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. 相似文献
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. 相似文献
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.
Kernel functions play an important role in defining new search directions for primal-dual interior-point algorithm for solving linear optimization problems. In this paper we present a new kernel function which yields an algorithm with the best known complexity bound for both large- and small-update methods. 相似文献
In this work, we have assessed the results of the local and nonlocal versions of Rousselier’s damage model, which have been used here for simulation of ductile crack growth. There are several issues regarding the accuracy of the results which has been addressed in this paper, e.g., accuracy in simulation of crack path, extent and width of the damaged region, fracture resistance behaviour in situations such as symmetric vs. non-symmetric boundary-value problems, mixed-mode loading vs. mode-I loading of the crack-tip, etc. It was also observed that the shape and orientation of the elements at the crack-tip, in addition to their size, influence the results of the local damage model. In this work, it was shown that the above issues can be resolved through the use of nonlocal damage models. The predictions of the nonlocal model are also consistent with the experimental observations unlike its local counterpart. Several examples were presented, where the results as obtained by both the local and nonlocal models were compared. From this experience, it is recommended that the local damage models should not be used blindly by the analysts for all kinds of mesh design, loading, boundary conditions, etc. 相似文献
Abstract The synthesis of a variety of substituted bisphenol A polysulfones, including nitro, amino, aminomethyl, ethyl, and methyl derivatives, is described. Nuclear magnetic resonance (NMR) (both proton and carbon, and several 2-D experiments) data confirm conclusions on the substitution site based on arguments on inductive effects in the phenyl rings. The proton ortho to the oxygen in the bisphenol A (BPA) residue is replaced in electrophilic substitution reactions. The degree of substitution was also calculated from the NMR results. The ethyl and methyl derivatives were expected, from the starting reactants, to each have a BPA ring substituted. The NMR data showed that, on the average, this is true. The nitro derivative also has substitution in every BPA ring, while the amino and aminomethyl derivatives have only intermittent BPA rings substituted. Measured degrees of substitution (DS) varied from 0.11 to 2.25. 相似文献
β-Amino ester enolate reacts readily with selected aldehydes and ketones. Deprotection via the N-oxide provides good yields of the 2-substituted acrylate ester. 相似文献