Column generation for vehicle routing problems with multiple synchronization constraints

Synchronization of workers and vehicles plays a major role in many industries such as logistics, healthcare or airport ground handling. In this paper, we focus on operational ground handling planning and model it as an archetype of vehicle routing problems with multiple synchronization constraints, coined as “abstract vehicle routing problem with worker and vehicle synchronization” (AVRPWVS). The AVRPWVS deals with routing workers to ground handling jobs such as unloading baggage or refuelling an aircraft, while meeting each job’s time window. Moreover, each job can be performed by a variable number of workers. As airports span vast distances and due to security regulations, workers use vehicles to travel between locations. Furthermore, each vehicle, moved by a driver, can carry several workers. We propose two mathematical multi-commodity flow formulations based on time-space networks to efficiently model five synchronization types including movement and load synchronization. Moreover, we develop a branch-and-price heuristic that employs both conventional variable branching and a novel variable fixing strategy. We demonstrate that the procedure achieves results close to the optimal solution in short time when compared to the two integer models.     

Solution-processed anodes from layer-structure materials for high-efficiency polymer light-emitting diodes

The development of low-cost, large-area electronic applications requires the deposition of active materials in simple and inexpensive techniques at room temperature, properties usually associated with polymer films. In this study, we demonstrate the integration of solution-processed inorganic films in light-emitting diodes. The layered transition metal dichalcogenide (LTMDC) films are deposited through Li intercalation and exfoliation in aqueous solution and partially oxidized in an oxygen plasma generator. The chemical composition and thickness of the LTMDC and corresponding transition metal oxide (TMO) films are investigated by X-ray photoelectron spectroscopy. The morphology and topography of the films are studied by atomic force microscopy. X-ray powder diffraction is used to determine the orientation of the LTMDC film. Finally, the LTMDC and their corresponding oxides are utilized as hole-injecting and electron-blocking materials in polymer light-emitting diodes with the general structure ITO/LTMDC/TMO/polyfluorene/Ca/Al. Efficient hole injection and electron blocking by the inorganic layers result in outstanding device performance and high efficiency.     

Die vielen Gesichter des Poly(ethylenglykol)s

Today, a life without poly(ethylene glycol) is hardly imaginable. One encounters PEG in nearly every aspect of our daily needs: from cosmetics to hairstyling products and from medicines to food. Even in maritime military technology and the preservation of recovered cultural possessions PEG can be found. This article deals with the synthesis, the surprising properties, and the application of this structurally simple yet fascinating and important polymer.     

Pathways of Enzymatic Phosphotransfer Reactions

Abstract

Mevalonate 5-pyrophosphate (MVAPP) decarboxylase catalyzes the decarboxylation of MVAPP to isopentenyl pyro-phosphate, an ATP-dependent process in which 3-phospho-MVAPP is a transient intermediate that undergoes concomitant decarboxylation and elimination of phosphate. Reaction of (S_p)-adenosine 5′-0-3-thio [3-17_{O 2},180] triphosphate in place of ATP produces (R)-[17O,18O] thiophosphate in place of phosphate. Therefore, the phosphotransfer step producing 3-phospho-MVAPP proceeds with inversion of configuration at P. Gentamicin nucleotidyl-transferase catalyzes the reaction of ATP with the C-2″ hydroxyl group of aminoglycoside antibiotics to produce AMP-2″-aminoglycosides, thereby inactivating the drugs. Enzymatic reaction of (S_p)-2′-deoxyadenosine 5′-O[α-17O] triphosphate with tobramycin produces (R_p)-[α-17O]dAMP-2″-tobramycin. Therefore, transfer of the 2′-deoxyadenosine 5′-phosphoryl group proceeds with inversion of configuration. Since both reactions are uncomplicated bisubstrate processes and both proceed with inversion at P, it is likely that both proceed by mechanisms involving direct, single-step phosphotransfer from the phospho-donor substrate to the acceptor, rather than by double-displacement mechanisms involving covalent, phosphoenzyme-intermediates.     

Self-Assembly and Fluorescence of Tetracationic Liquid Crystalline Tetraphenylethene

A series of tetraguanidinium tetraphenylethene (TPE) arylsulfonates with different chain lengths was prepared via ionic self-assembly of tetraguanidinium TPE chloride and the respective methyl arylsulfonates. Liquid crystalline properties were studied by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. Tetraguanidinium TPE arylsulfonates with chain lengths of C₈–C₁₂ displayed hexagonal columnar mesophases over a broad temperature range, while derivatives with longer chains showed oblique columnar phases. In solution all compounds displayed aggregation-induced emission behaviour. Temperature-dependent luminescence spectra of the bulk phase of the tetraguanidinium TPE arylsulfonate with C₁₄ side chains revealed a strong luminescence both in the solid state and the oblique columnar mesophase. The emission behaviour was rationalized by a unique combination of restriction of intramolecular rotation of the TPE core, Coulomb interaction between the guanidinium cations and π–π interactions of the anionic arylsulfonate moieties.     

Form fluctuations of carbosilane dendrimers in dilute solution: a study using neutron spin echo spectroscopy

A series of carbosilane dendrimers with perfluorinated end groups has been prepared. The structure of these molecules in dilute solution is studied using small angle neutron scattering. For generations g<3 we find a non-spherical shape of the particles and a tendency for aggregation. This result is supported by the analysis of the diffusion coefficient obtained from photon correlation spectroscopy. The overall shape of the molecules is that of a core-shell particle. The generation 4 molecule is obtained as a compact sphere. Neutron spin echo spectroscopy reveals a relaxation time which is attributed to the form fluctuations of this particle.     

Linear-dendritic nonionic poly(propylene oxide)-polyglycerol surfactants

A new type of linear-hyperbranched surfactant has been prepared by anionic ring-opening multibranching polymerization of glycidol onto an end-functional poly(propylene oxide) (PPO) macroinitiator. A hyperbranched, highly hydrophilic polyglycerol block is obtained as the polar segment of the structure. Molecular weights of the nonionic amphiphiles obtained were in the range of 390 to 8,600 g/mol. For comparison, initiators bearing a C16 alkyl chain have also been employed. Furthermore, hyperbranched polyglycerol homopolymers were investigated with respect to amphiphilic properties. All linear-dendritic amphiphiles have been characterized by SEC, DSC, ¹³C and ¹H NMR spectroscopy. A fluorescence-probe technique based on diphenyl hexatriene (DPH) as probe molecule was employed to determine the CMC (critical micelle concentration) of the samples in water. CMCs varied from 7.5×10⁻⁶ to 1.7×10⁻³ M and were found to depend on the copolymer architecture and the hydrophilic/hydrophobic balance. Measurements at pH 6.75 and 3.00 revealed an increase of the CMC by a factor of 10 for the amine containing copolymers upon lowering of the pH.     

Enantiodivergent [4+2] Cycloaddition of Dienolates by Polyfunctional Lewis Acid/Zwitterion Catalysis

Diels–Alder reactions have become established as one of the most effective ways to prepare stereochemically complex six-membered rings. Different catalysis concepts have been reported, including dienophile activation by Lewis acids or H-bond donors and diene activation by bases. Herein we report a new concept, in which an acidic prodiene is acidified by a Lewis acid to facilitate deprotonation by an imidazolium–aryloxide entity within a polyfunctional catalyst. A metal dienolate is thus formed, while an imidazolium–ArOH moiety probably forms hydrogen bonds with the dienophile. The catalyst type, readily prepared in few steps in high overall yield, was applied to 3-hydroxy-2-pyrone and 3-hydroxy-2-pyridone as well as cyclopentenone prodienes. Maleimide, maleic anhydride, and nitroolefin dienophiles were employed. Kinetic, spectroscopic, and control experiments support a cooperative mode of action. High enantioselectivity was observed even with unprecedented TONs of up to 3680.