Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis

In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS ¹⁸O/¹⁶O monitoring for future method development is proposed.     

On totally monotonic families of sequences

Summary. Total positivity is an important concept which has been studied by Gantmacher, Karlin and Schoenberg. In section 1, new properties of totally positive functions are given. The concept of totally monotonic families of sequences (TMFS), by mean of positivity of some determinant, is defined and studied. Applications to extrapolation algorithms are given. Received October 22, 1997 / Revised version received April 14, 1998 / Published online August 19, 1999     

Current partition in multiprobe conductors in the presence of slowly oscillating external potentials

In the presence of a static potential drop a carrier stream incident at a contact of the sample is partitioned into the other contacts according to the transmission probabilities of the sample. The bare response to oscillating potentials, on the other hand, violates current conservation due to the piling up of unscreened charges in the sample, and has to be modified by taking the induced screening potential into account. We present a novel derivation of the conductance response to oscillating external chemical potentials, find the response to an arbitrary internal potential in terms of functional derivatives with respect to the local potential of the scattering matrix of the conductor, and determine the screening potential for slowly oscillating potentials from the condition of local charge neutrality. We find that the current partitioning depends on ratios of local densities of states which reflect the injection and emission properties of the contacts of the sample.     

A canonical partition theorem for equivalence relations on Zt

A canonical version of the multidimensional version of van der Waerden's theorem on arithmetic progressions is proved.     

Ein Distributivitätskriterium für Verbände

Those one-place functions on a latticeL with values inL which can be obtained from the identityx and the constant functions by means of the fundamental operations ofL in a finite number of steps are called one-place polynomial functions. —It is shown that a latticeL is distributive iff all its one-place polynomial functions can be represented by words such that in every word the indeterminatex occurs at most once.     

Phosphine-mediated [4 + 2] annulation of bis(enones): a Lewis base catalyzed "mock Diels-Alder" reaction

Lewis-base-catalyzed cycloisomerization of bis(enones) to decalins has been demonstrated as an alternative to the traditional Lewis acid catalyzed Diels-Alder cycloaddition. In this process, a trialkylphosphine mediates both bond formation steps in two distinct catalytic cycles. The single-pot operation generates two carbon-carbon bonds and up to five contiguous stereocenters in one step, starting from achiral, aliphatic substrates; eight examples are provided. [reaction: see text]     

An efficient method to perform milliliter-scale PCR utilizing highly controlled microwave thermocycling

This communication describes the development of a controlled microwave methodology for rapid milliliter-scale PCR.     

Tetrahedral onsager crosses for solubility improvement and crystallization bypass

Pure organic molecules exhibiting a suitable concave rigid shape are expected to give porous glasses in the solid state. Such a feature opens new opportunities to avoid crystallization and to improve molecular solubility in relation to the high internal energy of these solid phases. To quantitatively explore the latter strategy, a series of rigid tetrahedral conjugated molecules nC and the corresponding models nR have been synthesized. Related to the present purpose, several properties have been investigated using UV absorption, steady-state fluorescence emission, differential scanning calorimetry, (1)H NMR translational self-diffusion, magic angle spinning (13)C NMR, and multiple-beam interferometry experiments. The present tetrahedral crosses are up to 8 orders of magnitude more soluble than the corresponding model compounds after normalization to the same molecular length. In addition, they give concentrated monomeric solutions that can be used to cover surfaces with homogeneous films whose thickness goes down to the nanometer range. Such attractive features make cross-like molecular architectures promising for many applications.     

Approximation and Prediction of the Numerical Solution of Some Burgers Problems

The Aitken's ²-prediction of Brezinski has already been used by Morandi Cecchi et al. in order to compute a numerical approximation of the solution of a parabolic initial-boundary value problem. This method consists in two consecutive steps: the first one is the approximation with a finite elements method, where the solution of the involved nonlinear system is computed by Gauss–Seidel method; the second one is a prediction of further terms with Aitken's ²-process. By comparison with this method, we use other methods of prediction in another way. First, we consider a generalization of ²-prediction, the so-called -prediction. In this paper, we only use vector prediction which is more stable than the scalar one. Then, the methods of prediction presented can be used in order to predict the starting vector of the Gauss–Seidel method.     

Solvation dynamics of Hoechst 33258 in water: an equilibrium and nonequilibrium molecular dynamics study

Integrated within an appropriate theoretical framework, molecular dynamics (MD) simulations are a powerful tool to complement experimental studies of solvation dynamics. Together, experiment, theory, and simulation have provided substantial insight into the dynamic behavior of polar solvents. MD investigations of solvation dynamics are especially valuable when applied to the heterogeneous environments found in biological systems, where the calculated response of the environment to the electrostatic perturbation of the probe molecule can easily be decomposed by component (e.g., aqueous solvent, biomolecule, ions), greatly aiding the molecular-level interpretation of experiments. A comprehensive equilibrium and nonequilibrium MD study of the solvation dynamics of the fluorescent dye Hoechst 33258 (H33258) in aqueous solution is presented. Many fluorescent probes employed in experimental studies of solvation dynamics in biological systems, such as the DNA minor groove binder H33258, have inherently more conformational flexibility than prototypical fused-ring chromophores. The role of solute flexibility was investigated by developing a fully flexible force-field for the H33258 molecule and by simulating its solvation response. While the timescales for the total solvation response calculated using both rigid (0.16 and 1.3 ps) and flexible (0.17 and 1.4 ps) models of the probe closely matched the experimentally measured solvation response (0.2 and 1.2 ps), there were subtle differences in the response profiles, including the presence of significant oscillations for the flexible probe. A decomposition of the total response of the flexible probe revealed that the aqueous solvent was responsible for the overall decay, while the oscillations result from fluctuations in the electrostatic terms in the solute intramolecular potential energy. A comparison of equilibrium and nonequilibrium approaches for the calculation of the solvation response confirmed that the solvation dynamics of H33258 in water is well-described by linear response theory for both rigid and flexible models of the probe.