Importance of the choice of assumptions and models in the estimation of analytical quality specifications

The validity of any model depends on its ability to imagine the situation or problem to which it is applied. Further, the assumptions made in relation to the model are determining for the actual outcome. Within the field of clinical biochemistry a lot of models for analytical quality specifications, based on a variety of concepts and ’clinical settings’, have been proposed. A hierarchical structure for application of these approaches and models has been agreed on at several occasions in 1999. In this hierarchy, the highest rank is given to evaluation of analytical quality specifications based on ’clinical settings’/’clinical outcome’ models, followed by specifications based on biological variation and on ’clinicians opinions’. This contribution, deals with the problems of combining random and systematic errors and the implications of application of different models to a variety of clinical settings. Received: 1 June, 2002 Accepted: 17 July 2002 Presented at the European Conference on Quality in the Spotlight in Medical Laboratories, 7–9 October 2001, Antwerp, Belgium     

Convolution semigroups and central limit theorem associated with a dual convolution structure

We consider hypergroups associated with Jacobi functions ⁽⁾ (x), (–1/2). We prove the existence of a dual convolution structure on [0,+[i(]0,s ₀]{{) =++1,s ₀=min(,–+1). Next we establish a Lévy-Khintchine type formula which permits to characterize the semigroup and the infinitely divisible probabilities associated with this dual convolution, finally we prove a central limit theorem.     

Gaussian,non-Gaussian critical fluctuations in the Curie-Weiss model

It is known that at the critical temperature the Curie-Weiss mean-field model has non-Gaussian fluctuations and that internal fluctuations can be Gaussian. Here we compute the distribution of theq-mode magnetization fluctuations as a function of the temperature, the wave vectorq, and a fading out external field. We obtain new classes of probability distributions generated by this external field as well as new critical behavior in terms of its rate of fading out. We discuss also the susceptibility as the limitq tending to zero.     

Some analytical semigroups occurring in probability theory

One-parameter semigroups occurring in operator-limit distributions are investigated. The topological-algebraic background of the relevant monoids is discussed and Lie semigroup theory is applied to the Urbanik Decomposability Semigroup.     

Distance distributions and dynamics of a zinc finger peptide from fluorescence resonance energy transfer measurements

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 Ų/ns), whereas for metal-free peptide a considerable amount of motion is occurring between the donor and the acceptor (D=12 Ų/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.     

A characterization of discrete unimodality with applications to variance upper bounds

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.     

Density Functional Theory Study on the Adsorption of Dioxygen on Small Pt-Pd Clusters

1 INTRODUCTION The bimetallic nanoclusters are of standing inte- rest since they can exhibit catalytic, electronic and optical properties distinct from those of corre- sponding pure nanoclusters[1～4]. Palladium and pla- tinum, well known for their catalytic properties, are often used as the catalyst in different fuel cells[5～8]. Several experimental results illustrate that for the oxygen reduction reaction (ORR), which is one of the primary reactions taking place in many fuel cells and…     

Sensitivity of sample values to parameter changes

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.     

脱水KFI沸石中钾离子分布的模拟退火研究

基于四个固定的参量设值：阳离子位能差E_M2-E_M1=25.50 kJ/mol、 E_M3-E_M1=-10.73 kJ/mol和最近邻阳离子对互作用能W₁₂=45.6 kJ/mol、 W₁₄=0.56 kJ/mol以及一个温度依赖的参量E_M4-E<     

A molecular theory of inhomogeneous broadening,including the correlation between different transitions,in liquids and glasses

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.