Electronic structure and vibrational spectra of cis-diammine(orotato)platinum(II), a potential cisplatin analogue: DFT and experimental study

Orotic acid (vitamin B₁₃) is a key intermediate in biosynthesis of the pyrimidine nucleotides in living organisms, moreover, it may serve as the biological carrier for some metal ions. cis-Diammine(orotato)platinum(II), cis-[Pt(C₅H₂N₂O₄)(NH₃)₂] can be considered as a new potential cisplatin analogue. The FT-Raman and FT-IR spectra of the title complex are reported, for the first time. The molecular structure, vibrational frequencies, and the theoretical infrared and Raman intensities have been calculated by the density functional mPW1PW91 method. The detailed vibrational assignment has been made on the basis of the calculated potential energy distribution. The theoretically predicted IR and Raman spectra show very good agreement with experiment. Natural bond orbital (NBO) analyses were performed for cisplatin, carboplatin and the title complex. The results provided new data on the nature of platinum–ligand bonding in these compounds. Strong intramolecular hydrogen bond between the orotate ligand and the coordinated ammonia group stabilizes the structure of the platinum(II) complex. Thus, it is suggested that the orotate ligand in the title complex is more inert to the substitution reactions than the chloride ligands in cisplatin.     

Coupled Thermo-Hydro-Mechanical and Chemical Analysis of Expansive Clay Subjected to Heating and Hydration

A fully coupled formulation combining reactive transport and an existing thermo-hydro-mechanical (THM) code is presented. Special attention has been given to phenomena likely to be encountered in clay barriers used as part of containment systems of nuclear waste. The types of processes considered include hydrolysis, complex formation, oxidation/reduction reactions, acid/base reactions, precipitation/dissolution of minerals and cation exchange. Both kinetically-controlled and equilibrium-controlled reactions have been incorporated. The total analytical concentrations (including precipitated minerals) are adopted as basic transport variables and chemical equilibrium is achieved by minimizing Gibbs Free Energy. The formulation has been incorporated in a general purpose computer code capable of performing numerical analysis of engineering problems. A validation exercise concerning a laboratory experiment involving the heating and hydration of an expansive compacted clay is described.     

An algebraic index theorem for orbifolds

Using the concept of a twisted trace density on a cyclic groupoid, a trace is constructed on a formal deformation quantization of a symplectic orbifold. An algebraic index theorem for orbifolds follows as a consequence of a local Riemann-Roch theorem for such densities. In the case of a reduced orbifold, this proves a conjecture by Fedosov, Schulze, and Tarkhanov. Finally, it is shown how the Kawasaki index theorem for elliptic operators on orbifolds follows from this algebraic index theorem.     

Adjugates in Banach algebras

A simple formula for the adjugate of a block triangle offers an alternative route to the determinant theory for Banach algebras.

     

A Ramsey‐type result for the hypercube

We prove that for every fixed k and ? ≥ 5 and for sufficiently large n, every edge coloring of the hypercube Q_n with k colors contains a monochromatic cycle of length 2 ?. This answers an open question of Chung. Our techniques provide also a characterization of all subgraphs H of the hypercube which are Ramsey, that is, have the property that for every k, any k‐edge coloring of a sufficiently large Q_n contains a monochromatic copy of H. © 2006 Wiley Periodicals, Inc. J Graph Theory 53: 196–208, 2006     

Converged properties of clean metal surfaces by all-electron first-principles calculations

All-electron full-potential linearized augmented plane-wave calculations of the surface energy, work function, and interlayer spacings of close-packed metal surfaces are presented, in particular, for the free-electron-like metal surfaces, Mg(0 0 0 1) and Al(1 1 1), and for the transition metal surfaces, Ti(0 0 0 1), Cu(1 1 1), Pd(1 1 1), and Pt(1 1 1). We investigate the convergence of the surface energy as a function of the number of layers in the slab, using the Cu(1 1 1) surface as an example. The results show that the surface energy, as obtained using total energies of the slab and bulk from separate calculations, converges well with respect to the number of layers in the slab. Obviously, it is necessary that bulk and surface calculations are performed with the same high accuracy. Furthermore, we discuss the performance of the local-density and generalized gradient approximations for the exchange-correlation functional in describing the various surface properties.     

Jack van Lint (1932-2004): A survey of his scientific work

When Jack van Lint was appointed as full professor at the Eindhoven University of Technology at the age of 26 he combined a PhD in number theory with a very open scientific mind. It took a sabbatical visit to Bell Laboratories in 1966 to make him understand that a new and fascinating field of applied mathematics was emerging: discrete mathematics. It fascinated and inspired him for the rest of his life. When he passed away on September 28, 2004, he left behind a legacy of 18 books and 177 articles, covering many aspects of coding theory, combinatorics, and finite geometry.van Lint was also a strong international advocate of the role that discrete mathematics ought to play in modern applied mathematics curricula. Quite a few departments sought his advice. Years later, four different universities showed their appreciation by awarding him an honorary degree.This overview is an homage to van Lint's academic achievements and can serve as an introduction to his work for younger generations.     

One-Parameter Fixed-Point Theory and Gradient Flows of Closed 1-Forms

We use the one-parameter fixed-point theory of Geoghegan and Nicas to get information about the closed orbit structure of transverse gradient flows of closed 1-forms on a closed manifold M. We define a noncommutative zeta function in an object related to the first Hochschild homology group of the Novikov ring associated to the 1-form and relate it to the torsion of a natural chain homotopy equivalence between the Novikov complex and a completed simplicial chain complex of the universal cover of M.     

Design and Cold Tests of Asymmetric Quasioptical Resonators

This paper presents the design and test of asymmetric quasioptical resonators for gyrotron applications, where most of the diffraction output coupling comes from the smaller of two mirrors. A computer code based on scalar diffraction theory is used to calculate the resonator losses and the electric field near the mirrors. Resonators with mirror separations approaching confocal have reduced side lobes in the diffraction patterns, which should allow for better power transmission and focusing. Cold tests have been performed at 94 and 141 GHz to measure the quality factor of the asymmetric resonators as a function of mirror separation and mirror misalignment. Typical resonator parameters include 65 cm mirror separation, 1-3% output coupling and 85% of the losses from the small mirror. A half-symmetric resonator with one flat and one curved mirror has also been investigated. The calculated values of Q are in reasonably good agreement with the cold test measurements.     

On the S-procedure and Some Variants

We give a concise review and extension of S-procedure that is an instrumental tool in control theory and robust optimization analysis. We also discuss the approximate S-Lemma as well as its applications in robust optimization.The many suggestions and detailed corrections of an anonymous referee are gratefully acknowledged.