1,8-bis(dimethylethyleneguanidino)naphthalene: tailoring the basicity of bisguanidine "proton sponges" by experiment and theory

1,8-bis(dimethylethyleneguanidino)naphthalene (DMEGN), the second example of a peralkyl guanidine "proton sponge" based on the 1,8-naphthalene backbone, was prepared and fully characterized. The crystal structure analysis of monoprotonated DMEGN reveals an unsymmetrical intramolecular hydrogen bridge. A decrease in the basicity with respect to the noncyclic parent 1,8-bis(tetramethylguanidino)naphthalene was found. Nevertheless, a new proton sponge provides a new crossbar in the ladder of highly basic neutral organic compounds. A detailed theoretical study of DMEGN and related cyclic guanidines explains this surprising experimental result. Homodesmotic reactions reveal that the intramolecular hydrogen bond contributes effectively 10 kcal/mol to proton affinity of DMEGN.     

Carbon nanodots revised: the thermal citric acid/urea reaction

Luminescent compounds obtained from the thermal reaction of citric acid and urea have been studied and utilized in different applications in the past few years. The identified reaction products range from carbon nitrides over graphitic carbon to distinct molecular fluorophores. On the other hand, the solid, non-fluorescent reaction product produced at higher temperatures has been found to be a valuable precursor for the CO₂-laser-assisted carbonization reaction in carbon laser-patterning. This work addresses the question of structural identification of both, the fluorescent and non-fluorescent reaction products obtained in the thermal reaction of citric acid and urea. The reaction products produced during autoclave–microwave reactions in the melt were thoroughly investigated as a function of the reaction temperature and the reaction products were subsequently separated by a series of solvent extractions and column chromatography. The evolution of a green molecular fluorophore, namely HPPT, was confirmed and a full characterization study on its structure and photophysical properties was conducted. The additional blue fluorescence is attributed to oligomeric ureas, which was confirmed by complementary optical and structural characterization. These two components form strong hydrogen-bond networks which eventually react to form solid, semi-crystalline particles with a size of ∼7 nm and an elemental composition of 46% C, 22% N, and 29% O. The structural features and properties of all three main components were investigated in a comprehensive characterization study.

Products of the thermal reaction of citric acid and urea have been identified as a complex mixture of fluorophores and particles.     

Deuterated ammonium formate as deuterium source in a mild catalytic deuterium transfer reaction of pyridines, pyrazines and isoquinolines

The application of deuterated ammonium formate as deuterium source in transfer deuteration reactions of aromatic heterocycles (4-6) for the synthesis of highly deuterated, substituted piperidines (1), piperazines (2) and tetrahydroisoquinolines (3) has been developed.     

Novel Redox-Active Cyclophanes Based on 3,3'-Biindolizines: Synthesis and Chirality

The first compounds of a new series of redox-active cyclophanes were prepared by dehydrocyclization of bridged indolizines of type 1. The bridged dipyridino-compounds 2a and 2b obtained by reaction of 2 mol of lithiated alpha-picolines with dihalides were used as starting materials. Subsequent treatment of 2a,b with 2 mol of alpha-bromo ketones gave quaternary pyridinium halides. Ring closure in an alkaline medium (Chichibabin reaction) yielded the starting material for the synthesis of the macrocycles. Oxidative C-C coupling gave the diastereomeric cyclophanes of type 3. In all cases one pair of the enantiomers was obtained in excess. CV-investigations have shown that the main products are reversible redox systems. To clarify their conformations, compounds 3c, 3d/1, and3d/2 were subjected to X-ray analysis.     

Electroexcitation of nucleon resonances

In these lectures the status of electromagnetic excitation of nucleon resonances is reviewed and some of the open problems of the structure and spectroscopy of light-quark baryons are discussed. The basic formalism for describing electromagnetic processes is introduced but not derived.Lecture given at the 8th Summer School on Intermediate-Energy Physics: Hadron Dynamics at Low and Intermediate Energies, Prague, July 10–14, 1995.     

Asymptotic behavior of -semigroups in Banach spaces

We present optimal estimates for the asymptotic behavior of
strongly continuous semigroups in terms of growth abscissas of the resolvent function of the generator . In particular we give Ljapunov's classical stability condition a definite form for (infinite dimensional) abstract Cauchy problems: The abscissa of boundedness of equals the growth bound of the classical solutions of .

     

Single-crystal structures of polyphenylene dendrimers

A series of first-generation polyphenylene dendrimers based on three different cores were prepared by Diels-Alder cycloaddition and their single-crystal structures were determined. Consisting exclusively of interlocked, twisted phenyl rings, these polyphenylene nanostructures have exciting structural and dynamic properties. Single crystals of dendrimers, suitable for X-ray structure analysis, were grown from different solvent mixtures by slow evaporation at room temperature. It should be pointed out that one of the described polyphenylene dendrimers represents up to now the biggest oligophenylene nanostructure from which crystallographic data is available.     

Quantitative depth profiling in glow discharge spectroscopies – A new deconvolution technique to separate effects of an uneven erosion crater shape

An algorithm is presented as a concept for the quantification in direct current and radiofrequency glow discharge (GD) modes for GD optical emission spectroscopy. The algorithm is divided into excitation and sputtering part and thus it is possible to distinguish between the different excitation processes and to consider equivalent sputtering crater formations in both modes. Intensity-time profiles are affected corresponding to the method by several effects. One important effect is that sputtering occurs at a single time in different depths because of curved crater bottoms, this is usually called crater effect. The main purpose is to introduce an iterative deconvolution technique which for the quantification numerically takes into account the curved sputtering crater bottom. Input data for the deconvolution technique are the calibrated mass-time profile, the partial densities of the sample constituents and the measured final shape of the sputtering crater. Using a relatively simple model for ion sputtering the deconvolution technique improves iteratively the calculated layer structure by means of information on crater formation. The mathematical handling is illustrated for the quantification of a depth profile of a multilayer sample of ten 100 nm layers. The resulting concentration-depth profile reflects excellently the real elemental distribution of the multilayer system.     

Glow discharge mass spectrometry

Over the past twenty years or so, glow discharge mass spectrometry (GDMS) has become the industry standard for the analysis of trace elements in metals and semiconductors. A review of its history is followed by a picture of the present situation and a look to where the future may lie. Applications are summarised, including the ability of GDMS to offer depth-resolved data and non-conductor analysis, and the well-documented quantitative nature of the results is reviewed. The effects resulting from the physical properties of the analyte material are discussed at length. Finally, recent work such as fast flow sources and pulsed glow discharges is reviewed.