Extraction, interpretation and validation of information for comparing samples in metabolic LC/MS data sets

LC/MS is an analytical technique that, due to its high sensitivity, has become increasingly popular for the generation of metabolic signatures in biological samples and for the building of metabolic data bases. However, to be able to create robust and interpretable (transparent) multivariate models for the comparison of many samples, the data must fulfil certain specific criteria: (i) that each sample is characterized by the same number of variables, (ii) that each of these variables is represented across all observations, and (iii) that a variable in one sample has the same biological meaning or represents the same metabolite in all other samples. In addition, the obtained models must have the ability to make predictions of, e.g. related and independent samples characterized accordingly to the model samples. This method involves the construction of a representative data set, including automatic peak detection, alignment, setting of retention time windows, summing in the chromatographic dimension and data compression by means of alternating regression, where the relevant metabolic variation is retained for further modelling using multivariate analysis. This approach has the advantage of allowing the comparison of large numbers of samples based on their LC/MS metabolic profiles, but also of creating a means for the interpretation of the investigated biological system. This includes finding relevant systematic patterns among samples, identifying influential variables, verifying the findings in the raw data, and finally using the models for predictions. The presented strategy was here applied to a population study using urine samples from two cohorts, Shanxi (People's Republic of China) and Honolulu (USA). The results showed that the evaluation of the extracted information data using partial least square discriminant analysis (PLS-DA) provided a robust, predictive and transparent model for the metabolic differences between the two populations. The presented findings suggest that this is a general approach for data handling, analysis, and evaluation of large metabolic LC/MS data sets.     

An efficient route to pentasubstituted acylferrocenes

A number of pentasubstituted acylferrocenes were selectively prepared from ferrous chloride, sodium acylcyclopentadienides, and the corresponding pentasubstituted lithium cyclopentadienides in good yields. The selectivity is governed by the different steric and electronic properties of the acylcyclopentadienides vs the pentasubstituted cyclopentadienides.     

SCF-CI MO treatment of radicals having degenerate ground states

A form of the configuration interaction method is described which accommodates radicals having a doubly degenerate molecular orbital occupied by one or three electrons. The procedure covers all types of excited configurations corresponding formally to one-electron promotions from the ground state. The matrix elements derived are based on the SCF MO's given by the half-electron method. The computational scheme is applied, in the CNDO and PPP-like approaches, to the interpretation of the electronic spectrum of the cyclopentadienyl radical.     

Large angle production of stable particles heavier than the proton and a search for quarks at the CERN intersecting storage rings

Measurements have been performed on production of particles with mass 1.5 GeV/c² and charge $\text{?}\text{2}\text{3}$ for θ_lab = 62.5° and $\text{s}\text{= 53}\text{GeV}$. At p_T = 0.7 GeV/c the relative rate of production of antideuterons to π^? is (5 ± 1) × 10^?5. The deuteron to antideuteron ratio is 3.7 ± 1.2. No new stable particle has been amongst 0.7 × 10⁸ charged particles entering our detector.     

Multivariate analysis to separate the signal given by cross-reactants in immunoassay with sample matrix dilution

This paper describes a new approach to achieve selectivity in an immunoassay by separating the signals given by two cross-reactive compounds present simultaneously in a complex sample matrix. The method is based on the sequential dilution of the sample containing a mixture of the two analytes, spiking each diluted sample with a reference compound, and the detection by enzyme-linked immunosorbent assay (ELISA). The obtained multivariate response was used for the individual calibrations of the assay for each of the two cross-reactants simultaneously by using principal component analysis (PCA) and partial least squares regression (PLSR) data modeling. The calibration models showed that the signal separation due the analytes 2,4-dinitrophenol (2,4-DNP) and 4-nitrophenol (4-NP) was possible with a prediction concentration error of 1.4 M and 72 M, respectively.     

Signatures of the handbag mechanism in wide-angle photoproduction of pseudoscalar mesons

Wide-angle photoproduction of pseudoscalar mesons is investigated under the assumption of dominance of the handbag mechanism, considering both quark helicity flip and non-flip. The partonic subprocess, meson photoproduction off quarks, is analysed with the help of a covariant decomposition of the subprocess amplitudes which is independent of a specific meson generation mechanism. As examples of subprocess dynamics, however, the twist-2 as well as two-particle twist-3 contributions are explicitly calculated. Characteristic features of the handbag approach are discussed in dependence upon the relative magnitudes of the invariant functions. Differential cross sections and spin correlations are predicted to show a characteristic behaviour which allows one to test the underlying assumption of handbag dominance.Received: 15 September 2003, Revised: 2 December 2003, Published online: 29 January 2004     

Side pumping of double-clad photonic crystal fibers

Side pumping of double-clad photonic crystal fibers is experimentally demonstrated. Optical access to the multimode cladding is obtained by collapsing the airholes over a short length of fiber while leaving the inner single-mode core undisturbed. Coupling efficiencies greater than 90% are obtained. A side-pumped Yb fiber laser with a slope efficiency of 81% is demonstrated with this method.     

Direct photomodulation of peptide backbone conformations

Significant photoswitching ability is found for secondary thioxopeptide bonds and can be used for the photomodulation of the backbone conformation of peptides or proteins.     

Calculation of the Steady State Waiting Time Distribution in GI/PH/c and MAP/PH/c Queues

We consider the waiting time (delay) W in a FCFS c-server queue with arrivals which are either renewal or governed by Neuts' Markovian arrival process, and (possibly heterogeneous) service time distributions of general phase-type F _i , with m _i phases for the ith server. The distribution of W is then again phase-type, with m ₁m _c phases for the general heterogeneous renewal case and phases for the homogeneous case F _i =F, m _i =m. We derive the phase-type representation in a form which is explicit up to the solution of a matrix fixed point problem; the key new ingredient is a careful study of the not-all-busy period where some or all servers are idle. Numerical examples are presented as well.