Steady Flows of Shear-Dependent Oldroyd-B Fluids around an Obstacle

This work is concerned with the study of steady flows of an incompressible viscoelastic fluid of Oldroyd type, with viscosity depending on the second invariant of the rate of deformation tensor in an exterior domain. We establish a result of existence and uniqueness of strong solutions for sufficiently small data and give estimates relating these solutions to those of the corresponding generalized Newtonian fluid.     

The Trifluoromethyl Anion

First evidence for the existence of free trifluoromethyl anion CF₃^? has been obtained. The 3D‐caged potassium cation in [K(crypt‐222)]⁺ is inaccessible to CF₃^?, thus rendering it uncoordinated (“naked”). Ionic [K(crypt‐222)]⁺ CF₃^? has been characterized by single‐crystal X‐ray diffraction, solution NMR spectroscopy, DFT calculations, and reactivity toward electrophiles.     

Highly Chemoselective Catalytic Coupling of Substituted Oxetanes and Carbon Dioxide

The chemoselective coupling of oxetanes and carbon dioxide to afford functional, heterocyclic organic compounds known as six‐membered cyclic carbonates remains a challenging topic. Here, an effective method for their synthesis relying on the use of Al catalysis is described. The catalytic reactions can be carried out with excellent selectivity for the cyclic carbonate product tolerating various (functional) groups present in the 2‐ and 3‐position(s) of the oxetane ring. The presented methodology is the first general approach towards the formation of six‐membered cyclic carbonates (6MCCs) through oxetane/CO₂ coupling chemistry. Apart from a series of substituted six‐membered cyclic carbonates, also the unprecedented room‐temperature coupling of oxetanes and CO₂ is disclosed giving, depending on the structural features of the substrate, a variety of five‐ and six‐membered heterocyclic products. A mechanistic rationale is presented for their formation and support for the intermediary presence of a carbonic acid derivative is given. The presented functional carbonates may hold great promise as building blocks in organic synthesis and the development of new, biodegradable polymers.     

Thionation of a cyanoxime derivative to form the sulphur-containing derivative,a novel ligand for complexation with transitional metal ions

Structural Chemistry - 2-Cyano-2-(hydroxyimino)dithioacetic acid was prepared starting from cyanoacetic acid methylester via 2-cyano-2-(hydroxyimino)acetic acid methylester. Before thionation, the...     

Autoregressive functions estimation in nonlinear bifurcating autoregressive models

Bifurcating autoregressive processes, which can be seen as an adaptation of autoregressive processes for a binary tree structure, have been extensively studied during the last decade in a parametric context. In this work we do not specify any a priori form for the two autoregressive functions and we use nonparametric techniques. We investigate both nonasymptotic and asymptotic behaviour of the Nadaraya–Watson type estimators of the autoregressive functions. We build our estimators observing the process on a finite subtree denoted by \(\mathbb {T}_n\), up to the depth n. Estimators achieve the classical rate \(|\mathbb {T}_n|^{-\beta /(2\beta +1)}\) in quadratic loss over Hölder classes of smoothness. We prove almost sure convergence, asymptotic normality giving the bias expression when choosing the optimal bandwidth. Finally, we address the question of asymmetry: we develop an asymptotic test for the equality of the two autoregressive functions which we implement both on simulated and real data.     

State-dependent importance sampling schemes via minimum cross-entropy

We present a method to obtain state- and time-dependent importance sampling estimators by repeatedly solving a minimum cross-entropy (MCE) program as the simulation progresses. This MCE-based approach lends a foundation to the natural notion to stop changing the measure when it is no longer needed. We use this method to obtain a state- and time-dependent estimator for the one-tailed probability of a light-tailed i.i.d. sum that is logarithmically efficient in general and strongly efficient when the jumps are Gaussian. We go on to construct an estimator for the two-tailed problem which is shown to be similarly efficient. We consider minor variants of the algorithm obtained via MCE, and present some numerical comparisons between our algorithms and others from the literature.     

Multi-stage solvers optimized for damping and propagation

Explicit multi-stage solvers are routinely used to solve the semi-discretized equations that arise in Computational Fluid Dynamics (CFD) problems. Often they are used in combination with multi-grid methods. In that case, the role of the multi-stage solver is to efficiently reduce the high frequency modes on the current grid and is called a smoother. In the past, when optimizing the coefficients of the scheme, only the damping characteristics of the smoother were taken into account and the interaction with the remainder of the multi-grid cycle was neglected. Recently it had been found that coefficients that result in less damping, but allow for a higher Courant-Friedrichs-Lewy (CFL) number are often superior to schemes that try to optimize damping alone. While this is certainly true for multi-stage schemes used as a stand-alone solver, we investigate in this paper if using higher CFL numbers also yields better results in a multi-grid setting. We compare the results with a previous study we conducted and where a more accurate model of the multi-grid cycle was used to optimize the various parameters of the solver.We show that the use of the more accurate model results in better coefficients and that in a multi-grid setting propagation is of little importance.We also look into the gains to be made when we allow the parameters to be different for the pre- and post-smoother and show that even better coefficients can be found in this way.