Electronic energy-transfer rate constants for geometrical isomers of a bichromophoric macrocyclic complex

The rate of electronic energy transfer (EET) between a naphthalene donor and an anthracene acceptor in [ZnL(3)](ClO(4))(2) and [ZnL(4)](ClO(4))(2) was determined by time-resolved fluorescence measurements, where L(3) and L(4) are the geometrical isomers of 6-[(anthracen-9-ylmethyl)amino]-trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-13-amine (L(2)), substituted with either a naphthalen-1-ylmethyl or naphthalen-2-ylmethyl donor, respectively. The energy-transfer rate constant, k(EET), was determined to be (0.92 +/- 0.02) x 10(9) s(-1) for the naphthalen-1-ylmethyl-substituted isomer, while that for the naphthalen-2-ylmethyl-substituted isomer is somewhat faster, with k(EET) = (1.31 +/- 0.01) x 10(9) s(-1). The solid-state structure of [ZnL(3)Cl]ClO(4) has been determined, and using molecular modeling calculations, the likely distributions of solution conformations in CH(3)CN have been evaluated for both complexes. The calculated conformational distributions in the common trans-III N-based isomeric form gave F?rster EET rate constants that account for the differences observed and are in excellent agreement with the experimental values. It is shown that the full range of conformers must be considered to accurately reproduce the observed EET kinetics.     

Influence of lattice interactions on the Jahn-Teller distortion of the [Cu(H2O)6]2+ ion: dependence of the crystal structure of K2[Cu(H2O)6](SO4)(2x)(SeO4)(2-2x) upon the sulfate/selenate ratio

The temperature dependence of the structure of the mixed-anion Tutton salt K2[Cu(H2O)6](SO4)(2x)(SeO4)(2-2x) has been determined for crystals with 0, 17, 25, 68, 78, and 100% sulfate over the temperature range of 85-320 K. In every case, the [Cu(H2O)6]2+ ion adopts a tetragonally elongated coordination geometry with an orthorhombic distortion. However, for the compounds with 0, 17, and 25% sulfate, the long and intermediate bonds occur on a different pair of water molecules from those with 68, 78, and 100% sulfate. A thermal equilibrium between the two forms is observed for each crystal, with this developing more readily as the proportions of the two counterions become more similar. Attempts to prepare a crystal with approximately equal amounts of sulfate and selenate were unsuccessful. The temperature dependence of the bond lengths has been analyzed using a model in which the Jahn-Teller potential surface of the [Cu(H2O)6]2+ ion is perturbed by a lattice-strain interaction. The magnitude and sign of the orthorhombic component of this strain interaction depends on the proportion of sulfate to selenate. Significant deviations from Boltzmann statistics are observed for those crystals exhibiting a large temperature dependence of the average bond lengths, and this may be explained by cooperative interactions between neighboring complexes.     

Reactions of TpRu(CO)(NCMe)(Ph) with electron-rich olefins: examples of stoichiometric C-S, C-O and C-H bond cleavage

Stoichiometric reactions of TpRu(CO)(NCMe)(Ph) with electron-rich olefins result in metal-mediated cleavage of C-S and C-O bonds.     

The Dehn Function of Stallings’ Group

We prove that the Dehn function of a group of Stallings that is finitely presented but not of type F₃{\mathcal{F}_3} is quadratic.     

Simulation modelling is 50! Do we need a reality check?

Simulation modelling is a fascinating research field. The techniques and tools of simulation modelling have been used to research and investigate the behaviour of various systems in a wide range of areas such as commerce, computer networks, defence, health, manufacturing and transportation. Indeed, the study of the use of these techniques and tools, and the development of new forms of these, are a rich source of research in their own right. Simulation modelling is about to reach the 50th anniversary of the development of GSP (General Simulation Program), the first simulation modelling language (Tocher and Owen, 1960). There have been several historical accounts of simulation modelling research. To complement these, we have performed a review of the recent history of simulation modelling. This study targeted three leading journals dedicated to this field. These are the ACM Transactions of Modeling and Computer Simulation, Simulation: Transactions of The Society for Modeling and Simulation International and Simulation Modelling Practice and Theory (formerly Simulation Practice and Theory). The study covered the first 6 years of this century (2000–2005) and included 576 papers. The key observation of this work was the relative lack of ‘real world’ involvement in simulation modelling research and an even greater lack of evidence of ‘real world’ benefit, arguably very alarming outcomes for an applied field. To further investigate this observation two additional surveys were carried out, one to study if real world papers appeared in the more widely known OR/MS literature (837 papers in 12 journals) and one to study if such papers appeared in Manufacturing and Logistics, an application area closely associated with simulation modelling (1077 papers in 10 journals). The results of these surveys confirmed our observations. We ask if this is the natural evolution of a field that has existed for half a century or an indication of a worrying problem? This paper reports on our findings and discusses whether or not simulation modelling research urgently needs to face a ‘reality check.’