A tabu search heuristic for ship routing and scheduling with flexible cargo quantities

This paper presents a planning problem faced by many shipping companies dealing with the transport of bulk products. These shipping companies typically have a certain amount of contract cargoes that they are committed to carry, while trying to maximize their profit from optional spot cargoes. The cargo quantities are often flexible within an interval. Therefore, interwoven with the routing and scheduling decisions, the planner also has to decide the optimal cargo quantities. A tabu search algorithm embedding a specialized heuristic for deciding the optimal cargo quantities in each route is proposed to solve the problem. Computational results show that the heuristic gives optimal or near-optimal solutions to real-life cases of the problem within reasonable time. It is also shown that utilizing the flexibility in cargo quantities gives significantly improved solutions.     

Detailed in situ XRD and calorimetric study of the formation of silicate/mixed surfactant mesophases under alkaline conditions. Influence of surfactant chain length and synthesis temperature

The formation of mesoscopically ordered silica/surfactant composites under alkaline synthesis conditions has been studied by time-resolved in situ small-angle X-ray diffraction with synchrotron radiation. Alkyltrimethylammoniumbromide surfactants, C(n)()TAB, of different chain lengths (n = 14, 16, and 18) as well as mixtures thereof were used as structure directing agents and the measurements were carried out at two different temperatures. A linear relationship between the mean surfactant chain length and the d spacing of the hexagonal phase was observed, suggesting an ideal mixing of the surfactants in the supramolecular surfactant aggregates. It is shown that the formation of the hexagonal phase is kinetically controlled mainly by the rate of silicate condensation, while the effect of changes in the surfactant chain length on the kinetics is small under the studied conditions. Two concominant, albeit partly interlinked, processes, suggested being intra- and intermicellar condensation, followed by aggregate-aggregate condensation, govern the nucleation and growth of the hexagonal phase. The two-step mechanism is confirmed by a microcalorimetric study where the heat evolved during the hydrolysis-condensation reactions is followed as a function of time.     

Fluid self-diffusion in Scots pine sapwood tracheid cells

The self-diffusion coefficients of water and toluene in Scots pine sapwood was measured using low field pulsed field gradient nuclear magnetic resonance (PFG-NMR). Wood chips of 8 mm diameter were saturated with the respective liquids, and liquid self-diffusion was then traced in one dimension orthogonal to the tracheid cell walls in the wood's radial direction. The experimental echo attenuation curves were exponential, and characteristic self-diffusion coefficients were produced for diffusion times spanning from very short times to times on the order of magnitude of seconds. Observed self-diffusion coefficients were decaying asymptotically as a function of diffusion time, an effect which was ascribed to the cell walls' restriction on confined liquid diffusion. The observed self-diffusion behavior in Scots pine sapwood was compared to self-diffusion coefficients obtained from simulations of diffusion in a square. Principles of molecular displacements in confined geometries were used for elucidating the wood's cellular structure from the observed diffusion coefficients. The results were compared with a mathematical model for diffusion between parallel planes.     

Recombination and transport processes in dye-sensitized solar cells investigated under working conditions

The transport and recombination of electrons in dye-sensitized TiO(2) solar cells were studied by analysis of the current and voltage response to a small square-wave light-intensity modulation. Solar cells were studied under working conditions by using potentiostatic and galvanostatic conditions. An increase in applied voltage, that is, from 0 V toward open-circuit voltage, was found to lead to faster electron transport at low light intensities, while it slowed transport at higher light intensities. This observation seems to be conflicting with the multiple trapping model with diffusive transport. An effective diffusion length at the maximum power point was calculated, and it was shown that it decreases with increasing light intensity.     

C?H Activation of Benzene by a Photoactivated NiII(azide): Formation of a Transient Nickel Nitrido Complex

Photochemical activation of nickel‐azido complex 2 [Ni(N₃)(PNP)] (PN^HP=2,2′‐di(isopropylphosphino)‐4,4′‐ditolylamine) in neat benzene produces diamagnetic complex 3 [Ni(Ph)(PN^PN^H)], which is crystallographically characterized. DFT calculations support photoinitiated N₂‐loss of the azido complex to generate a rare, transient Ni^IV nitrido species, which bears significant nitridyl radical character. Subsequent trapping of this nitrido through insertion into the Ni P bond generates a coordinatively unsaturated Ni^II imidophosphorane PN donor. This species shows unprecedented reactivity toward 1,2‐addition of a C H bond of benzene to form 3 . The structurally characterized chlorido complex 4 [Ni(Cl)(PN^PN^H)] is generated by reaction of 3 with HCl or by direct photolysis of 2 in chlorobenzene. This is the first report of aromatic C H bond activation by a trapped transient nitrido species of a late transition metal.     

Engineering Crystals Using sp3-C Centred Tetrel Bonding Interactions

1,1,2,2-Tetracyanocyclopropane derivatives 1 and 2 were designed and synthesized to probe the utility of sp³-C centred tetrel bonding interactions in crystal engineering. The crystal packing of 1 and 2 and their 1,4-dioxane cocrystals is dominated by sp³-C(CN)₂⋅⋅⋅O interactions, has significant C⋅⋅⋅O van der Waals overlap (≤0.266 Å) and DFT calculations indicate interaction energies of up to −11.0 kcal mol⁻¹. A cocrystal of 2 with 1,4-thioxane reveals that the cyclopropane synthon prefers interacting with O over S. Computational analyses revealed that the electropositive C₂(CN)₄ pocket in 1 and 2 can be seen as a strongly directional ‘tetrel-bond donor’, similar to halogen bond or hydrogen bond donors. This disclosure is expected to have implications for the utility of such ‘tetrel bond donors’ in molecular disciplines such as crystal engineering, supramolecular chemistry, molecular recognition and medicinal chemistry.     

Relation Between Aggregation and Heterogeneity of Obtained Structure in Sol-Gel Derived CaO-P2O5-SiO2

Potentially bioactive sol-gel derived CaO-P2O5-SiO2 systems are studied and the influence of aggregation mechanism on the gel structure is discussed. A rheological measuring technique is used to monitor the aggregation process and the results are related to heterogeneity of the obtained gel structure. The results indicate that heterogeneity is produced in the sol-gel transition when calcium nitrate and phosphoric acid are used as precursors of CaO and P2O5. This destroys the correlation between bioactivity and the calcium and phosphorus content of the gel derived glasses.     

Platinum-catalyzed hydroformylation of terminal and internal octenes

A brief historic overview of Pt/Sn-catalyzed hydroformylation as well as recent advances in the hydroformylation of internal alkenes is provided. This serves as background for the results obtained with the [Pt(Sixantphos)Cl(2)] system, for which the molecular structure and the spectroscopic data are described. Insitu UV/Vis-spectroscopic studies have revealed rapid formation of the corresponding Pt-stannate complex upon reaction with SnCl(2), whereas high-pressure insitu IR-spectroscopy showed formation of a Pt-CO species and a short-lived Pt-H species under syngas, as well as rapid evolution of aldehyde product upon addition of 1-octene to the preformed catalyst in the IR autoclave. The hydroformylation of 1-octene and the i-octenes has been performed. For the internal alkenes, selective tandem isomerization/hydroformylation towards n-nonanal is observed with this catalyst system.     

Mixed electrolytes producing very weak electroacoustic signal

The electrokinetic potential of powders dispersed in concentrated solutions of salts can be determined by electroacoustic methods when the ESA (electrokinetic sonic amplitude) signal of electrolyte is properly corrected for. We propose an alternative solution to the problem of electroacoustic measurements at high ionic strengths; that is, the composition of mixed electrolytes with common ions can be adjusted to minimize the ESA signal of the electrolyte. The measurement of electrokinetic potential of powders dispersed in such mixed electrolytes does not require electrolyte background correction. Mixed electrolytes, which produce very weak ESA signals, were prepared from the following salts with common ions: Li+ (LiNO3 + LiCl), Na+ (NaNO3 + NaBr), K+ (KBr + KNO3), and NO(-)3 (LiNO3 + KNO3). Proportions of the components in these mixed electrolytes are concentration dependent. The electrokinetic potentials of alumina in these mixed electrolytes determined with and without background correction were only marginally different.