the case of the all SiO2 analogue of AlPO4-16. A large number of additional zero-frequency RUM modes also exist in the case of AlPO4-16. 相似文献
48.
Mohamed Habibullah S. K. Katti 《Annals of the Institute of Statistical Mathematics》1991,43(2):391-404
In maximizing a non-linear function G(), it is well known that the steepest descent method has a slow convergence rate. Here we propose a systematic procedure to obtain a 1–1 transformation on the variables , so that in the space of the transformed variables, the steepest descent method produces the solution faster. The final solution in the original space is obtained by taking the inverse transformation. We apply the procedure in maximizing the likelihood functions of some generalized distributions which are widely used in modeling count data. It was shown that for these distributions, the steepest descent method via transformations produced the solutions very fast. It is also observed that the proposed procedure can be used to expedite the convergence rate of the first derivative based algorithms, such as Polak-Ribiere, Fletcher and Reeves conjugate gradient methods as well. 相似文献
49.
The rate-of-convergence problem in the central limit theorem is considered for -stable distributions on the noncommutative group of motions in d. The method used here is based on the theory of probability metrics. 相似文献
50.
Peter Hald Martin Bremholm Jacques Chevallier Bo B. Iversen 《Journal of solid state chemistry》2006,179(8):2674-2680
Highly crystalline anatase TiO2 nanoparticles have been synthesised in less than 1 min in a supercritical propanol-water mixture using a continuous flow reactor. The synthesis parameter space (T, P, concentration) has been explored and the average particle size can be accurately controlled within 10-18 nm with narrow size distributions (2-3 nm). At subcritical conditions amorphous products are obtained, whereas a broad range of T and P in the supercritical regime gives 11-14 nm particles. At high temperature and pressure, the particles size increase to 18 nm. The nanoparticles have been extensively characterised with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) with excellent agreement on size and size distribution parameters. The SAXS analysis suggests disk-shaped particles with diameters that are approximately double the height. For comparison, a series of conventional autoclave sol-gel syntheses have been carried out. These also produce phase-pure anatase nanoparticles, but with much broader size distributions and at much longer synthesis times (hours). The study demonstrates that synthesis in supercritical fluids is a very promising method for manipulating the size and size distribution of nanoparticles, thus removing one of the key limitations in many applications of nanomaterials. 相似文献