Competitive binding exchange between alkali metal ions (K+, Rb+, and Cs+) and Na+ ions bound to the dimeric quadruplex [d(G4T4G4)]2: a 23Na and 1H NMR study

A comparative study of the competitive cation exchange between the alkali metal ions K⁺, Rb⁺, and Cs⁺ and the Na⁺ ions bound to the dimeric quadruplex [d(G₄T₄G₄)]₂ was performed in aqueous solution by a combined use of the ²³Na and ¹H NMR spectroscopy. The titration data confirm the different binding affinities of these ions for the G‐quadruplex and, in particular, major differences in the behavior of Cs⁺ as compared to the other ions were found. Accordingly, Cs⁺ competes with Na⁺ only for the binding sites at the quadruplex surface (primarily phosphate groups), while K⁺ and Rb⁺ are also able to replace sodium ions located inside the quadruplex. Furthermore, the ¹H NMR results relative to the CsCl titration evidence a close approach of Cs⁺ ions to the phosphate groups in the narrow groove of [d(G₄T₄G₄)]₂. Based on a three‐site exchange model, the ²³Na NMR relaxation data lead to an estimate of the relative binding affinity of Cs⁺ versus Na⁺ for the quadruplex surface of 0.5 at 298 K. Comparing this value to those reported in the literature for the surface of the G‐quadruplex formed by 5′‐guanosinemonophosphate and for the surface of double‐helical DNA suggests that topology factors may have an important influence on the cation affinity for the phosphate groups on DNA. Copyright © 2009 John Wiley & Sons, Ltd.     

Unexpected transformation of quinones to spirolactones and to naturally occurring naphthalenic compounds

In the last few years, natural quinones of the lapachol group have been used as starting points for the preparation of several bioactive heterocyclic compounds. Herein, we announce that lapachones, derivatives of lapachol, under certain conditions in the presence of inorganic reagents give unexpected products, spirolactones and naphthalenic derivatives, nordihydrolapachenone and tetrahydrotectol, both naturally occurring compounds. Nordihydrolapachenone was identified by X-ray analysis. Lapachol itself can also be converted to tetrahydrotectol.     

Synthesis and structural analysis of 5‐cyanodihydropyrazolo[3,4‐b]pyridines

Several new 3‐aryl‐5‐cyanopyrazolo[3,4‐b]pyridines were easily prepared from 3‐amino‐5‐arylpyrazoles and α‐cyanochalcones. Structural analysis using NMR solution studies revealed the 2H‐tautomers as the preferred tautomer in solution (DMSO‐d₆). X‐ray diffraction confirmed the 2H‐tautomers as the unique tau‐tomer species in the crystalline state as well. Geometry optimization of 1H and 2H‐tautomers at semi‐empirical levels (AM1, MINDO/3) were performed, indicating that in all cases the 2H‐tautomers are more stable than the corresponding 1H‐tautomers.     

The Painlevé Property for Quasihomogenous Systems and a Many-Body Problem in the Plane

We investigate a many-body problem in the plane introduced by Calogero and intensively studied by Calogero, Françoise and Sommacal. An ad hoc complexification transforms the many-body problem to a system of second order autonomous complex equations depending on some complex constants that describe the two-body interactions. We investigate the sets of two-body interaction constants that make the complexified equation have the Painlevé Property, this is, its solutions are given by single-valued meromorphic functions. In this case the original system has only periodic isochronous solutions. We exhibit a family of settings where the system displays this property and show that it is not present in the three- and four-body problems that do not fall within our class. For this, we introduce a necessary condition for the presence of the Painlevé Property in some quasihomogenous systems.     

Totally Permutable Products of Finite Groups Satisfying SC or PST

Finite groups G=AB factorized by two subgroups A and B such that every subgroup of A permutes with every subgroup of B are studied in this paper. The behaviour of such products with respect to the class of finite groups in which Sylow-permutability is transitive is analyzed.     

Dimensional crossover in alternating spin chains

The effect of antiferromagnetic interchain coupling in alternating spin chains is studied by means of spin wave (SW) theory and density matrix renormalization group (DMRG). Two limiting cases are investigated, the two-leg ladder and its two-dimensional (2D) generalization. For the 2D case, SW approximation predicts a smooth-dimensional crossover keeping the ground state ordered, whereas in the ladder case the DMRG results show a gapped ground state for any J>0. Furthermore, the behavior of the correlation functions closely resemble the uniform spin- ladder. However, for small J, the gap behaves quadratically as Δ0.6J². Similarly to uniform spin chains, it is conjectured an analogous spin gap behavior for an arbitrary number of mixed spin chains.     

The Exact Poincaré Lemma in Crystalline Cohomology of Higher Level

We prove a formal Poincaré Lemma in crystalline cohomology of higher level and we derive a de Rham interpretation of crystalline cohomology of higher level. We also define the Spencer complex of higher level and show that it can be used to compute the cohomology of arithmetic -modules.     

Band-gap problem in semiconductors revisited: effects of core states and many-body self-consistency

A novel picture of the quasiparticle (QP) gap in prototype semiconductors Si and Ge emerges from an analysis based on all-electron, self-consistent, GW calculations. The deep-core electrons are shown to play a key role via the exchange diagram-if this effect is neglected, Si becomes a semimetal. Contrary to current lore, the Ge 3d semicore states (e.g., their polarization) have no impact on the GW gap. Self-consistency improves the calculated gaps-a first clear-cut success story for the Baym-Kadanoff method in the study of real-materials spectroscopy; it also has a significant impact on the QP lifetimes. Our results embody a new paradigm for ab initio QP theory.