Roles of rhenium diimine complexes as metal‐ion probes and photosensitizers in functional polyurethanes

Polyurethanes incorporated with rhenium diimine complexes were synthesized. The polymers exhibited interesting morphologies and solution properties. Results from gel permeation chromatography suggested the formation of polymer aggregates in solutions. The polymers could act as probes for metal ions. The addition of metal ions to polymer solutions led to significant changes in the electronic absorption properties of the polymer solutions. This was attributed to the interactions between the polyether moieties and metal ions. The metal complexes could also act as efficient photosensitizers. After doping with charge‐transport viologens, the photoconductivity of the polymers was greatly enhanced. The experimental quantum efficiency was simulated with Onsager's theory. The thermalization distances and the primary yields were typically 12–14 Å and 10^?3, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1708–1715, 2003     

Grafting of styrene onto low molecular weight polymers and copolymers of butadiene

The grafting of styrene onto low molecular weight polybutadienes and butadiene–styrene co-polymers was studied. A mathematical method was used for the design of experiments and for the determination of the optimum grafting conditions with respect to the conversion of styrene and the efficiency of grafting. The reaction parameters were temperature (65–105°C), time (2–10 hr), concentration of the initiator, polymer to monomer ratio (10/90–90/10) and dilution by solvent (toluene). The optimum grafting conditions were chosen under which 50–60 wt-% of styrene was grafted onto backbone polymer at a high conversion of the monomer. It was found that the reactions producing graft copolymer prevailed over the styrene homopolymerization when the temperatures employed were lower (65–85°C), and the reaction time (8–10 hr), backbone polymer/monomer ratio, and the dilution by solvent were higher. The efficiency, density, and degree of grafting were found to increase with the increase in the molecular weight of the backbone polymer. The efficiencies and densities of grafting onto low molecular weight polybutedienes were higher than those of grafting onto low molecular weight butadiene–styrene copolymers. Grafting efficiencies and grafting densities were in the ranges 37.8–61.6 wt % and 0.06–0.26, respectively, in the studied range of number-average molecular weights (M?_n = 2400–6000).     

Anion-pi interactions in cyanuric acids: a combined crystallographic and computational study

Several structures of pi complexes of isocyanuric acid and of several thio derivatives with anions have been computed by using high level ab initio calculations. The nature of the complexes has been studied by means of the method of molecular interaction potential with polarization (MIPp) and Bader's theory of atoms-in-molecules. These molecules form favorable complexes with anions and can be used as binding units for building receptors for the molecular recognition of anions. In several cases, the anion-pi interaction has been demonstrated experimentally by means of X-ray crystallography.     

Modulatory Effect of Diosmin and Diosmetin on Metalloproteinase Activity and Inflammatory Mediators in Human Skin Fibroblasts Treated with Lipopolysaccharide

Diosmin is widely used as a venoactive drug in the pharmacological treatment of chronic venous disorders. It exerts a strong protective effect on blood vessels via an increase in the elasticity of vessel walls and reduces the permeability of capillary walls, thereby producing an anti-edematous effect. In this paper, we investigated the effectiveness of diosmin and diosmetin in modulating the level of proinflammatory factors in human skin fibroblasts treated with lipopolysaccharide (LPS). Two variants of the experiments were performed: the flavonoid was added 2 h prior to or 24 h after LPS stimulation. Our study revealed that both flavonoids reduced the levels of IL-6 and Il-1β as well as COX-2 and PGE2 but had no impact on IL-10. However, the addition of the compounds prior to the LPS addition was more effective. Moreover, diosmetin modulated the proinflammatory factors more strongly than diosmin. Our investigations also showed that both flavonoids were potent inhibitors of elastase and collagenase activity, and no differences between the glycoside and aglycone forms were observed.     

Novel C60 Fullerenol-Gentamicin Conjugate–Physicochemical Characterization and Evaluation of Antibacterial and Cytotoxic Properties

This study aimed to develop, characterize, and evaluate antibacterial and cytotoxic properties of novel fullerene derivative composed of C₆₀ fullerenol and standard aminoglycoside antibiotic–gentamicin (C₆₀ fullerenol-gentamicin conjugate). The successful introduction of gentamicin to fullerenol was confirmed by X-ray photoelectron spectroscopy which together with thermogravimetric and spectroscopic analysis revealing the formula of the composition as C₆₀(OH)₁₂(GLYMO)₁₁(Gentamicin)_0.8. The dynamic light scattering (DLS) revealed that conjugate possessed ability to form agglomerates in water (size around 115 nm), while Zeta potential measurements demonstrated that such agglomerates possessed neutral character. In vitro biological assays indicated that obtained C₆₀ fullerenol-gentamicin conjugate possessed the same antibacterial activity as standard gentamicin against Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa, and Escherichia coli, which proves that combination of fullerenol with gentamicin does not cause the loss of antibacterial activity of antibiotic. Moreover, cytotoxicity assessment demonstrated that obtained fullerenol-gentamicin derivative did not decrease viability of normal human fibroblasts (model eukaryotic cells) compared to control fibroblasts. Thus, taking into account all of the results, it can be stated that this research presents effective method to fabricate C₆₀ fullerenol-gentamicin conjugate and proves that such derivative possesses desired antibacterial properties without unfavorable cytotoxic effects towards eukaryotic cells in vitro. These promising preliminary results indicate that obtained C₆₀ fullerenol-gentamicin conjugate could have biomedical potential. It may be presumed that obtained fullerenol may be used as an effective carrier for antibiotic, and developed fullerenol-gentamicin conjugate may be apply locally (i.e., at the wound site). Moreover, in future we will evaluate possibility of its applications in inter alia tissue engineering, namely as a component of wound dressings and implantable biomaterials.     

Gold Nanoparticles as Effective ion Traps in Poly(dimethylsiloxane) Cross-Linked by Metal-Ligand Coordination

At this time, the development of advanced elastic dielectric materials for use in organic devices, particularly in organic field-effect transistors, is of considerable interest to the scientific community. In the present work, flexible poly(dimethylsiloxane) (PDMS) specimens cross-linked by means of ZnCl₂-bipyridine coordination with an addition of 0.001 wt. %, 0.0025 wt. %, 0.005 wt. %, 0.04 wt. %, 0.2 wt. %, and 0.4 wt. % of gold nanoparticles (AuNPs) were prepared in order to understand the effect of AuNPs on the electrical properties of the composite materials formed. The broadband dielectric spectroscopy measurements revealed one order of magnitude decrease in loss tangent, compared to the coordinated system, upon an introduction of 0.001 wt. % of AuNPs into the polymeric matrix. An introduction of AuNPs causes damping of conductivity within the low-temperature range investigated. These effects can be explained as a result of trapping the Cl⁻ counter ions by the nanoparticles. The study has shown that even a very low concentration of AuNPs (0.001 wt. %) still brings about effective trapping of Cl⁻ counter anions, therefore improving the dielectric properties of the investigated systems. The modification proposed reveals new perspectives for using AuNPs in polymers cross-linked by metal-ligand coordination systems.     

On the Generalized Strongly Nil-Clean Property of Matrix Rings

Let R be an associative unital ring and not necessarily commutative.We analyze conditions under which every n × n matrix A over R is expressible as a sum A =E1 +…+ Es + N of (commuting) idempotent matrices Ei and a nilpotent matrix N.     

Characterization of CaTi0.9Fe0.1O3/La0.98Mg0.02NbO4 composite

A composite of CaTi_0.9Fe_0.1O₃ and electrolyte material, i.e. magnesium doped La_0.98Mg_0.02NbO₄ was prepared and studied. The phase content and the sample microstructure was examined by an X-ray diffraction method and scanning electron microscopy. EDS measurements were done both for composite samples and the diffusion couple. The electrical properties were studied by four terminal DC method. The high-temperature interaction between the two components of the composite has been observed. It has been suggested that lanthanum diffused into the perovskite phase and substituted for calcium whereas calcium and niobium formed the Ca₂Nb₂O₇ pyrochlore phase. At 1500°C very large crystallites of the pyrochlore were observed. Regardless of strong interaction between the composite components, its total conductivity was weakly dependent on the sintering temperature.     

Cascade assembly of the benzo[a]anthraquinone ring system common to the angucycline antibiotics

A benzo[a]anthraquinone ring system, common to a group of angucycline antibiotics, has been prepared by a unique cascade of reactions. The reaction sequence was initiated by a Suzuki-Miyaura cross-coupling between a bromoquinone and vinyl boronic anhdyride. The reaction product is proposed to undergo a 6π-electron cyclization triggered by reductive activation of the quinone. The reaction process is proposed to be autocatalytic.     

Influence of pyridine-based ligands on photostability of MAPbI3 thin films

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