Continuation theorems of the extremes under power normalization

In this paper an important stability property of the extremes under power normalizations is discussed. It is proved that the restricted convergence of the power normalized extremes on an arbitrary nondegenerate interval implies the weak convergence. Moreover, this implication, in an important practical situation, is obtained when the sample size is considered as a random variable distributed geometrically with meann.     

A note on the convergence of trivariate extreme order statistics and extension

Necessary and sufficient conditions, under which there exists (at least) a sequence of vectors of real numbers for which the distribution function (d.f.) of any vector of extreme order statistics converges to a nondegenerate limit, are derived. The interesting thing is that these conditions solely depend on the univariate marginals. Moreover, the limit splits into the product of the limit univariate marginals if all the bivariate marginals of the trivariate d.f., from which the sample is drawn, is of negative quadrant dependent random variables (r.v.'s). Finally, all these results are stated for the multivariate extremes with arbitrary dimensions.     

Asymptotic dependence between random central quasi-ranges and random empirical quantiles

The asymptotic dependence between the central quasi-ranges and empirical quantiles was studied. The asymptotic dependence are obtained when the sample size is a positive integer valued random variable (r.v.). The dependence conditions and limit forms are obtained under generl conditions such as: the interrelation of the basic variables (the original random sample) and the random sample size is not restricted. In addition the normalizing constants do not depend on the random size.     

Extreme value modeling under power normalization

In this paper the mathematical modeling of extremes under power normalization is developed. An estimate of the shape parameter within the generalized extreme value distribution under power normalization is suggested. The statistical inference about the upper tail of a distribution function by using the power normalization is studied. Two models for generalized Pareto distribution under power normalization (GPDP) are given. Estimates for the shape and scale parameters within these GPDP’s are obtained. Finally, a simulation study illustrates and corroborates theoretical results.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.