Indium

Ohne Zusammenfassung     

über die Einwirkung von Acetamid auf Aldehyde und von Formamid auf Acetophenon

Ohne ZusammenfassungEs sei mir gestattet, meinem hochverehrten Lehrer, dem Herrn Hofrat Prof. Dr. Ad. Lieben, meinen innigsten Dank für die mir bei der Ausführung dieser Arbeit gütigst erteilten Ratschläge auszusprechen.     

Fluorescence Detection of the Ornamental Fish Cardinal Tetra (Paracheirodon axelrodi)

The fluorescence spectra of the tropical fish, Cardinal Tetra ( Paracheirodon axelrodi ), originating in the Amazon region of Brazil, were determined. These spectra were then treated using factor analysis, generating two contributing spectra and separating out the noise. Time-resolved fluorescence results indicated that the fluorescent system in the epidermis undergoes excited state reaction. Excited state proton transfer is suggested as being present. Both intentionally stressed and nonstressed individuals were used and some small differences were noted in the contributions of the two calculated contributing spectra to the experimental spectra, presumably as a function of stress. The results are compared with those obtained by the standard determination of cortisol level using the whole body extraction method and it is suggested that the method could be tested as an improved, nondestructive way to determine stress in this species, which is a necessary step in the development of "best management practices" of methods for storage and transport of the fish.     

Numerical analysis and computational testing of a high accuracy Leray‐deconvolution model of turbulence

We study a computationally attractive algorithm (based on an extrapolated Crank‐Nicolson method) for a recently proposed family of high accuracy turbulence models, the Leray‐deconvolution family. First we prove convergence of the algorithm to the solution of the Navier‐Stokes equations and delineate its (optimal) accuracy. Numerical experiments are presented which confirm the convergence theory. Our 3d experiments also give a careful comparison of various related approaches. They show the combination of the Leray‐deconvolution regularization with the extrapolated Crank‐Nicolson method can be more accurate at higher Reynolds number that the classical extrapolated trapezoidal method of Baker (Report, Harvard University, 1976). We also show the higher order Leray‐deconvolution models (e.g. N = 1,2,3) have greater accuracy than the N = 0 case of the Leray‐α model. Numerical experiments for the 2d step problem are also successfully investigated. Around the critical Reynolds number, the low order models inhibit vortex shedding behind the step. The higher order models, correctly, do not. To estimate the complexity of using Leray‐deconvolution models for turbulent flow simulations we estimate the models' microscale.© 2007 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2008     

The regioselectivity of addition of organolithium reagents to enones and enals: the role of HMPA.

The role of polar solvents (particularly HMPA) in controlling the ratio of 1,2 to 1,4 addition of sulfur-substituted organolithium reagents to cyclohexenones and hexenal was studied. Low-temperature, multinuclear NMR studies provided quantitative information about the ratio of contact (CIP) and solvent-separated (SIP) ion pairs in solutions of dithianyllithiums and phenylthiobenzyllithiums in THF-HMPA solutions. The ratio of contact and separated ion pairs was manipulated by changes in the strength of solvation (generally through the addition of HMPA). Although the results are consistent with the CIP/SIP distribution being an important factor in determining the regioselectivity of these additions (Curtin-Hammett limitations prevent a direct correlation), it cannot be the only one. Changes in diastereomeric product ratios upon addition of HMPA suggest that complexation of HMPA to lithium has two effects. First, it causes ion pair separation, which enhances 1,4 addition. Second, it lowers the Lewis acidity and catalytic effectiveness of the lithium cation, which also favors 1,4 addition. For most sulfur-stabilized lithium reagents, 2 equiv of HMPA suffice to achieve >95% 1,4 addition, whereas 4 equiv of DMPU are required to achieve identical regiochemical and stereochemical results.     

Reaction of 4,5,6‐triaminopyrimidine and 2,4,5,6‐tetraaminopyrimidine with 3‐dimethylaminopropiophenones. Synthesis of new 4‐aryl‐2,3‐dihydropyrimido[4,5‐b][1,4]diazepines

Several new 6‐amino‐ and 6,8‐diamino‐4‐aryl‐2,3‐dihydropyrimido[4,5‐b][1,4]diazepines were obtained from the reaction of 4,5,6‐triaminopyrimidine 1a and 2,4,5,6‐tetraaminopyrimidine 1b with one equivalent of 3‐dimethylaminopropiophenones 2 in absolute ethanol. Structure analysis of 6‐amino‐ and 6,8‐diamino‐4‐aryl‐2,3‐dihydropyrimido[4,5‐b][1,4]diazepines 3a‐i , determined by detailed nmr measurements, reveals a high regioselectivity of this reaction.     

A general framework for the construction of piecewise-polynomial local interpolants of minimum degree

In this paper we consider the problem of designing piecewise polynomial local interpolants of non-uniformly spaced data. We provide a constructive approach that, for any assigned degree of polynomial reproduction, continuity order, and support width, allows for generating the fundamental spline functions of minimum degree having the desired properties. Finally, the proposed construction is extended to handle open sets of data and to the case of multiple knots.     

Associative formal power series in two indeterminates

Investigating the associativity equation for formal power series in two variables we show that the transcendental associative formal power series are of order one or two and that they can be represented by an invertible formal power series in one variable. We also discuss the convergence of associative formal power series.     

Computer‐Aided Optimization of Conditions for Fast and Controlled ICAR ATRP of n‐Butyl Acrylate

The potential of initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) for the synthesis of well‐defined poly(n‐butyl acrylate) is analyzed by means of simulations. The kinetic model accounts for reactivity differences between secondary and tertiary macrospecies and considers the possible influence of diffusional limitations. CuBr₂ is used as transition metal salt and the commercially available N,N,N′,N″,N″‐pentamethyldiethylenetriamine as ligand. For targeted chain lengths (TCLs) up to 1000, the ICAR ATRP can be performed relatively quickly, and with ppm levels of ATRP catalyst. For moderate TCLs, slightly higher ppm levels are required if excellent control over chain length is also desired. In all cases, limited loss of end‐group functionality (EGF) results.