Thorpe–Ingold Effect in Branch‐Selective Alkylation of Unactivated Aryl Fluorides

Presented herein is a general protocol for the alkylation of simple aryl fluorides with unbiased secondary Grignard reagents by means of nickel catalysis. This study revealed a general Thorpe–Ingold effect in the ligand backbone which confers a high degree of selectivity for the secondary carbon center in the C?C coupling event. This protocol is characterized by mild reaction conditions, robustness, and simplicity. Both electron‐rich and electron‐deficient aryl fluorides are suitable candidates in this transformation. Equally amenable are a variety of heterocycles, permitting the coupling without over alkylation at the electrophilic sites.     

A Simple Analytical Model for Predicting the Detectable Ion Current in Ion Mobility Spectrometry Using Corona Discharge Ionization Sources

Corona discharge ionization sources are often used in ion mobility spectrometers (IMS) when a non-radioactive ion source with high ion currents is required. Typically, the corona discharge is followed by a reaction region where analyte ions are formed from the reactant ions. In this work, we present a simple yet sufficiently accurate model for predicting the ion current available at the end of this reaction region when operating at reduced pressure as in High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) or most IMS-MS instruments. It yields excellent qualitative agreement with measurement results and is even able to calculate the ion current within an error of 15%. Additional interesting findings of this model are the ion current at the end of the reaction region being independent from the ion current generated by the corona discharge and the ion current in High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) growing quadratically when scaling down the length of the reaction region.

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Validation of a coupled FE-model for the simulation of methane oxidation via thermal imaging

To simulate the processes of methane oxidation in landfill cover layers, a new computational model was created. The purpose of the model is to allow a forecast on the performance of methanotrophic activity in landfill cover layers under changing environmental conditions. Therefore, a thermodynamic consistent model based on the well-known Theory of Porous Media (TPM) combined with the mixture theory was developed, which analyzes the relevant gas productions of methane, oxygen and carbon dioxide. Diffusion, advection and conversion processes are considered as well as the energy production during methane oxidation. With the help of the thermal imaging technique a new experimental setup was developed in order to validate the coupled model in terms of the heat generation. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hölder exponents and box dimension for self-affine fractal functions

We consider some self-affine fractal functions previously studied by Barnsleyet al. The graphs of these functions are invariant under certain affine scalings, and we extend their definition to allow the use of nonlinear scalings. The Hölder exponent,h, for these fractal functions is calculated and we show that there is a larger Hölder exponent,h , defined at almost every point (with respect to Lebesgue measure). For a class of such functions defined using linear affinities these exponents are related to the box dimensionD _B of the graph byh2–D _Bh .Communicated by Michael F. Barnsley.     

A shift sequence based approach for nurse scheduling and a new benchmark dataset

This paper investigates an adaptive constructive method for solving nurse rostering problems. The constraints considered in the problems are categorised into three classes: those that are sequence related, those that are nurse schedule related and those that are roster related. We propose a decomposition approach (to construct solutions) that consists of two stages: (1) to construct high quality sequences for nurses by only considering the sequence constraints, and (2) to iteratively construct schedules for nurses and the overall rosters, based on the sequences built and considering the schedule and roster constraints. In the second stage of the schedule construction, nurses are ordered and selected adaptively according to the quality of the schedules they were assigned to in the last iteration. Greedy local search is carried out during and after the roster construction, in order to improve the (partial) rosters built. We show that the local search heuristic during the roster construction can further improve the constructed solutions for the benchmark problems tested.     

Double Hall algebras and derived equivalences

We show that the reduced Drinfeld double of the Ringel-Hall algebra of a hereditary category is invariant under derived equivalences. By associating an explicit isomorphism to a given derived equivalence, we also extend the results of Burban and Schiffmann [5] and [006], Sevenhant and Van den Bergh (1999) [25], and Xiao and Yang (2001) [31].     

A Global Optimization Algorithm using Lagrangian Underestimates and the Interval Newton Method

Convex relaxations can be used to obtain lower bounds on the optimal objective function value of nonconvex quadratically constrained quadratic programs. However, for some problems, significantly better bounds can be obtained by minimizing the restricted Lagrangian function for a given estimate of the Lagrange multipliers. The difficulty in utilizing Lagrangian duality within a global optimization context is that the restricted Lagrangian is often nonconvex. Minimizing a convex underestimate of the restricted Lagrangian overcomes this difficulty and facilitates the use of Lagrangian duality within a global optimization framework. A branch-and-bound algorithm is presented that relies on these Lagrangian underestimates to provide lower bounds and on the interval Newton method to facilitate convergence in the neighborhood of the global solution. Computational results show that the algorithm compares favorably to the Reformulation–Linearization Technique for problems with a favorable structure.     

Novel approach for modelling of nanomachining using a mesh-less method

In this paper, a mesh-less method, called Smoothed Particle Hydrodynamics (SPH) is used to simulate the nanomachining operation in order to assist with the understanding of the fundamental mechanisms of nano scale material deformation and the characteristics of the post machined surface. An elasto-plastic nano-machining analysis is used to form a nano-groove using a conical tool on a copper specimen. The SPH solutions are validated against nano scale machining experiments conducted using a nanoindenter. The simulated results showed that the normal force is greater than the cutting force in this nano scale machining operation, which is consistent with the experimental results. Both the ploughing and cutting mechanisms were observed in these machining conditions and increased with the increase of the depth of cut. Moreover, the results reveal that the larger negative rake angle reduced the ploughing mechanism and caused higher residual stress and strain along the machined surface. Therefore, the effect of machining parameters on the nano deformation mechanism and the quality of the machined surface can be rapidly assessed using SPH.