Substituent effect on formation of heterometallic molecular wheels: synthesis, crystal structure, and magnetic properties

The reaction of manganese(III) Schiff bases of the type salen(2-) (N,N'-ethylenebis(salicylideneaminato)) with X-substituted (X = CH(3), Cl) pyridinecarboxamide dicyanoferrite(III) [Fe(X-bpb)(CN)(2)](-) gave rise to a series of cyanide-bridged Mn(6)Fe(6) molecular wheels, [Mn(III)(salen)](6)[Fe(III)(bpmb)(CN)(2)](6) x 7H(2)O (1), [Mn(salen)](6)[Fe(bpClb)(CN)(2)](6) x 4H(2)O x 2CH(3)OH (2), [Mn(salen)](6)[Fe(bpdmb)(CN)(2)](6) x 10H(2)O x 5CH(3)OH (3), [Mn(5-Br(salpn))](6)[Fe(bpmb)(CN)(2)](6) x 24H(2)O x 8CH(3)CN (4), and [Mn(5-Cl(salpn))](6)[Fe(bpmb)(CN)(2)](6) x 25H(2)O x 5CH(3)CN (5). Compared with [Fe(bpb)(CN)(2)](-), which always gives rise to 1D or polynuclear species when reacting with Mn(III) Schiff bases, the introduction of substituents (X) to the bpb(2-) ligand has a driving force in formation of the novel wheel structure. Magnetic studies reveal that high-spin ground state S = 15 is present in the wheel compounds originated from the ferromagnetic Mn(III)-Fe(III) coupling. For the first time, the quantum Monte Carlo study has been used to modulate the magnetic susceptibility of the huge Mn(6)Fe(6) metallomacrocycles, showing that the magnetic coupling constants J range from 3.0 to 8.0 K on the basis of the spin Hamiltonian [Formula: see text]. Hysteresis loops for 1 have been observed below 0.8 K, indicative of a single-molecule magnet with a blocking temperature (TB) of 0.8 K. Molecular wheels 2-5 exhibit frequency dependence of alternating-current magnetic susceptibility under zero direct-current magnetic field, signifying the slow magnetization relaxation similar to that of 1. Significantly, an unprecedented archlike Mn(2)Fe(2) cluster, [Mn(5-Cl(salpn))](2)[Fe(bpmb)(CN)(2)](2) x 3H(2)O x CH(3)CN (6), has been isolated as an intermediate of the Mn(6)Fe(6) wheel 5. Ferromagnetic Mn(III)-Fe(III) coupling results in a high-spin S = 5 ground state. Combination of the high-spin state and a negative magnetic anisotropy (D) results in the observation of slow magnetization relaxation in 6.     

Non-steroidal antiinflammatory drug-copper(II) complexes: structure and biological perspectives

Copper(II) complexes with the non-steroidal antiinflammatory drug mefenamic acid in the presence of aqua or nitrogen donor heterocyclic ligands (2,2'-bipyridine, 1,10-phenanthroline, 2,2'-bipyridylamine or pyridine) have been synthesized and characterized. The crystal structures of [(2,2'-bipyridine)bis(mefenamato)copper(II)], 2, [(2,2'-bipyridylamine)bis(mefenamato)copper(II)], 4, and [bis(pyridine)bis(methanol)bis(mefenamato)copper(II)], 5, have been determined by X-ray crystallography. UV study of the interaction of the complexes with calf-thymus DNA (CT DNA) has shown that the complexes can bind to CT DNA and [bis(aqua)tetrakis(mefenamato)dicopper(II)] exhibits the highest binding constant to CT DNA. The cyclic voltammograms of the complexes in the presence of CT DNA solution have shown that the complexes can bind to CT DNA by the intercalative binding mode verified also by DNA solution viscosity measurements. Competitive studies with ethidium bromide (EB) indicate that the complexes can displace the DNA-bound EB suggesting strong competition with EB. Mefenamic acid and its complexes exhibit good binding propensity to human or bovine serum albumin protein having relatively high binding constant values. All the compounds have been tested for their antioxidant and free radical scavenging activity as well as for their in vitro inhibitory activity against soybean lipoxygenase showing significant activity.     

Renormalized perturbation theory flow equations for the Anderson impurity model

We apply the renormalized perturbation theory (RPT) to the symmetric Anderson impurity model. Within the RPT framework exact results for physical observables such as the spin and charge susceptibility can be obtained in terms of the renormalized values \(\tilde \mu = (\tilde \Delta ,\tilde U)\) of the hybridization Δ and Coulomb interaction U of the model. The main difficulty in the RPT approach usually lies in the calculation of the renormalized values themselves. In the present work we show how this can be accomplished by deriving differential flow equations describing the evolution of \(\tilde \mu = (\tilde \Delta )\) with Δ. By exploiting the fact that \(\tilde \mu = (\tilde \Delta )\) can be determined analytically in the limit Δ → ∞ we solve the flow equations numerically to obtain estimates for the renormalized parameters in the range 0 <U/πΔ< 3.5.     

Effect of Reaction Conditions and Catalyst Design on the Rheological Properties of Polyolefins Produced in Gas‐Phase Olefin Polymerization Reactors

A model is developed to predict the viscoelastic behavior of polyolefins produced in catalytic polymerization reactors. The approach is based on the solution of different sub‐models (e.g., a kinetic model, a single particle model, a macroscopic reactor model and a rheological model). From the calculated rheological curve, the polymer melt index is determined. The ability of the proposed model to predict the viscoelastic behavior of linear polymer melts quantitatively is examined for the operation of a catalytic olefin polymerization cascade‐loop reactor process. In addition, the transient rheological properties of polyolefins produced in a Ziegler‐Natta gas‐phase olefin polymerization fluidized‐bed reactor are calculated.

     

Synthetic Amphoteric Cryogels as an Antidote against Acute Heavy Metal Poisoning

The effectiveness of an amphoteric cryogel (AAC) as an oral sorbent (enerosorbent) for the treatment of acute poisoning of small animals (rats) with heavy metals (HMs) was studied in in vivo experiments. The morphological structure of the cryogel was examined using scanning electron microscopy/energy-dispersive X-ray analysis and confocal microscopy. The use of the cryogel in the treatment of rats administered an LD₅₀ dose of Cd(NO₃)₂, CsNO₃, Sr(NO₃)₂, or HgCl₂ in aqueous solution showed their high survival rate compared to the control group, which did not receive such treatment. The histological and chemical analysis of internal tissues and the biochemical analysis of the blood of the experimental animals showed the effectiveness of the cryogel in protecting the animals against the damaging effect of HMs on the organism comparable with unithiol, a chelating agent based on 2,3-dimercapto-1-propane sulfonic acid sodium salt (DMPS) approved for the treatment of acute poisoning with some heavy metals.     

Enhanced algebraic substructuring for symmetric generalized eigenvalue problems

This article proposes a new substructuring algorithm to approximate the algebraically smallest eigenvalues and corresponding eigenvectors of a symmetric positive-definite matrix pencil $(A,M)$. The proposed approach partitions the graph associated with $(A,M)$ into a number of algebraic substructures and builds a Rayleigh–Ritz projection subspace by combining spectral information associated with the interior and interface variables of the algebraic domain. The subspace associated with interior variables is built by computing substructural eigenvectors and truncated Neumann series expansions of resolvent matrices. The subspace associated with interface variables is built by computing eigenvectors and associated leading derivatives of linearized spectral Schur complements. The proposed algorithm can take advantage of multilevel partitionings when the size of the pencil. Experiments performed on problems stemming from discretizations of model problems showcase the efficiency of the proposed algorithm and verify that adding eigenvector derivatives can enhance the overall accuracy of the approximate eigenpairs, especially those associated with eigenvalues located near the origin.