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.     

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     

Twin Paradox and the Logical Foundation of Relativity Theory

We study the foundation of space-time theory in the framework of first-order logic (FOL). Since the foundation of mathematics has been successfully carried through (via set theory) in FOL, it is not entirely impossible to do the same for space-time theory (or relativity). First we recall a simple and streamlined FOL-axiomatization Specrel of special relativity from the literature. Specrel is complete with respect to questions about inertial motion. Then we ask ourselves whether we can prove the usual relativistic properties of accelerated motion (e.g., clocks in acceleration) in Specrel. As it turns out, this is practically equivalent to asking whether Specrel is strong enough to “handle” (or treat) accelerated observers. We show that there is a mathematical principle called induction (IND) coming from real analysis which needs to be added to Specrel in order to handle situations involving relativistic acceleration. We present an extended version AccRel of Specrel which is strong enough to handle accelerated motion, in particular, accelerated observers. Among others, we show that~the Twin Paradox becomes provable in AccRel, but it is not provable without IND.     

A Model for Spacetime: The Role of Interpretation in Some Grothendieck Topoi

We analyse the proposition that the spacetime structure is modified at short distances or at high energies due to weakening of classical logic. The logic assigned to the regions of spacetime is intuitionistic logic of some topoi. Several cases of special topoi are considered. The quantum mechanical effects can be generated by such semi-classical spacetimes. The issues of: background independence and general relativity covariance, field theoretic renormalization of divergent expressions, the existence and definition of path integral measures, are briefly discussed in the proposal. The connection with some problems in foundations of mathematics and differential topology are also discussed.     

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.     

Density functional theory investigation of the structure of SO2 and SO3 on Cu(1 1 1) and Ni(1 1 1)

Density functional theory (DFT) slab calculations, mainly using the generalised gradient approximation, have been used to investigate the minimum energy structures of molecular SO₂ and SO₃ on Cu(1 1 1) and Ni(1 1 1) surfaces. On Ni(1 1 1) the optimal local adsorption structures are in close agreement with experimental results for both molecular species obtained using the X-ray standing wavefield technique, although for adsorbed SO₂ the energetic difference between two alternative lateral positions of the lying-down molecule on the surface is marginally significant. On Cu(1 1 1) the results for adsorbed SO₂, in particular, were sensitive to the DFT functional used in the calculations, but in all cases failed to reproduce the experimentally-established preference for adsorption with the molecular plane perpendicular to the surface. This result is discussed in the context of previously published DFT results for these species adsorbed on Cu(1 0 0). The optimal geometry found for SO₃ on Cu(1 1 1) is similar to that on Ni(1 1 1), providing agreement with experiment regarding the molecular orientation but not the adsorption site.     

Existence and multiplicity of solutions for a nonlinear Neumann problem

We consider a Neumann problem of the type -εΔu+F ^′(u(x))=0 in an open bounded subset Ω of R ⁿ , where F is a real function which has exactly k maximum points. Using Morse theory we find that, for ε suitably small, there are at least 2k nontrivial solutions of the problem and we give some qualitative information about them. Received: October 30, 1999 Published online: December 19, 2001