2017, Cabrero-Antonino, Jose R., Adam, Rosa, Junge, Kathrin, Beller, Matthias

The direct CH-alkylation of indoles using carboxylic acids is presented for the first time. The catalytic system based on the combination of Co(acac)3 and 1,1,1-tris(diphenylphosphinomethyl)-ethane (Triphos, L1), in the presence of Al(OTf)3 as co-catalyst, is able to perform the reductive alkylation of 2-methyl-1H-indole with a wide range of carboxylic acids. The utility of the protocol was further demonstrated through the C3 alkylation of several substituted indole derivatives using acetic, phenylacetic or diphenylacetic acids. In addition, a careful selection of the reaction conditions allowed to perform the selective C3 alkenylation of some indole derivatives. Moreover, the alkenylation of C2 position of 3-methyl-1H-indole was also possible. Control experiments indicate that the aldehyde, in situ formed from the carboxylic acid hydrogenation, plays a central role in the overall process. This new protocol enables the direct functionalization of indoles with readily available and stable carboxylic acids using a non-precious metal based catalyst and hydrogen as reductant.

2020, Ma, Chao, Dong, Jingjin, Viviani, Marco, Tulini, Isotta, Pontillo, Nicola, Maity, Sourav, Zhou, Yu, Roos, Wouter H., Liu, Kai, Herrmann, Andreas, Portale, Giuseppe

Proton translocation enables important processes in nature and man-made technologies. However, controlling proton conduction and fabrication of devices exploiting biomaterials remains a challenge. Even more difficult is the design of protein-based bulk materials without any functional starting scaffold for further optimization. Here, we show the rational design of proton-conducting, protein materials exceeding reported proteinaceous systems. The carboxylic acid-rich structures were evolved step by step by exploring various sequences from intrinsically disordered coils over supercharged nanobarrels to hierarchically spider β sheet containing protein-supercharged polypeptide chimeras. The latter material is characterized by interconnected β sheet nanodomains decorated on their surface by carboxylic acid groups, forming self-supportive membranes and allowing for proton conduction in the hydrated state. The membranes showed an extraordinary proton conductivity of 18.5 ± 5 mS/cm at RH = 90%, one magnitude higher than other protein devices. This design paradigm offers great potential for bioprotonic device fabrication interfacing artificial and biological systems. Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

2012, Glampedaki, P., Calvimontes, A., Dutschk, V., Warmoeskerken, M.M.C.G.

A new approach to functionalize the surface of polyester textiles is described in this study. Functionalization was achieved by incorporating pH/temperature-responsive polyelectrolyte microgels into the textile surface layer using UV irradiation. The aim of functionalization was to regulate polyester wettability according to ambient conditions by imparting stimuli-responsiveness from the microgel to the textile itself. Microgels consisted of pH/thermo-responsive microparticles of poly(N-isopropylacrylamide- co-acrylic acid) either alone or complexed with the pH-responsive natural polysaccharide chitosan. Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy, ζ-potential measurements, and topographical analysis were used for surface characterization. Wettability of polyester textiles was assessed by dynamic wetting, water vapor transfer, and moisture regain measurements. One of the main findings showed that the polyester surface was rendered pH-responsive, both in acidic and alkaline pH region, owing to the microgel incorporation. With a marked relaxation in their structure and an increase in their microporosity, the functionalized textiles exhibited higher water vapor transfer rates both at 20 and 40 °C, and 65% relative humidity compared with the reference polyester. Also, at 40 °C, i.e., above the microgel Lower Critical Solution Temperature, the functionalized polyester textiles had lower moisture regains than the reference. Finally, the type of the incorporated microgel affected significantly the polyester total absorption times, with an up to 300% increase in one case and an up to 80% decrease in another case. These findings are promising for the development of functional textile materials with possible applications in biotechnology, technical, and protective clothing.

2016, Nisa, Riffat Un, Mahmood, Tariq, Ludwig, Ralf, Ayub, Khurshid

The mechanism of the Zn(II) catalyzed oxidation of benzylic alcohol to benzaldehyde and ester by H2O2 oxidant was investigated through density functional theory methods and compared with the similar oxidation mechanisms of other late transition metals. Both inner sphere and intermediate sphere mechanisms have been analyzed in the presence and absence of pyridine-2-carboxylic acid (ligand). An intermediate sphere mechanism involving the transfer of hydrogen from alcohol to H2O2 was found to be preferred over the competitive inner sphere mechanism involving β-hydride elimination. Kinetic barriers associated with the intermediate sphere mechanism are consistent with the experimental observations, suggesting that the intermediate sphere mechanism is a plausible mechanism under these reaction conditions. The oxidation of alcohols to aldehydes (first step) is kinetically more demanding than the oxidation of hemiacetals to esters (second step). Changing the oxidant to tert-butyl hydrogen peroxide (TBHP) increases the activation barrier for the oxidation of alcohol to aldehyde by 0.4 kcal mol−1, but decreases the activation barrier by 3.24 kcal mol−1 for oxidation of hemiacetal to ester. Replacement of zinc bromide with zinc iodide causes the second step to be more demanding than the first step. Pyridine-2-carboxylic acid ligand remarkably decreases the activation barriers for the intermediate sphere pathway, whereas a less pronounced inverse effect is estimated for the inner sphere mechanism.

2011, Müller, M., Keßler, B., Fröhlich, J., Poeschla, S., Torger, B.

In this contribution we outline polyelectrolyte (PEL) complex (PEC) nanoparticles, prepared by mixing solutions of the low cost PEL components poly(ethyleneimine) (PEI) and poly(acrylic acid) (PAC). It was found, that the size and internal structure of PEI/PAC particles can be regulated by process, media and structural parameters. Especially, mixing order, mixing ratio, PEL concentration, pH and molecular weight, were found to be sensible parameters to regulate the size (diameter) of spherical PEI/PAC nanoparticles, in the range between 80-1,000 nm, in a defined way. Finally, applications of dispersed PEI/PAC particles as additives for the paper making process, as well as for drug delivery, are outlined. PEI/PAC nanoparticles mixed directly on model cellulose film showed a higher adsorption level applying the mixing order 1. PAC 2. PEI compared to 1. PEI 2. PAC. Surface bound PEI/PAC nanoparticles were found to release a model drug compound and to stay immobilized due to the contact with the aqueous release medium.