A Water-Soluble Iridium Photocatalyst for Chemical Modification of Dehydroalanines in Peptides and Proteins

Dehydroalanine (Dha) residues are attractive noncanonical amino acids that occur naturally in ribosomally synthesised and post-translationally modified peptides (RiPPs). Dha residues are attractive targets for selective late-stage modification of these complex biomolecules. In this work, we show the selective photocatalytic modification of dehydroalanine residues in the antimicrobial peptide nisin and in the proteins small ubiquitin-like modifier (SUMO) and superfolder green fluorescent protein (sfGFP). For this purpose, a new water-soluble iridium(III) photoredox catalyst was used. The design and synthesis of this new photocatalyst, [Ir(dF(CF₃)ppy)₂(dNMe₃bpy)]Cl₃, is presented. In contrast to commonly used iridium photocatalysts, this complex is highly water soluble and allows peptides and proteins to be modified in water and aqueous solvents under physiologically relevant conditions, with short reaction times and with low reagent and catalyst loadings. This work suggests that photoredox catalysis using this newly designed catalyst is a promising strategy to modify dehydroalanine-containing natural products and thus could have great potential for novel bioconjugation strategies.     

Light‐induced degradation of PECVD aluminium oxide passivated silicon solar cells

Light‐induced degradation (LID) has been identified to be a critical issue for solar cells processed on boron‐doped silicon substrates. Typically, Czochralski‐grown silicon (Cz‐Si) has been reported to suffer from stronger LID than block‐cast multicrystalline silicon (mc‐Si) due to higher oxygen concentrations. This work investigates LID under conditions practically relevant under module operation on different cell types. It is shown that aluminium oxide (AlOx) passivated mc‐Si solar cells degrade more than a reference aluminium back surface field mc‐Si cell and, remarkably, an AlOx passivated Cz‐Si solar cell. The defect which is activated by illumination is shown to be doubtful a sole bulk effect while the AlOx passivation might play a certain role. This work may contribute to a re‐evaluation of the suitability of boron‐doped Cz‐ and mc‐Si for solar cells with very high efficiencies. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Nonlinear Stability of Homogeneous Models in Newtonian Cosmology

We consider the Vlasov‐Poisson system in a cosmological setting as studied in [18] and prove nonlinear stability of homogeneous solutions against small, spatially periodic perturbations in the L ^∞‐norm of the spatial mass density. This result is connected with the question of how large scale structures such as galaxies have evolved out of the homogeneous state of the early universe. (Accepted June 28, 1996)     

Coupling between experimental measurements and polycrystal finite element calculations for micromechanical study of metallic materials

This paper presents a methodology for multiscale coupling between the morphology and texture of a microstructure as has been characterised experimentally, and the results of mechanical strain field analysis. This methodology is based on a coupling between experimental characterisation of the microstructure, in situ and/or ex situ mechanical tests, local strain field measurements performed at the grain scale, and finite element simulations. First, with orientation imaging microscopy, a map of the microstructure is generated that can be meshed. Then, finite element calculations are carried out on this mesh, using a constitutive law which takes into account the crystallographic orientation of each grain, as has been determined by the orientation imaging itself. These numerical results are then compared to the experimental strain field as obtained by digital image correlation at the scale of the grains.     

High pressure differential thermal analysis of nematic compounds with different molecular shapes

Abstract

By means of high pressure differential thermal analysis we measured the pressure/temperature phase diagrams of several nematic compounds with different molecular structures. Using pressures up to about 500 M Pa we found strongly nonlinear clearing curves. This behaviour is interpreted as changes from ‘weak’ intermolecular potentials to ‘hard’ potentials, or using thermodynarmic arguments, strong pressure dependence of the volume discontinuity at the clearing transitions.     

Inter-laboratory exercise with an aim to compare methods for 90Sr and 239,240Pu determination in environmental soil samples

In order to deliver reliable results for a multitude of different scenarios, e.g. emergency preparedness, environmental monitoring, nuclear decommissioning and waste management, there is a constant process of method development in the field of radioanalytical chemistry. This work presents the results of a method comparison exercise aimed at quantifying ⁹⁰Sr and ^239,240Pu in environmental soil samples, with the intention of evaluating the performance and applicability of different methods. From the methods examined in this work, recommendations are given in order to find a radioanalytical measurement procedure, for ⁹⁰Sr and ^239,240Pu analysis, which is fit-for-purpose for a particular scenario.

     

Click‐chemistry of polymersomes on nanoporous polymeric surfaces

A facile click chemistry method of immobilizing surface‐functionalized polymer vesicles on casted polymeric PAN substrates is described. Microporous PAN membranes were subjected to hydrochloric acid hydrolysis to obtain surface carboxylates. The carboxylic groups were activated with EDC/NHS‐solution and were then reacted with propargylamine to introduce alkyne groups for CuAAC reactions. The alkyne functionality of the modified membrane surface was verified by reaction with an azide functional click dye both before and after the immobilization of azide‐functionalized ABA vesicles. The efficient postfunctionalization of the membrane with alkyne allowed quantitative coverage of the membrane surface with a polymersome monolayer, as confirmed by immobilization of polymerzomes loaded with a fluorescent dye. Polymersome monolayers immobilized on alkyne functionalized PAN‐membranes were characterized by cryo‐SEM and monolayers were confirmed by atom force microscopy. These methods opens up new avenues for preparing membrane based filtration and sensor technologies. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2032–2039