A Missing Reaction Step in Dithiobenzoate-Mediated RAFT Polymerization

The debate on the mechanism of dithiobenzoate-mediated RAFT polymerization may be overcome by taking the so-called “missing step” reaction between a highly reactive propagating radical and the three-arm star-shaped product of the combination reaction of an intermediate RAFT radical and a propagating radical into account. The “missing step” reaction transforms a propagating radical and a not overly stable three-arm star species into a resonance-stabilized RAFT intermediate radical and a stable polymer molecule. The enormous driving force behind the “missing step” reaction is estimated via DFT calculations of reaction enthalpies and reaction free enthalpies.     

A Cross-Shaped Monomer as Building Block for Molecular Textiles

The exploration of new materials is timeless. Especially 2D-materials have gotten much interest in the last decades. This work proposes a new route towards a fascinating class of 2D materials: molecular textiles. The suggested bottom-up approach focuses on the 2D self-assembly of a cross-shaped monomer at the water/air interface. A 3D cross-shaped motive was designed, synthesized, and characterized, which exhibits the required structural features, i. e., static and dynamic control. Analysis of the cross-shaped motive by ¹H-NMR spectroscopy, X-ray structure, and chiral stationary phase HPLC proved the rigidity and stability of the system, and thus also its potential for the here suggested new strategy towards molecular textiles. Three variants of a Schiff-base precursor pair functionalized monomer were synthesized and characterized by ¹H-NMR spectroscopy, ¹³C-NMR spectroscopy, and mass spectrometry. Finally, the network formation of the monomer is shown to be triggered by deprotonation of its ammonium salt, corroborated with FT-IR analysis.     

Some heuristics about the ecosystem of mathematics research data

Like in other sciences, research data play a growing role in mathematics, but in contrast to classical objects like measurements in physics they are much more heterogeneous. They may take the shape of abstract objects like the collection of integer sequences in OEIS, algorithms and their implementations as mathematical software, libraries of test problems or statistical data. From an infrastructure viewpoint, which aims at sustainable and connected data repositories which facilitate researchers to use existing information efficiently, it is essential to define an appropriate framework that allows not just storage but also connection and retrieval of the various types of data. Recently, there have been promising attempts to define standards for mathematical software, but the general task remains a big challenge, which is also addressed within the recently initiated GDML working group of the IMU. This is especially important in the fields of applied mathematics where research is often connected to research data originating from applications. The goal of this talk is a first attempt to analyse the diverse ecosystem of research data based on reference data from zbMATH. This approach has worked quite well for mathematical software, resulting in the formation of the swMATH database. Though reference data involve always a bias, the collected information of about 16 million reference data in zbMATH may be useful to identify the recent needs of researchers in different fields pertaining mathematical research data, and we discuss several aspects of such an analysis. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Resorbable initiators for polymerizations of lactones

Numerous nontoxic (resorbable) salts were prepared from cations and anions belonging to the human metabolism, such as Na, K, Mg, Ca, Zn and Fe in combination with chloride, iodide, hydroxide, carbonate, acetate, stearate, glycolate, L‐lactate, D‐mandelate and various N‐substituted α‐amino acids. All these salts were used as initiators for polymerizations of L‐lactide in bulk at 100–180°C. Furthermore, Grignard reagents, hemin and hematin were included in this study. Zn L‐lactate was found to be the most useful initiator in terms of reactivity, maximum molecular weight of the isolated poly(L‐lactide) and its optical purity. Zn L‐lactate initiated copolymerizations of L‐lactide and glycolid or L‐lactide and ϵ‐caprolactone were also studied. Finally, first studies of the polymerization mechanism of zinc stearate and zin 2‐ethylhexanoate were performed. They suggest that zinc carboxylates combined with an alcohol as coinitiator form reactive zinc alkoxides which are the true initiators at temperatures < 150°C.