Selbstheilende Polymere

Even though the field of self‐healing is rarely known so far – self healing materials are already present at our market. Nevertheless just due to modern scientific concepts we are now able to understand the basic mechanistic steps in a more detailed way. Further progress on this field will open access to materials with a wide range of adjustable properties. Therefore, applications of such self healing materials are not limited – assuming the market‐price is competitive and the elongated lifetime delivers an appropriate advantage. Already demonstrated for concrete and clear coatings for cars, the investigations done so far have generated materials with improved properties and prolonged durability.     

Bis-Cyclometalated Indazole Chiral-at-Rhodium Catalyst for Asymmetric Photoredox Cyanoalkylations

A new class of bis-cyclometalated rhodium(III) catalysts containing two inert cyclometalated 6-tert-butyl-2-phenyl-2H-indazole ligands and two labile acetonitriles is introduced. Single enantiomers (>99 % ee) were obtained through a chiral-auxiliary-mediated approach using a monofluorinated salicyloxazoline. The new chiral-at-metal complex is capable of catalyzing the visible-light-induced enantioselective α-cyanoalkylation of 2-acyl imidazoles in which it serves a dual function as the chiral Lewis acid catalyst for the asymmetric radical chemistry and at the same time as the photoredox catalyst for the visible-light-induced redox chemistry (up to 80 % yield, 4:1 d.r., and 95 % ee, 12 examples).     

Mixed ab initio QM/MM modeling using frozen orbitals and tests with alanine dipeptide and tetrapeptide

Methodology is discussed for mixed ab initio quantum mechanics/molecular mechanics modeling of systems where the quantum mechanics (QM) and molecular mechanics (MM) regions are within the same molecule. The ab initio QM calculations are at the restricted Hartree–Fock level using the pseudospectral method of the Jaguar program while the MM part is treated with the OPLS force fields implemented in the IMPACT program. The interface between the QM and MM regions, in particular, is elaborated upon, as it is dealt with by “breaking” bonds at the boundaries and using Boys-localized orbitals found from model molecules in place of the bonds. These orbitals are kept frozen during QM calculations. Results from tests of the method to find relative conformational energies and geometries of alanine dipeptides and alanine tetrapeptides are presented along with comparisons to pure QM and pure MM calculations. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1468–1494, 1999     

Increased structural complexity leads to higher activity: peptides as efficient and versatile catalysts for asymmetric aldol reactions

[reaction: see text] Peptides containing a secondary amine and a carboxylic acid in a specific orientation to each other are presented as highly efficient catalysts for asymmetric aldol reactions: (1) their activity is considerably higher compared to that of proline, and (2) the enantioselectivity of the peptidic catalysts can be changed from (R)- to (S)-selectivity by simple modifications of the secondary structure.     

In Situ Grignard Metalation Method for the Synthesis of Hauser Bases

The in situ Grignard Metalation Method (iGMM) is a straightforward one-pot procedure to quickly produce multigram amounts of Hauser bases R₂N-MgBr which are valuable and vastly used metalation reagents and novel electrolytes for magnesium batteries. During addition of bromoethane to a suspension of Mg metal and secondary amine at room temperature in an ethereal solvent, a smooth reaction yields R₂N-MgBr under evolution of ethane within a few hours. A Schlenk equilibrium is operative, interconverting the Hauser bases into their solvated homoleptic congeners Mg(NR₂)₂ and MgBr₂ depending on the solvent. Scope and preconditions are studied, and side reactions limiting the yield have been investigated. DOSY NMR experiments and X-ray crystal structures of characteristic examples clarify aggregation in solution and the solid state.     

Optimizing the sputter deposition process of polymers for the Storing Matter technique using PMMA

Quantitative analyses in secondary ion mass spectrometry (SIMS) become possible only if ionization processes are controlled. The Storing Matter technique has been developed to circumvent this so‐called matrix effect, primarily for inorganic samples, but has also been extended to organic samples. For the latter, it has been applied to polystyrene in order to investigate the extent of damage in the polymer, its fragmentation during the sputter deposition process and the effect of the deposition process on the spectra taken by Time‐of‐Flight SIMS (ToF‐SIMS). In this work, a multi‐technique approach, which employs the Storing Matter technique for deposition and ToF‐SIMS and X‐ray photoelectron spectroscopy for characterization, is used to enhance the control of the deposition process, including the thickness of the deposit, the alteration of the source film and the influence of polymer composition on the Storing Matter process. Poly (methyl methacrylate) (PMMA) is used for this work. More detailed information about the sticking of polymer fragments on the metal collector is obtained by density functional theory calculations. This work allows for the conclusion that a part of the fragments deposited on the collector surface diffuses on the latter, reacts and recombines to form larger fragments. The behaviour observed for PMMA is similar to polystyrene, showing that oxygen has no major influence on the processes occurring during the sputter deposition process. Additionally, we have developed a new methodology using 2D ToF‐SIMS images of the deposit to monitor the deposit thickness and to identify surface contaminations. The latter are not only located at the position of the deposit but all over the collector surface. Copyright © 2016 John Wiley & Sons, Ltd.     

Two-dimensional condensation in camphor-10-sulphonic acid films at the mercury/electrolyte interface

The electrosorption properties of camphor-10-sulphonic acid (CS) in different electrolytes (Na₂SO₄, LiClO₄, KNO₃, KCl, KBr, KJ) were investigated experimentally by ac polarographic measurements at different temperatures. Depending on the type of electrolyte and on the temperature, film condensation was observed.The Frumkin interaction coefficient, determined from the critical degree of coverage, does not depend linearly on the reciprocal temperature as would be the case in correspondence to the temperature dependence of the pit width. This contradiction does not occur if the interaction coefficient is determined from the critical degree of coverage using the lattice gas model. The temperature dependence of the pit width of the differential capacity-potential curves, found in the experiment, can be theoretically described by both these models. The interaction coefficient in the models is inversely proportional to the temperature. Furthermore, the parameters of the standard free energy of adsorption, the interaction energy, the interaction coefficient of the Frumkin isotherm, the adsorption coefficient, and the maximal surface concentration of CS in the film were estimated and compared.