H MAS NMR monitoring of the C-labeled carbon scrambling for propane in zeolite H-ZSM-5

It has been demonstrated that ¹H MAS NMR spectroscopy can be used as a tool for in situ monitoring the reaction kinetics of ¹³C-labeled carbon scrambling in alkane molecules adsorbed on zeolite catalysts at the reaction temperature of 540–570 K. The accuracy of the results and the time resolution are improved compared to ¹³C MAS NMR spectroscopy.     

Physical foundation of quantitative Auger analysis

The possibility of using an Auger peak height in the dN (E) /dE spectrum and an integrated N (E) spectrum as a measure of the Auger current is discussed and necessary relations are presented. The methods of the background determination are reviewed and discussed.

The relation between the Auger current and the atomic cancentration of a corresponding sample component is derived and the state of art in the field of theoretical and experimental determination of factors appearing in this relation (ionization cross-section, Auger transition probability. backscattering factor, and inelastic mean free path of Auger electrons) is presented.

Approaches to the quantitative Auger analysis (QAA) of homogeneous, isotropic samples, including corrections for matrix factors, are presented and discussed. Problems arising when heterogeneous samples are analyzed are discussed and practical approaches to such an analysis are presented.

The role of crystalline effects (the dependence of the Auger signal from crystalline samples on the direction of the primary electron beam and angular distribution of Auger electron emission from such samples) in QAA is discussed and examples of such crystalline effects are presented together with their physical foundation.

Some rules are suggested allowing the quantitative Auger analysis to be performed with the smallest possible error.     

Liquid crystalline hexa-amides and side chain polysiloxanes of azacrown [18]-N6

The hexa-4-dodecyloxybenzoyl derivative 1 of azacrown [18]-N₆ was originally reported to have a 'tubular' mesophase on the basis of its large central ring and 6-fold symmetry. Starting in the mesophase, annealing of 1 under a cover slip results in formation of a new crystalline phase that melts directly to an isotropic liquid at the temperature previously observed for the mesophase to isotropic transition. Thus the phase behaviour of 1 is kinetically controlled. The analogous hexa-3,4-bisdodecyloxybenzoyl derivative 2 of azacrown [18]-N₆ has no kinetic limitations to its phase changes and has an enantiotropic columnar liquid crystalline phase. We have synthesized side chain copolysiloxanes with a (CH₂)₁₁ spacer and 75-84 per cent by weight of the same 4-dodecyloxybenzoyl-[18]-N₆ mesogen. The polysiloxanes also display a liquid crystalline phase.     

Optimal control of unsteady compressible viscous flows

The control of complex, unsteady flows is a pacing technology for advances in fluid mechanics. Recently, optimal control theory has become popular as a means of predicting best case controls that can guide the design of practical flow control systems. However, most of the prior work in this area has focused on incompressible flow which precludes many of the important physical flow phenomena that must be controlled in practice including the coupling of fluid dynamics, acoustics, and heat transfer. This paper presents the formulation and numerical solution of a class of optimal boundary control problems governed by the unsteady two‐dimensional compressible Navier–Stokes equations. Fundamental issues including the choice of the control space and the associated regularization term in the objective function, as well as issues in the gradient computation via the adjoint equation method are discussed. Numerical results are presented for a model problem consisting of two counter‐rotating viscous vortices above an infinite wall which, due to the self‐induced velocity field, propagate downward and interact with the wall. The wall boundary control is the temporal and spatial distribution of wall‐normal velocity. Optimal controls for objective functions that target kinetic energy, heat transfer, and wall shear stress are presented along with the influence of control regularization for each case. Copyright © 2002 John Wiley & Sons, Ltd.     

Determination of iphosphamide and seven metabolites in blood plasma,as stable trifluoroacetyl derivatives,by electron capture chemical ionization GC-MS

A method is described for the determination of the antitumor agent iphosphamide and seven of its metabolites in the plasma of cancer patients by multiple ion monitoring (MIM) GC-MS, mainly using the electron capture chemical ionization mode, of stable methyl and/or trifluoroacetyl derivatives. The metabolites determined were 2- and 3-dechloroethyliphosphamide, 4-ketoiphosphamide, carboxyiphosphamide, iphosphamide mustard, and two previously undetected metabolites, chloroethylamine and 1,3-oxazolidine-2-one. The isolation of the acidic and neutral metabolites was performed by solid phase extraction on to C₁₈ adsorbent at pH 4. The weakly acidic iphosphamide mustard, isolated under these conditions with a yield of ca 50%, was measured as a stable methyltrifluoroacetyl derivative, in contrast to the corresponding phosphoramide mustard of the isomer cyclophosphamide which decomposes during derivatization. Chloroethylamine and 1,3-oxazolidine-2-one were isolated with high yield by liquid extraction with ethyl acetate at pH 10. Selective measurement of several metabolite derivatives with similar retention times was performed by multiple ion monitoring MS of specific ion masses, using a methyl phenyl siloxane capillary column previously employed in the study of cyclophosphamide metabolites. Quantitation of metabolites in patient plasma samples could be performed in the concentration range 3 ng to 20 μg per ml of original plasma.     

Atomistic phenomena in dense fluid shock waves

The shock structure problem is one of the classical problems of fluid mechanics and at least for non-reacting dilute gases it has been considered essentially solved. Here we present a few recent findings, to show that this is not the case. There are still new physical effects to be discovered provided that the numerical technique is general enough to not rule them out a priori. While the results have been obtained for dense fluids, some of the effects might also be observable for shocks in dilute gases.     

Stable model categories are categories of modules

A stable model category is a setting for homotopy theory where the suspension functor is invertible. The prototypical examples are the category of spectra in the sense of stable homotopy theory and the category of unbounded chain complexes of modules over a ring. In this paper we develop methods for deciding when two stable model categories represent ‘the same homotopy theory’. We show that stable model categories with a single compact generator are equivalent to modules over a ring spectrum. More generally stable model categories with a set of generators are characterized as modules over a ‘ring spectrum with several objects’, i.e., as spectrum valued diagram categories. We also prove a Morita theorem which shows how equivalences between module categories over ring spectra can be realized by smashing with a pair of bimodules. Finally, we characterize stable model categories which represent the derived category of a ring. This is a slight generalization of Rickard's work on derived equivalent rings. We also include a proof of the model category equivalence of modules over the Eilenberg-Mac Lane spectrum HR and (unbounded) chain complexes of R-modules for a ring R.