Wasser‐ und Salzhaushalt im Gefüge zementgebundener Baustoffe – Modellierung der auftretenden Mechanismen

Water and Salt in the Pore Structure of Cementitious Building Materials – Modelling the mechanisms Moisture and salt penetration can lead to significant damage in reinforced concrete structures. Thus a realistic calculation of moisture and salt distributions in cementitious building materials is essential to estimate the service life of reinforced concrete structures. The main mechanisms and interactions affecting moisture and salt transport in cementitious building materials were observed and described mathematically with the aim of developing a numerical model. As well as the effect of salt on known moisture transport phenomena, the cause of the self‐sealing effect of concrete against penetrating water was investigated using nuclear magnetic resonance tomography (NMR) and gamma ray absorption. Based on the results, a model was developed which describes the capillary transport of moisture and salt in concrete taking the self‐sealing effect into account.     

Pyrazinium Salts as Efficient Organocatalysts of Mild Oxidations with Hydrogen Peroxide

A series of 3‐substituted pyrazinium tetrafluoroborates was prepared as simple analogues of flavinium salts which are efficient organocatalysts for oxidations with hydrogen peroxide. It was shown that pyrazinium derivatives with an electron‐withdrawing substituent catalyze mild oxidations of sulfides to sulfoxides and Baeyer–Villiger oxidations in a similar way to flavinium catalysts. The most reactive catalyst, 3‐cyanopyrazinium tetrafluoroborate, was efficiently employed in preparative sulfoxidations of aromatic and aliphatic sulfides as well as in Baeyer–Villiger oxidations of cyclobutanones. A proposed mechanism for the catalysis is based on the formation of pyrazine hydroperoxide which is the agent oxidizing the substrate.     

Non‐Racemic Halohydrins via Biocatalytic Hydrogen‐Transfer Reduction of Halo‐Ketones and One‐Pot Cascade Reaction to Enantiopure Epoxides

Biocatalytic hydrogen‐transfer reduction of α‐chloro‐ketones furnished non‐racemic chlorohydrins by employing either Rhodococcus ruber as lyophilized cell catalyst or an alcohol dehydrogenase preparation from Pseudomonas fluorescens DSM 50106 (PF‐ADH). For all substrates investigated, Rhodococcus ruber gave strictly the “Prelog” product, whereas PF‐ADH showed scattered stereopreference. One possibility for a follow‐up reaction of halohydrins is the ring closure to the corresponding epoxide. A novel “one pot‐one step strategy” was employed to obtain the enantiopure epoxide from the α‐chloro‐ketone in a cascade like fashion at pH>12 involving biocatalytic hydrogen transfer reduction and in situ chemo‐catalyzed ring closure.     

An Advanced ‘clickECM’ That Can be Modified by the Inverse-Electron-Demand Diels-Alder Reaction

The extracellular matrix (ECM) represents the natural environment of cells in tissue and therefore is a promising biomaterial in a variety of applications. Depending on the purpose, it is necessary to equip the ECM with specific addressable functional groups for further modification with bioactive molecules, for controllable cross-linking and/or covalent binding to surfaces. Metabolic glycoengineering (MGE) enables the specific modification of the ECM with such functional groups without affecting the native structure of the ECM. In a previous approach (S. M. Ruff, S. Keller, D. E. Wieland, V. Wittmann, G. E. M. Tovar, M. Bach, P. J. Kluger, Acta Biomater. 2017 , 52, 159–170), we demonstrated the modification of an ECM with azido groups, which can be addressed by bioorthogonal copper-catalyzed azide-alkyne cycloaddition (CuAAC). Here, we demonstrate the modification of an ECM with dienophiles (terminal alkenes, cyclopropene), which can be addressed by an inverse-electron-demand Diels-Alder (IEDDA) reaction. This reaction is cell friendly as there are no cytotoxic catalysts needed. We show the equipment of the ECM with a bioactive molecule (enzyme) and prove that the functional groups do not influence cellular behavior. Thus, this new material has great potential for use as a biomaterial, which can be individually modified in a wide range of applications.