Metal ion-assisted transformations of 2-pyridinealdoxime and hexafluorophosphate

Metal-ion mediated reactions of 2-pyridinealdoxime and hexafluorophosphate lead to Zn(II) complexes containing picolinic acid, picolinamide and monofluorophosphate (-2) as ligands.     

Large sets of <Emphasis Type="Italic">t</Emphasis>-designs from groups

This paper addresses questions related to the existence and construction of large sets of t-(v, k, λ) designs. It contains material from my talk in the Combinatorial Designs Conference in honor of Alex Rosa’s 70th birthday, which took place in beautiful Bratislava, in July, 2007. Naturally, only a small number of “highlight” topics could be included, and for the most part these involve the use of symmetry, that is, it is assumed that the particular designs or large sets of designs, are invariant under a prescribed group of automorphisms. I present almost no proofs, but give references so that the reader can find a much wider repertory of theorems and constructions in the literature. For completeness, I include the statement of a few recursive constructions. The latter are extremely important on their own right, and deserve extensive attention elsewhere. I hope the reader becomes interested in the intriguing open problems posed at the end of the paper and succeeds in solving some of them. (Communicated by Peter Horák)     

Mechanical behavior and wrinkling of lined pipes

The paper focuses on wrinkling of lined pipes (sometimes referred to as clad pipes) under bending loading, where a corrosion-resistant thin-walled liner is fitted inside a carbon–steel outer pipe. The problem is solved numerically, using nonlinear finite elements to simulate liner pipe deformation and its interaction with the outer pipe. Stresses and strains are monitored throughout the deformation stage, detecting possible detachment of the liner from the outer pipe and the formation of wrinkles. The wrinkling behavior of elastic and elastic–plastic (steel) lined pipes under bending is examined. The results indicate that the lateral confinement of the liner pipe due to the deformable outer pipe and its interaction with the outer pipe has a decisive influence on the wrinkling behavior of the lined pipe. It is also shown that the behavior is characterized by a first bifurcation in a uniform wrinkling pattern, followed by a secondary bifurcation. The values of corresponding buckling curvature are determined and comparison with available experimental results is conducted in terms of wrinkle height development and the corresponding buckling wavelength. The results of the present research can be used for safer design of lined pipes in pipeline applications.     

Singular Ricci Solitons and Their Stability under the Ricci Flow

We introduce certain spherically symmetric singular Ricci solitons and study their stability under the Ricci flow from a dynamical PDE point of view. The solitons in question exist for all dimensions n + 1 ≥ 3, and all have a point singularity where the curvature blows up; their evolution under the Ricci flow is in sharp contrast to the evolution of their smooth counterparts. In particular, the family of diffeomorphisms associated with the Ricci flow “pushes away” from the singularity causing the evolving soliton to open up immediately becoming an incomplete (but non-singular) metric. The main objective of this paper is to study the local-in time stability of this dynamical evolution, under spherically symmetric perturbations of the singular initial metric. We prove a local well-posedness result for the Ricci flow in suitably weighted Sobolev spaces, which in particular implies that the “opening up” of the singularity persists for the perturbations as well.     

A family of enneanuclear iron(II) single-molecule magnets

Complexes [Fe₉(X)₂(O₂CMe)₈{(2‐py)₂CO₂}₄] (X^?=OH^? ( 1 ), N₃^? ( 2 ), and NCO^? ( 3 )) have been prepared by a route previously employed for the synthesis of analogous Co₉ and Ni₉ complexes, involving hydroxide substitution by pseudohalides (N₃^?, NCO^?). As indicated by DC magnetic susceptibility measurements, this substitution induced higher ferromagnetic couplings in complexes 2 and 3 , leading to higher ground spin states compared to that of 1 . Variable‐field experiments have shown that the ground state is not well isolated from excited states, as a result of which it cannot be unambiguously determined. AC susceptometry has revealed out‐of‐phase signals, which suggests that these complexes exhibit a slow relaxation of magnetization that follows Arrhenius behavior, as observed in single‐molecule magnets, with energy barriers of 41 K for 2 (τ₀=3.4×10^?12 s) and 44 K for 3 (τ₀=2.0×10^?11 s). Slow magnetic relaxation has also been observed by zero‐field ⁵⁷Fe Mössbauer spectroscopy. Characteristic integer‐spin electron paramagnetic resonance (EPR) signals have been observed at X‐band for 1 , whereas 2 and 3 were found to be EPR‐silent at this frequency. ¹H NMR spectrometry in CD₃CN has shown that complexes 1 – 3 are stable in solution.     

Catalytic selective oxidation of benzyl alcohols to aldehydes with rhenium complexes

The system (ⁿBu₄N)ReO₄ 5/PhIO/CH₂Cl₂, T = 298 K catalyses effectively and with total selectivity the anaerobic oxidation of a range of primary substituted benzyl alcohols (o-, m-, p-X-C₆H₄-CH₂OH, X = H, Me, MeO, Cl, NO₂, CF₃) to the corresponding aldehydes; in contrast, it is unreactive towards secondary benzyl and aliphatic (primary and secondary) alcohols. This may prove of interest in synthetic organic transformations, when several alcoholic functionalities are present in the same molecule.     

High intensity ultrasound-assisted reduction of sterically demanding nitroaromatics

Sterically demanding nitroaromatic compounds have been prepared and reduced to their corresponding amines with high intensity ultrasound using hydrazine in the presence of a Raney nickel catalyst. These reactions were dependent on catalyst quality, solvent and ultrasonic amplitude and, in comparison to their silent reactions, proceeded much faster and afforded higher yields.     

Local chain motions of poly(β-hydroxyoctanoate) in the bulk. 13C NMR relaxation study

Variable-temperature ¹³C NMR spin-lattice relaxation times (T₁) and Nuclear Overhauser Enhancements (NOE) at two magnetic fields have been used to study the dynamics of the amorphous part of a semicrystalline sample (33% of crystallinity) of poly(β-hydroxyoctanoate) (PHO). The interpretation of the relaxation data of the backbone carbons was made by employing a number of motional models. Among these, the DLM model offered the best interpretation of the relaxation data in terms of conformational transitions and librational motions of the backbone C? H vectors, and proved to be superior to unimodal distribution functions. The interpretation of temperature- and frequency-dependent T₁ and NOE data of the carbon nuclei in the n-pentyl side chain was made by employing a newly developed composite spectral density function for multiple internal C? C bond rotations of restricted amplitude and chain segmental motion. The temperature dependence of the linewidths of the various protonated carbon resonances of PHO has been discussed in terms of the semicrystalline character of this polymer. © 1995 John Wiley & Sons, Inc.