Multi-train trajectory optimization for energy-efficient timetabling

This paper proposes a novel approach for energy-efficient timetabling by adjusting the running time allocation of given timetables using train trajectory optimization. The approach first converts the arrival and departure times to time window constraints in order to relax the given timetable. Then a train trajectory optimization method is developed to find optimal arrival/departure times and optimal energy-efficient speed profiles within the relaxed time windows. The proposed train trajectory optimization method includes two types, a single-train trajectory optimization (STTO), which focuses on optimizing individual train movements within the relaxed arrival and departure time windows, and a multi-train trajectory optimization (MTTO), which computes multi-train trajectories simultaneously with a shared objective of minimizing multi-train energy consumption and an additional target of eliminating conflicts between trains. The STTO and MTTO are re-formulated as a multiple-phase optimal control problem, which has the advantage of accurately incorporating varying gradients, curves and speed limits and different train routes. The multiple-phase optimal control problem is then solved by a pseudospectral method. The proposed approach is applied in case studies to fine-tune two timetables, for a single-track railway corridor and a double-track corridor of the Dutch railway. The results suggest that the proposed approach is able to improve the energy efficiency of a timetable.     

Binaural intelligibility prediction based on the speech transmission index

Although the speech transmission index (STI) is a well-accepted and standardized method for objective prediction of speech intelligibility in a wide range of environments and applications, it is essentially a monaural model. Advantages of binaural hearing in speech intelligibility are disregarded. In specific conditions, this leads to considerable mismatches between subjective intelligibility and the STI. A binaural version of the STI was developed based on interaural cross correlograms, which shows a considerably improved correspondence with subjective intelligibility in dichotic listening conditions. The new binaural STI is designed to be a relatively simple model, which adds only few parameters to the original standardized STI and changes none of the existing model parameters. For monaural conditions, the outcome is identical to the standardized STI. The new model was validated on a set of 39 dichotic listening conditions, featuring anechoic, classroom, listening room, and strongly echoic environments. For these 39 conditions, speech intelligibility [consonant-vowel-consonant (CVC) word score] and binaural STI were measured. On the basis of these conditions, the relation between binaural STI and CVC word scores closely matches the STI reference curve (standardized relation between STI and CVC word score) for monaural listening. A better-ear STI appears to perform quite well in relation to the binaural STI model; the monaural STI performs poorly in these cases.     

Ionization of methane in strong and ultrastrong relativistic fields

The photoionization of methane is reported for intensities up to 10(19) W/cm2 with linear and circular polarized light. While fragmental ions (e.g., CH3+, CH+, C+, C2+) created from 10(14) W/cm2 to 10(15) W/cm2 are formed by Coulomb explosion, ionization to form C3+ and C4+ involves Coulomb explosion and tunneling ionization. In ultrastrong fields, removal of a carbon K-shell electron from methane proceeds via tunneling and rescattering ionization, without the influence of molecular channels. Photoelectrons from methane at 10(19) W/cm2 extend up to kinetic energies of 0.6 MeV.     

Organometallic Polyelectrolytes: Synthesis,Characterization and Layer‐By‐Layer Deposition of Cationic Poly(ferrocenyl(3‐ammoniumpropyl)‐methylsilane)

The water soluble poly(ferrocenylsilane) polycation, poly(ferrocenyl(3‐ammoniumpropyl)methylsilane), was synthesized by transition metal‐catalyzed ring‐opening polymerization of the novel [1]ferrocenophane Fe(η‐C₅H₄)₂SiCH₃(CH₂)₃Cl and by subsequent side group modification. Amination of the chloropropyl moieties using potassium 1,1,3,3‐tetramethyldisilazide followed by acidic hydrolysis produced the polycation. The polycation was employed together with poly(sodium vinylsulfonate) in the electrostatic layer‐by‐layer self‐assembly process to form organometallic multilayers on quartz. The multilayer fabrication process was monitored using UV/Vis absorption spectroscopy and XPS.     

Metal-Free Electrocatalytic Diacetoxylation of Alkenes

1,2-Dioxygenation of alkenes leads to a structural motif ubiquitous in organic synthons, natural products and active pharmaceutical ingredients. Straightforward and green synthesis protocols starting from abundant raw materials are required for facile and sustainable access to these crucial moieties. Especially industrially abundant aliphatic alkenes have proven to be arduous substrates in sustainable 1,2-dioxygenation methods. Here, we report a highly efficient electrocatalytic diacetoxylation of alkenes under ambient conditions using a simple iodobenzene mediator and acetic acid as both the solvent and an atom-efficient reactant. This transition metal-free method is applicable to a wide range of alkenes, even challenging feedstock alkenes such as ethylene and propylene, with a broad functional group tolerance and excellent faradaic efficiencies up to 87 %. In addition, this protocol can be extrapolated to alkenoic acids, resulting in cyclization of the starting materials to valuable lactone derivatives. With aromatic alkenes, a competing mechanism of direct anodic oxidation exists which enables reaction under catalyst-free conditions. The synthetic method is extensively investigated with cyclic voltammetry.     

Electrochemical AFM on surface grafted poly(ferrocenylsilanes)

Ethylenesulfide and trimethylenesulfide end‐functionalized poly(ferrocenyldimethylsilanes) (ES‐PFS and TMS‐PFS) with different degrees of polymerization were prepared via anionic ring‐opening polymerization. Molecular characterization of ES‐PFS was carried out by using ¹H‐NMR, GPC, FTIR, and elemental analysis. Thin films of ES‐PFS were prepared by immersing gold(111) substrates into 1.0 mg/ml solutions of the polymers in toluene. The polymeric films were characterized by FTIR, XPS, and contact angle measurements. Thicknesses of the grafted films were measured by SPR. Thicknesses determined by SPR and the theoretically calculated values are in a reasonable agreement. The morphology of the films was studied by tapping mode AFM. The electrochemical behavior of the films was monitored by cyclic voltammetry (CV). CVs show two reversible redox peaks, indicating a stepwise oxidation of the iron atoms in the polymer chains. Scanning Electrochemical Force Microscopy (SEFM) allowed us to study in situ the morphological changes occurring in the film upon electrochemical oxidation or reduction. AFM images indicated that in the oxidized form the chains were stretched due to electrostatic repulsion.     

The Role of Cytochrome P450 AbyV in the Final Stages of Abyssomicin C Biosynthesis

Abyssomicin C and its atropisomer are potent inhibitors of bacterial folate metabolism. They possess complex polycyclic structures, and their biosynthesis has been shown to involve several unusual enzymatic transformations. Using a combination of synthesis and in vitro assays we reveal that AbyV, a cytochrome P450 enzyme from the aby gene cluster, catalyses a key late-stage epoxidation required for the installation of the characteristic ether-bridged core of abyssomicin C. The X-ray crystal structure of AbyV has been determined, which in combination with molecular dynamics simulations provides a structural framework for our functional data. This work demonstrates the power of combining selective carbon-13 labelling with NMR spectroscopy as a sensitive tool to interrogate enzyme-catalysed reactions in vitro with no need for purification.