Electrospray ionization mass spectrometric characterization and quantitation of xanthine derivatives using isotopically labelled analogues: an application for equine doping control analysis

Isotope-dilution mass spectrometry has been employed successfully in numerous fields of analytical chemistry enabling the establishment of fast and reliable procedures. In equine sports, xanthine derivatives such as caffeine and theobromine are prohibited, and doping control laboratories analyze horse urine specimens regarding these illicit performance-enhancing drugs. Theobromine has to exceed a threshold level of 2 microg/mL, hence a robust and reliable quantitation is required. Stably deuterated theobromine and caffeine were synthesized by the reaction of xanthine or theobromine with iodomethane-d3 in the presence of N-methyl-N-trimethylsilyltrifluoroacetamide or potassium carbonate in acetonitrile, respectively. Both compounds were characterized by nuclear magnetic resonance spectroscopy and electrospray ionization tandem mass spectrometry, and a robust and fast assay for the qualitative and quantitative analysis of theobromine in equine urine samples was validated. Urine specimens were extracted by means of solid-phase extraction cartridges, and concentrated extracts were analyzed by liquid chromatography interfaced to a triple-quadrupole mass spectrometer. In addition, the dissociation behavior of deuterated analogues to caffeine and theobromine allowed proposals for fragmentation routes of xanthine derivatives after atmospheric pressure ionization and collisionally activated dissociation.     

Disc-shaped triphenylenes in a smectic organisation

A layered phase (SmA) was observed in a novel linked disc-rod mesogen, containing a triphenylene mesogen and attached to three cyanobiphenyl moieties.     

Global Solutions of an Obstacle-Problem-Like Equation with Two Phases

Concerning the obstacle-problem-like equation , where ₊ > 0 and _– > 0, we give a complete characterization of all global two-phase solutions with quadratic growth both at 0 and infinity.     

Cycle Range Distributions for Gaussian Processes Exact and Approximative Results

Wave cycles, i.e. pairs of local maxima and minima, play an important role in many engineering fields. Many cycle definitions are used for specific purposes, such as crest–trough cycles in wave studies in ocean engineering and rainflow cycles for fatigue life predicition in mechanical engineering. The simplest cycle, that of a pair of local maximum and the following local minimum is also of interest as a basis for the study of more complicated cycles. This paper presents and illustrates modern computational tools for the analysis of different cycle distributions for stationary Gaussian processes with general spectrum. It is shown that numerically exact but slow methods will produce distributions in almost complete agreement with simulated data, but also that approximate and quick methods work well in most cases. Of special interest is the dependence relation between the cycle average and the cycle range for the simple maximum–minimum cycle and its implication for the range distribution. It is observed that for a Gaussian process with rectangular box spectrum, these quantities are almost independent and that the range is not far from a Rayleigh distribution. It will also be shown that had there been a Gaussian process where exact independence hold then the range would have had an exact Rayleigh distribution. Unfortunately no such Gaussian process exists.This revised version was published online in March 2005 with corrections to the cover date.     

Regenerative amplification of femtosecond laser pulses in Ti:sapphire at multikilohertz repetition rates

We have generated and applied noncoherent x-ray radiation in an all-solid-state laser system operating at repetition rates up to 20 kHz. Based on a model that takes into account the strong thermal loading of the Ti:sapphire rod, a laser cavity with low sensitivity to thermal lensing was chosen. With a maximum pump power of 80 W, an output power as high as 27 W was obtained in gain-switched operation, and, with a seeding from a femtosecond oscillator, 60-fs, 0.8-mJ (8-W) pulses at 10 kHz and 0.32-mJ (6.5-W) pulses at 20 kHz were generated. High power femtosecond output was used to generate x-ray continuum radiation up to 5 keV from a liquid-gallium jet target.     

Persistence of zero velocity fronts in reaction diffusion systems

Steady, nonpropagating, fronts in reaction diffusion systems usually exist only for special sets of control parameters. When varying one control parameter, the front velocity may become zero only at isolated values (where the Maxwell condition is satisfied, for potential systems). The experimental observation of fronts with a zero velocity over a finite interval of parameters, e.g., in catalytic experiments [Barelko et al., Chem. Eng. Sci., 33, 805 (1978)], therefore, seems paradoxical. We show that the velocity dependence on the control parameter may be such that velocity is very small over a finite interval, and much larger outside. This happens in a class of reaction diffusion systems with two components, with the extra assumptions that (i) the two diffusion coefficients are very different, and that (ii) the slowly diffusing variables has two stable states over a control parameter range. The ratio of the two velocity scales vanishes when the smallest diffusion coefficient goes to zero. A complete study of the effect is carried out in a model of catalytic reaction. (c) 2000 American Institute of Physics.     

Synthesis and structure‐activity relationship of several aromatic ketone‐based two‐photon initiators

Several novel aromatic ketone‐based two‐photon initiators containing triple bonds and dialkylamino groups were synthesized and the structure‐activity relationships were evaluated. Branched alkyl chains were used at the terminal donor groups to improve the solubility in the multifunctional monomers. Because of the long conjugation length and good coplanarity, the evaluated initiators showed large two‐photon cross section values, while their fluorescence lifetimes and quantum yields strongly depend on the solvent polarity. All novel initiators exhibited high activity in terms of two‐photon‐induced microfabrication. This is especially true for fluorenone‐based derivatives, which displayed much broader processing windows than well‐known highly active initiators from the literature and commercially available initiators. While the new photoinitiators gave high reactivity in two‐photon‐induced photopolymerization at concentration as low as 0.1% wt, these compounds are surprisingly stable under one photon condition and nearly no photo initiation activity was found in classical photo DSC experiment. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011