Structure and Mechanism of an Aspartimide‐Dependent Peptide Ligase in Human Legumain

Peptide ligases expand the repertoire of genetically encoded protein architectures by synthesizing new peptide bonds, energetically driven by ATP or NTPs. Here, we report the discovery of a genuine ligase activity in human legumain (AEP) which has important roles in immunity and tumor progression that were believed to be due to its established cysteine protease activity. Defying dogma, the ligase reaction is independent of the catalytic cysteine but exploits an endogenous energy reservoir that results from the conversion of a conserved aspartate to a metastable aspartimide. Legumain’s dual protease–ligase activities are pH‐ and thus localization controlled, dominating at acidic and neutral pH, respectively. Their relevance includes reversible on–off switching of cystatin inhibitors and enzyme (in)activation, and may affect the generation of three‐dimensional MHC epitopes. The aspartate–aspartimide (succinimide) pair represents a new paradigm of coupling endergonic reactions in ATP‐scarce environments.     

Porous and Shape‐Anisotropic Single Crystals of the Semiconductor Perovskite CH3NH3PbI3 from a Single‐Source Precursor

Significant progress in solar‐cell research is currently made by the development of metal–organic perovskites (MOPs) owing to their superior properties, such as high absorption coefficients and effective transport of photogenerated charges. As for other semiconductors, it is expected that the properties of MOPs may be significantly improved by a defined nanostructure. However, their chemical sensitivity (e.g., towards hydrolysis) prohibits the application of methods already known for the synthesis of other nanomaterials. A new and general method for the synthesis of various (CH₃NH₃)PbI₃ nanostructures from a novel single‐source precursor is presented. Nanoporous MOP single crystals are obtained by a crystal‐to‐crystal transformation that is accompanied by spinodal demixing of the triethylene glycol containing precursor structure. Selective binding of a capping agent can be used to tune the particle shape of the MOP nanocrystals.     

Selective Template Removal by Thermal Depolymerization to Obtain Mesostructured Molybdenum Oxycarbide

The carbon content of mesostructured organic‐inorganic hybrid material of a cylindrical block copolymer template of poly(2‐vinylpyridine)‐block‐poly(allyl methacrylate) (P2VP‐b‐PAMA) and ammonium paramolybdate (APM) could be reduced by thermal depolymerization. By calcination in vacuo at 320 °C the PAMA core can be completely removed while the remaining P2VP brush preserves the mesostructure. The P2VP‐APM composite can then be carburized in‐situ to MoO_xC_y in a second pyrolysis step without any additional carbon source but P2VP. The molybdenum oxycarbide nanotubes obtained, form hierarchically porous non‐woven structures, which were tested as catalyst in the decomposition of NH₃. They proved to be catalytically active at temperatures above 450 °C. The activation energy was estimated from an Arrhenius Plot to be 127 kJ · mol^–1.     

PPV Polymerization through the Gilch Route: Diradical Character of Monomers

Despite various studies on the polymerization of poly(p‐phenylene vinylene) (PPV) through different precursor routes, detailed mechanistic knowledge on the individual reaction steps and intermediates is still incomplete. The present study aims to gain more insight into the radical polymerization of PPV through the Gilch route. The initial steps of the polymerization involve the formation of a p‐quinodimethane intermediate, which spontaneously self‐initiates through a dimerization process leading to the formation of diradical species; chain propagation ensues on both sides of the diradical or chain termination occurs by the formation of side products, such as [2.2]paracyclophanes. Furthermore, different p‐quinodimethane systems were assessed with respect to the size of their aromatic core as well as the presence of heteroatoms in/on the conjugated system. The nature of the aromatic core and the specific substituents alter the electronic structure of the p‐quinodimethane monomers, affecting the mechanism of polymerization. The diradical character of the monomers has been investigated with several advanced methodologies, such as spin‐projected UHF, CASSCF, CASPT2, and DMRG calculations. It was shown that larger aromatic cores led to a higher diradical character in the monomers, which in turn is proposed to cause rapid initiation.     

Cell Decompositions of Quiver Flag Varieties for Nilpotent Representations of the Cyclic Quiver

Generalizing Schubert cells in type A and a cell decomposition of Springer fibres in type A found by L. Fresse we prove that varieties of complete flags in nilpotent representations of a cyclic quiver admit an affine cell decomposition parametrized by multi-tableaux. We show that they carry a torus operation with finitely many fixpoints. As an application of the cell decomposition we obtain a vector space basis of certain modules (for quiver Hecke algebras of nilpotent representations of this quiver), similar modules have been studied by Kato as analogues of standard modules.     

Flip or flop? Students’ perspectives of a flipped lecture in mathematics

This paper describes students’ perspectives of a one-off flipped lecture in a large undergraduate mathematics service course. The focus was on calculating matrix determinants and was designed specifically to introduce debate and argumentation into a mathematics lecture. The intention was to promote a deeper learning and understanding through engagement with the added hope of instilling some passion for the subject. During the lecture, students were asked to vote with their feet, literally moving around the lecture theatre to form groups according to their shared favourite technique for calculating matrix determinants. Group discussions were then followed by a whole class debate facilitated by the lecturers, before they wrapped up the lecture by resolving the professional disagreements that had come to light during the debate. Following the lecture, data on student perspectives was gathered using both surveys and focus groups. Within this paper, we share the data and reveal the interesting results that emerged from our analysis. Despite remaining unconvinced as to whether flipped lectures are better for learning, students reported greater engagement and increased understanding of the material covered.     

Aspects of computational homogenization in magneto-mechanics

In the present work, the behavior of heterogeneous magnetorheological elastomers undergoing large deformations under the action of magnetic fields is studied. First-order computational homogenization is used to derive the homogenized stresses and magnetic inductions of the macro-structure from the response of the underlying micro-structure. Different types of boundary conditions are applied to solve the micro problem where the constitutive law is assumed to be known. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Computational Homogenisation using Reduced-Order Modelling applied to Hyperelasticity

Within this study nonlinear reduced-order modelling for hyperelastic material is applied for the boundary value problem on the micro-scale which arises in the context of computational homogenisation. This involves the Proper Orthogonal Decomposition and the Discrete Empirical Interpolation Method for the nonlinear term. Considered error measures are the errors of the displacement field, the averaged stresses and the effective elasticity tensor. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)