A combined molecular dynamics-phase-field modelling approach to fracture

In order to better understand and ease the determination of material and model parameters required for the macroscopic modelling of brittle fracture, a bottom-up comparative study between molecular dynamics (MD) simulations and the continuum phase-field modelling (PFM) is carried out. In particular, based on the MD simulations of fracture of a highly brittle material, a number of PFM parameters such as the width of the transition zone between the damaged and the undamaged material, the crack resistance and the elasticity modulus are estimated. This study opens the door for an efficient way for multi-scale modelling of fracture. To illustrate this approach, a comparative two-dimensional numerical initial-boundary-value problem (IBVP) for the highly brittle aragonite (CaCO₃) is presented. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Slow light with cavity electromagnetically induced transparency

We report an experimental observation of slow light propagation in cold Rb atoms exhibiting cavity electromagnetically induced transparency (EIT). The steep slope of the atomic dispersion manifested by EIT reduces the light group velocity. The cavity filtering and feedback further contribute to the slowdown and delay of the light pulse propagation. A combination of the cavity and the EIT atomic system significantly improves the performance of the slow light propagation. A propagation time delay of approximately 200 ns was observed in the cavity and Rb EIT system, which is approximately 70 times greater than the time delay calculated for the light pulse propagation through the same Rb EIT system without the cavity.     

Using the KKT matrix in an augmented Lagrangian SQP method for sparse constrained optimization

The augmented Lagrangian SQP subroutine OPALQP was originally designed for small-to-medium sized constrained optimization problems in which the main calculation on each iteration, the solution of a quadratic program, involves dense, rather than sparse, matrices. In this paper, we consider some reformulations of OPALQP which are better able to take advantage of sparsity in the objective function and constraints.The modified versions of OPALQP differ from the original in using sparse data structures for the Jacobian matrix of constraints and in replacing the dense quasi-Newton estimate of the inverse Hessian of the Lagrangian by a sparse approximation to the Hessian. We consider a very simple sparse update for estimating ² L and also investigate the benefits of using exact second derivatives, noting in the latter case that safeguards are needed to ensure that a suitable search direction is obtained when ² L is not positive definite on the null space of the active constraints.The authors are grateful to John Reid and Nick Gould of the Rutherford Appleton Laboratory for a number of helpful and interesting discussions. Thanks are also due to Laurence Dixon for comments which led to the clarification of some parts of the paper.This work has been partly supported by a CAPES Research Studentship funded by the Brazilian Government.     

Direct Aroylation of Olefins through a Cobalt/Photoredox-Catalyzed Decarboxylative and Dehydrogenative Coupling with α-Oxo Acids

A photoredox/cobalt dual catalytic procedure has been developed that allows benzoylation of olefins. Here the photoredox catalyst effects the decarboxylation of α-ketoacids to form benzoyl radicals. After addition of this radical to styrenes, the cobalt catalyst abstracts a H-atom. Hydrogen evolution from the putative cobalt hydride intermediate allows a Heck-like aroylation without the need for a stoichiometric oxidant. Mechanistic studies reveal that electronically different styrenes lead to a curved Hammett plot, thus suggesting a change in product-determining step in the catalytic mechanism.     

Organocatalysis applied to the ring‐opening polymerization of β‐lactones: A brief overview

Organocatalysis offers a number of prospects in the polymer community and presents advantages over metal based and bio‐organic methods. The use of organic molecules for performing chemical reactions is not a new concept, and any research into organocatalytic reactions builds on a respected history. Compared to the organocatalysis of large lactones, which began in the early 2000s, the examples presented here will demonstrate that few metal‐free initiating systems had been applied to β‐lactones well before the beginning of the current millennium. These metal‐free initiating systems present indisputable advantages over metal‐based processes. In the following paper, ring‐opening polymerizations (ROPs) of various β‐lactones for the preparation of poly(hydroxyalkanoate)s will be presented, as will the types of mechanisms involved, that is, zwitterionic and anionic, and cationic or supramolecular‐based ROPs. The advantages and drawbacks of the different technics will be discussed in the domain, which, for us, is important in the overall production of bioplastics. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 657–672     

Synchronized On/Off Switching of Four Binding Sites for Water in a Molecular Solomon Link

A molecular Solomon link adopts different conformations in acetonitrile ( 1 ) and in water ( 2 ). Contrary to expectations, the main driving force of the transformation is not the change in medium polarity, but the cooperative binding of about four molecules of water, forming a tiny droplet in the central cavity of 2 . Mechanistic studies reveal that the four binding sites can simultaneously switch between an inactive state (unable to bind water) and an active state (able to bind water) during the transformation. Spatial and temporal coordination of switching events is commonly observed in biological systems but has been rarely achieved in artificial systems. Here, the concerted activation of the four switchable sites is controlled by the topology of the whole molecule.     

Increasing specificity of tandem mass spectrometry by laser‐induced dissociation

Mass spectrometry offers an arsenal of tools for diverse proteomic investigations. This perspective article reviews some of the recent developments in the field of coupling laser‐induced dissociation with mass spectrometry (LID‐MS). Strategies involving labelling with a chromophore to induce specific photo‐absorption properties are considered, with a focus on specific amino acid derivatization. Some of the opportunities and challenges of LID‐MS after targeted labelling for increasing specificity in complex sample analysis are discussed.     

Chemo-Enzymatic Synthesis of S. mansoni O-Glycans and Their Evaluation as Ligands for C-Type Lectin Receptors MGL,DC-SIGN,and DC-SIGNR

Due to their interactions with C-type lectin receptors (CLRs), glycans from the helminth Schistosoma mansoni represent promising leads for treatment of autoimmune diseases, allergies or cancer. We chemo-enzymatically synthesized nine O-glycans based on the two predominant O-glycan cores observed in the infectious stages of schistosomiasis, the mucin core 2 and the S. mansoni core. The O-glycans were fucosylated next to a selection of N-glycans directly on a microarray slide using a recombinant fucosyltransferase and GDP-fucose or GDP-6-azidofucose as donor. Binding assays with fluorescently labelled human CLRs DC-SIGN, DC-SIGNR and MGL revealed the novel O-glycan O8 as the best ligand for MGL from our panel. Significant binding to DC-SIGN was also found for azido-fucosylated glycans. Contrasting binding specificities were observed between the monovalent carbohydrate recognition domain (CRD) and the tetravalent extracellular domain (ECD) of DC-SIGNR.