Triangular Ni2Ln and Ni2Y complexes derived from di-2-pyridyl ketone: Synthesis, structures and magnetic properties

The synthetic investigation of the Ni^II/M(NO₃)₃·6H₂O/di-2-pyridyl ketone [(py)₂CO] tertiary reaction system in EtOH has yielded triangular Ni₂M cationic complexes (M = lanthanide, Y). The reaction between Ln(NO₃)₃·6H₂O, Ni(ClO₄)₂·6H₂O, (py)₂CO and base (1:3:3:3) in EtOH under gentle heating gave the isostructural complexes [Ni₂Ln{(py)₂C(OEt)(O)}₃{(py)₂C(OH)(O)}(NO₃)(H₂O)](ClO₄)₂ (Ln = Gd, 2; Ln = Tb, 3) in high yields. The ligands (py)₂C(OEt)(O)⁻ and (py)₂C(OH)(O)⁻ are the monoanions of the hemiketal and gem-diol derivatives of (py)₂CO, respectively, formed in situ in the presence of the metal ions. The cations of 2 and 3 consist of one 8-coordinate Ln^III and two distorted octahedral Ni^II atoms in an essentially isosceles, triangular arrangement capped by a central μ₃-Ο⁻ atom of the unique 3.3011 (Harris notation) (py)₂C(OH)(O)⁻ ligand. Each metal-metal edge is bridged by the deprotonated O atom of one 2.2011 (py)₂C(OEt)(O)⁻ ligand. The isostructural complexes [Ni₂M{(py)₂C(OEt)(O)}₄(NO₃)(H₂O)]₂[M(NO₃)₅](ClO₄)₂ (M = Y, 4 ; M = Tb, 5 ; M = Dy, 6) were prepared by the 1:1 reaction of the mononuclear “metalloligand” [Ni(O₂CMe){(py)₂CO}{(py)₂C(OH)₂}](ClO₄) (1) and M(NO₃)₃·6H₂O in EtOH under mild heating in moderate to good yields. The structures of the dications of 4-6 are similar to those in 2 and 3, the only difference being the replacement of the unique 3.3011 (py)₂C(OH)(O)⁻ ligand of the latter by one 3.3011 (py)₂C(OEt)(O)⁻ group in the former. The Y^III, Tb^III and Dy^III atoms in [M(NO₃)₅]²⁻ are coordinated by five bidentate chelating nitrato groups. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the ligands. Variable temperature, solid-state direct current magnetic susceptibility and magnetization studies were carried out on dried samples of 2-4. The data indicate ferromagnetic Ni?Ni and Ni?Gd exchange interactions, and an S_T = 11/2 ground state for 2. Complex 3 is characterized by a high-spin ground state while the ferromagnetic Ni?Ni interaction for 2 is independently supported by the study of 4. No out-of-phase, alternating current susceptibility signals have been detected for 3 that would be indicative of SMM behavior.     

Synthesis of 1,2,3-triazole linked galactopyranosides and evaluation of cholera toxin inhibition

We report the synthesis of a series of bivalent 1,2,3-triazole linked galactopyranosides as potential inhibitors of cholera toxin (CT). The inhibitory activity of the bivalent series was examined (ELISA) and the series showed low inhibitory activity (millimolar IC(50)s). Conversely, the monomeric galactotriazole analogues were strong inhibitors of cholera toxin (IC(50) = 71-75 μM).     

Sharp integral inequalities for the dyadic maximal operator and applications

Mathematische Zeitschrift - We prove a sharp integral inequality for the dyadic maximal function of $$\phi \in L^p$$ . This inequality connects certain quantities related to integrals of $$\phi $$...     

Sorption of Arsenic Oxyanions from Aqueous Solution on Goethite: a Study of Process Modelling

In the course of researching methods of sampling and monitoring toxic metals (as arsenic ions) in water and wastewaters, we selected the use of sorption for in-depth examination. Among other things, sorption modelling was investigated by the mechanism of surface complexation in order to describe the process or even predict the outcome for the expected rate, and in general, to develop this detection technique for pollutants. This investigation will include the application of goethite mineral as the suitable metal ion sorbent and the use of appropriate computer software. The relative thermodynamic aqueous speciation of the solution, in similar experimental conditions, was also studied.     

Geometry and Physics Today

“Geometry,” in the sense of the classical differential geometry of smooth manifolds (CDG), is put under scrutiny from the point of view of Abstract Differential Geometry (ADG). We explore potential physical implications of viewing things under the light of ADG, especially matters concerning the “gauge theories” of modern physics, when the latter are viewed (as they are actually regarded currently) as “physical theories of a geometrical character.” Thence, “physical geometry,” in connection with physical laws and the associated with them, within the background spacetime manifoldless context of ADG, “differential” equations, are also being discussed.     

Relation empirique entre la viscosite intrinseque et la masse moleculaire d'un polymere dissout dans un bon solvant

We propose the following empirical relationship between the intrinsic viscosity of a polymer and its molecular weight M.

$\text{{[η]?[η]}{}_{\mathrm{\theta }}\text{/[η][η]}{}_{\mathrm{\theta }}\text{=?Δρ}{}_{\mathrm{\infty }}\text{+}\text{A′}\text{M}\text{1}\text{2}$

[η] and [η]₀ are the intrinsic viscosities in a good solvent and in θ conditions respectively. Δ?, and A′ are constants characteristic of a system polymer-solvent. This relationship is valid for PS and PMMA in various good solvents and for a range of molecular weight from 3000 to 250,000. It is in this range that the Mark-Houwink-Sakurada equation is least applicable.     

Tensor products and harmonic analysis

Mathematische Annalen -     

A Plasticity Principle of Closed Hexahedra in the Three-Dimensional Euclidean Space

We prove a plasticity principle of closed hexahedra in the three dimensional Euclidean space which states that: Suppose that the closed hexahedron A ₁ A ₂?A ₅ has an interior weighted Fermat-Torricelli point A ₀ with respects to the weights B _i and let α _i0j =∠A _i A ₀ A _j . Then these 10 angles are determined completely by 7 of them and considering these five prescribed rays which meet at the weighted Fermat-Torricelli point A ₀, such that their endpoints form a closed hexahedron, a decrease on the weights that correspond to the first, third and fourth ray, causes an increase to the weights that correspond to the second and fifth ray, where the fourth endpoint is upper from the plane which is formed from the first ray and second ray and the third and fifth endpoint is under the plane which is formed from the first ray and second ray. By applying the plasticity principle of closed hexahedra to the n-inverse weighted Fermat-Torricelli problem, we derive some new evolutionary structures of closed polyhedra for n>5. Finally, we derive some evolutionary structures of pentagons in the two dimensional Euclidean space from the plasticity of weighted hexahedra as a limiting case.     

Aryne-Enabled C−N Arylation of Anilines

Anilines are potentially high-value arylating agents, but are limited by the low reactivity of the strong C−N bond. We show that the reactive intermediate benzyne can be used to both activate anilines, and set-up an aryl transfer reaction in a single step. The reaction does not require any transition metal catalysts or stoichiometric organometallics, and establishes a metal-free route to valuable biaryl products by functionalizing the aniline C−N bond.