Characterization of low molecular weight hydrocarbon oligomers by laser desorption/ionization time-of-flight mass spectrometry using a solvent-free sample preparation method.

A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards.     

Design of neutral, mono- or di-cationic water-soluble trihydrazidophosphoradamantanes

The versatile behavior of a trihydrazidophosphoradamantane allowing the synthesis of a variety of neutral, mono- or di-cationic water-soluble molecules of potential interest for biphasic catalysis is reported.     

IFS attractors and Cantor sets

We build a metric space which is homeomorphic to a Cantor set but cannot be realized as the attractor of an iterated function system. We give also an example of a Cantor set K in R³ such that every homeomorphism f of R³ which preserves K coincides with the identity on K.     

Integral Inequalities and Global Solutions of Semilinear Evolution Equations

A criterion for the nonexplosion of solutions to semilinear evolution equations on Banach spaces is proved. The result is obtained by applying a modification of the Bihari type inequality to the case of a weakly singular nonlinear integral inequality.     

Asymptotic Analysis of the Current-Voltage Curve of a pnpn Semiconductor Device

We consider the one-dimensional steady-state semiconductor deviceequations modelling a pnpn device. There are two relevant scalingsof the equations corresponding to small and large applied voltages.In both scalings, the semiconductor equations can be consideredas singularly perturbed. It turns out that the small-voltagescaling breaks down for current values between two saturationcurrents. In that interval, the large-voltage scaling has tobe employed. For both scalings, we derive the first-order termsof an asymptotic expansion and show that the reduced problemhas a solution. An example verifies that the current-voltagecurves obtained have the expected qualitative structure.     

Expected Reflection Distance in G(r, 1, n) after a Fixed Number of Reflections

Extending to r > 1 a formula of the authors, we compute the expected reflection distance of a product of t random reflections in the complex reflection group G(r, 1, n). The result relies on an explicit decomposition of the reflection distance function into irreducible G(r, 1, n)-characters and on the eigenvalues of certain adjacency matrices.Received December 8, 2003     

Recent advances in the analysis of steroid hormones and related drugs.

The development during the last 15 years and the state-of-the-art in the analysis of bulk steroid hormone drugs and hormone-like structures and pharmaceutical formulations made thereof are summarized. Other steroids (sterols, bile acids, cardiac glycosides, vitamins D) as well as biological-clinical aspects and pharmacokinetic and metabolic studies are excluded from this review. The state-of-the-art is summarized based on comparisons of monographs in the latest editions of the European Pharmacopoeia, United States Pharmacopoeia and the Japanese Pharmacopoeia. This is followed by sections dealing with new developments in the methodology for the fields of spectroscopic and spectrophotometric, chromatographic, electrophoretic and hyphenated techniques as well electroanalytical methods. The review is terminated by two problem-oriented sections: examples on impurity and degradation profiling as well as enantiomeric analysis.     

Electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols in aprotic media.

The electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols on graphite electrodes was studied using cyclic voltammetry, chronoamperometry, constant-potential coulometry and preparative constant-potential electrolysis techniques. The data revealed that the reduction on graphite was irreversible and followed an EC mechanism. The diffusion coefficients and the number of electrons transferred were determined using the chronoamperometric Cottrell slope and the ultramicro disc Pt-electrode steady-state current. The number of electrons was also determined by bulk electrolysis. The compounds were subjected to constant-potential preparative electrolysis and the electrolysis products were purified and identified by spectroscopic methods. Based on these findings, a mechanism for the electro-reduction process is proposed.     

Synthesis of paramagnetic BODIPY dyes as new double (spin and fluorescence) sensors

Paramagnetic pyrroline and 1,2,3,6-tetrahydropyridine derivatives of BODIPY and their diamagnetic analogs have been synthesized and characterized as novel redox double sensor and cation sensitive reagents.     

The Interaction of Shocks with Dispersive Waves II. Incompressible-Integrable Limit

This is the second in a two-part series of articles in which we analyze a system similar in structure to the well-known Zakharov equations from weak plasma turbulence theory, but with a nonlinear conservation equation allowing finite time shock formation. In this article we analyze the incompressible limit in which the shock speed is large compared to the underlying group velocity of the dispersive wave (a situation typically encountered in applications). After presenting some exact solutions of the full system, a multiscale perturbation method is used to resolve several basic wave interactions. The analysis breaks down into two categories: the nonlinear limit and the linear limit, corresponding to the form of the equations when the group velocity to shock speed ratio, denoted by ε, is zero. The former case is an integrable limit in which the model reduces to the cubic nonlinear Schrödinger equation governing the dispersive wave envelope. We focus on the interaction of a “fast” shock wave and a single hump soliton. In the latter case, the ε=0 problem reduces to the linear Schrödinger equation, and the focus is on a fast shock interacting with a dispersive wave whose amplitude is cusped and exponentially decaying. To motivate the time scales and structure of the shock-dispersive wave interactions at lowest orders, we first analyze a simpler system of ordinary differential equations structurally similar to the original system. Then we return to the fully coupled partial differential equations and develop a multiscale asymptotic method to derive the effective leading-order shock equations and the leading-order modulation equations governing the phase and amplitude of the dispersive wave envelope. The leading-order interaction equations admit a fairly complete analysis based on characteristic methods. Conditions are derived in which: (a) the shock passes through the soliton, (b) the shock is completely blocked by the soliton, or (c) the shock reverses direction. In the linear limit, a phenomenon is described in which the dispersive wave induces the formation of a second, transient shock front in the rapidly moving hyperbolic wave. In all cases, we can characterize the long-time dynamics of the shock. The influence of the shock on the dispersive wave is manifested, to leading order, in the generalized frequency of the dispersive wave: the fast-time part of the frequency is the shock wave itself. Hence, the frequency undergoes a sudden jump across the shock layer.In the last section, a sequence of numerical experiments depicting some of the interesting interactions predicted by the analysis is performed on the leading-order shock equations.