Tetrapyridoxycalix[4]arene and its copper(II) complex: an ionic crystal engineering tecton for self-inclusion polymers

The crystal structures of a tetradentate pyridylcalix[4]arene ligand and its first copper(II) complex are discussed. The metal free ligand is mainly self-assembled by dipole–dipole interactions and a combination of CH–N bonds and CH–π interactions. The corresponding copper(II) perchlorate complex exhibits a self-inclusion behaviour to supramolecular zig-zag polymers.     

Detector based on time-resolved ion-induced voltage in laser multiphoton ionization and laser-induced fluorescence

The time-resolved ion-induced voltages obtained from multiphoton ionization (MPI) in gases were applied, for the first time, together with time-resolved laser-induced fluorescence (TR-LIF) for fast detection of organic compounds in ambient air. The target compounds were polycyclic aromatic hydrocarbons (PAHs) and nitroaromatics. The concepts of the proposed method are presented and examined. It is shown that the MPI signals allow for estimation of the molecular weight, while the fluorescence data supply additional quantitative and qualitative information. A 3D data presentation is suggested for obtaining selectivity. The proposed dimensions are the MPI-based mass estimation, the maximum LIF wavelength and the measured fluorescence lifetime. Since all required data are acquired simultaneously and since the setup can be continuously operated, this analytical concept is suggested for on-line applications. The common air components are not ionized at the selected wavelengths and only the organic pollutants are detected under these conditions. Moreover, it is shown that the resonant MPI mode provides a certain level of selectivity. Therefore, this setup may become the basis of an air sniffer.     

Pyrimidine synthesis - A new method

A new one-step-method for the synthesis of 2-phenylpyrimidines of type I was developed by reacting benzotrichloride with various nitriles in the presence of aluminum chloride.     

The synthesis of (Z)-trisubstituted allylic alcohols by the selective 1,4-hydrogenation of dienol esters: improved synthesis of (-)-β-santalol

(E)-Trisubstituted allylic alcohols are commonly prepared from the corresponding (E)-enals, themselves readily accessible by a simple aldol condensation reaction. We demonstrate that these very same (E)-enals can be converted into (Z)-trisubstituted allylic acetates (and thus alcohols) by a ruthenium-catalyzed 1,4-hydrogenation of the corresponding dienol acetates. This simple solution to a long-lasting problem was applied to an industrially feasible synthesis of (-)-β-santalol.     

An iron-catalysed chemo- and regioselective tetrahydrofuran synthesis

An intermolecular ring expansion reaction of an aryl epoxide with several dienes, acrylates, enynes or styrenes under iron catalysis, generated tetrahydrofuran derivatives in a highly chemo- and regioselective fashion. The process could be used in an unprecedented way for the one step synthesis of racemic calyxolane A and calyxolane B with acceptable diastereoselectivity.     

Fatou Components of Attracting Skew-Products

We investigate the existence of wandering Fatou components for polynomial skew-products in two complex variables. In 2004, the non-existence of wandering domains near a super-attracting invariant fiber was shown in Lilov (Fatou theory in two dimensions, PhD thesis, University of Michigan, 2004). In 2014, it was shown in Astorg et al. (Ann Math, arXiv:1411.1188 [math.DS], 2014) that wandering domains can exist near a parabolic invariant fiber. In Peters and Vivas (Math Z, arXiv:1408.0498, 2014), the geometrically attracting case was studied, and we continue this study here. We prove the non-existence of wandering domains for subhyperbolic attracting skew-products; this class contains the maps studied in Peters and Vivas (Math Z, arXiv:1408.0498, 2014). Using expansion properties on the Julia set in the invariant fiber, we prove bounds on the rate of escape of critical orbits in almost all fibers. Our main tool in describing these critical orbits is a possibly singular linearization map of unstable manifolds.     

Optimising a general repair kit problem with a service constraint

Field services are a particular type of after-sales service performed at the customer’s location where technicians repair malfunctioning machines. The inventory decisions about which spare part types to take to the repair site and in what quantities is called the repair kit problem. This problem is characterized by an order-based performance measure since a customer is only satisfied when all required spare parts are available to fix the machine. As a result, the service level in the decision making process is defined as a job fill rate. In this paper we derive a closed-form expression for the expected service level and total costs for the repair kit problem in a general setting, where multiple units of each part type can be used in a multi-period problem. Such an all-or-nothing strategy is a new characteristic to investigate, but commonly used in practice. Namely, items are only taken from the inventory when all items to perform the repair are available in the right quantity. We develop a new algorithm to determine the contents of the repair kit both for a service and cost model while incorporating this new expression for the job fill rate. We show that the algorithm finds solutions which differ on average 0.2% from optimal costs. We perform a case study to test the performance of the algorithm in practice. Our approach results in service level improvements of more than 30% against similar holding costs.     

Effect of the shear layer on the etching behavior of 6060 aluminum extrusion alloys

The occurrence of preferential grain etching (PGE) during alkaline etching of aluminum extrusion alloys from the 6XXX series is often linked to the presence of certain impurity elements such as zinc, causing an undesired etching appearance. In the presented work, an additional culprit in this context is identified, which has not been investigated yet. A clear relation between PGE and the presence of a subsurface shear layer is identified for extruded Al 6060 alloys containing 0.02 and 0.06 wt% Zn. This shear layer can be distinguished from the bulk of the metal by its difference in crystallographic texture as visualized by electron backscatter diffraction (EBSD). For the Zn enriched alloy, the <111>//ND grains are etched away faster than grains with other orientations, resulting in the grainy appearance typical for PGE. Independent of the Zn content in the alloy, once the shear layer is removed and <111>//ND grains are practically absent on the new surface, the depths variations caused by preferential etching disappear. Instead, the surface of the alloy is attacked uniformly by the caustic etch bath.     

Scaling and mesostructure of Carbopol dispersions

Rheological measurements were performed on aqueous dispersions of two commercial crosslinked polymer microgels, Carbopol Ultrez 10 and Carbopol ETD 2050, prepared over a wide range of concentration and pH. For all concentrations studied, both the yield stress and the elastic modulus initially increased dramatically with pH and displayed broad peaks at intermediate pH. This is consistent with the onset of jamming of the Carbopol particles due to a rapid increase in particle size caused by osmotic swelling in the presence of NaOH. Scaling of both yield stress and elasticity with concentration was observed only at higher concentrations, which we believe indicates a change from a percolated structure at low volume fractions to a space filling network of compressed particles at high volume fractions. This model is supported by confocal microscopy of fluorescently dyed Carbopol dispersions.