Photochemistry of bicyclo[2.2.2]oct-7-ene-2,5-diones and the corresponding 5-hydroxyimino and 5-methylene derivatives

Synthesis and photochemistry of several title compounds 1-3 containing multiple chromophoric systems are described. The Diels-Alder reactions of 2,6,6-trimethylcyclohexa-2,4-dienone (5) with acetylenes 6a-d provided the adducts 7a-d, which upon hydrolysis furnished the desired bicyclo[2.2.2]octenediones 1a-d. Oximes 2a-d were prepared from diones 1a-d by treatment with hydroxylamine hydrochloride in pyridine. 5-Methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d were obtained via chemoselective Wittig reaction of the corresponding diones 1a-d. Bicyclo[2.2.2]octenediones 1a-c underwent chemoselective oxa-di-pi-methane rearrangement under sensitized conditions and suffered formal ketene extrusion upon direct irradiation. Direct irradiation of 1d afforded 11d via formal ketene extrusion but under sensitization it remained unchanged. Oximes 2a-d suffered ketene extrusion upon direct irradiation and E/Z isomerization under sensitized conditions. On the other hand, 5-methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d generally underwent 1,3-acyl shift. The plausible courses of all these photochemical processes are discussed.     

Convergence theory of extrapolated iterative methods for a certain class of non-symmetric linear systems

Summary A variety of iterative methods considered in [3] are applied to linear algebraic systems of the formAu=b, where the matrixA is consistently ordered [12] and the iteration matrix of the Jacobi method is skew-symmetric. The related theory of convergence is developed and the optimum values of the involved parameters for each considered scheme are determined. It reveals that under the aforementioned assumptions the Extrapolated Successive Underrelaxation method attains a rate of convergence which is clearly superior over the Successive Underrelaxation method [5] when the Jacobi iteration matrix is non-singular.     

The extrapolated first order method for solving systems with complex eigenvalues

An extrapolated form of the basic first order stationary iterative method for solving linear systems when the associated iteration matrix possesses complex eigenvalues, is investigated. Sufficient (and necessary) conditions are given such that convergence is assured. An analytic determination of good (and sometimes optimum) values of the involved real parameter is presented in terms of certain bounds on the eigenvalues of the iteration matrix. The usefulness of the developed theory is shown through a simple application to the conventional Jacobi method.     

Amphiphilic hydrogel nanoparticles. Preparation, characterization, and preliminary assessment as new colloidal drug carriers

Inverse emulsion photopolymerization of acrylated poly(ethylene glycol)-bl-poly(propylene glycol)-bl-poly(ethylene glycol) and poly(ethylene glycol) was successfully employed to prepare stable, cross-linked, amphiphilic nanoparticles. Even at low emulsifier concentrations (2%) and high water-to-hexane weight ratios (35/65), the stability of the inverse emulsion allowed for the formation of well-defined colloidal material. Inverse emulsion characteristics and polymerization conditions could be controlled to vary the size of the nanoparticles between 50 and 500 nm. The presence of hydrophobic nanodomains within these otherwise hydrophilic nanoparticles was verified by using pyrene as a microenvironmentally sensitive probe. The hydrophobic poly(propylene glycol)-rich domains appear to be suitable for incorporation of hydrophobic drugs, encapsulating Doxorubicin up to 9.8% (w/w). We believe that the complex nano-architecture of these materials makes them a potentially interesting colloidal drug delivery carrier system and that the method should be useful for a number of amphiphilic macromolecular precursors.     

Staphylococcus epidermidis adhesion to He, He/O(2) plasma treated PET films and aged materials: contributions of surface free energy and shear rate

Adhesion studies of bacteria (Staphylococcus epidermidis) to plasma modified PET films were conducted in order to determine the role of the surface free energy under static and dynamic conditions. In particular, we investigated the effect of the ageing time on the physicochemical surface properties of helium (He) and 20% of oxygen in helium (He/O₂) plasma treated polyethylene terephthalate (PET) as well as on the bacterial adhesion. Treatment conditions especially known to result in ageing sensitive hydrophilicity (hydrophobic recovery) were intentionally chosen in an effort to obtain the widest possible range of surface energy specimens and also to avoid strong changes in the morphological properties of the surface. Both plasma treatments are shown to significantly reduce bacterial adhesion in comparison to the untreated PET. However, the ageing effect and the subsequent decrease in the surface free energy of the substratum surfaces with time – especially in the case of He treated samples – seem to favor bacterial adhesion and aggregation. The dispersion-polar and the Lifshitz–van der Waals (LW) acid–base (AB) thermodynamic approaches were applied to calculate the Gibbs free energy changes of adhesion (ΔG_adh) of S. epidermidis interacting with the substrates. There was a strong correlation between the thermodynamic predictions and the measured values of bacterial adhesion, when adhesion was performed under static conditions. By decoupling the (ΔG_adh) values into their components, we observed that polar/acid–base interactions dominated the interactions of bacteria with the substrates in aqueous media. However, under flow conditions, the increase in the shear rate restricted the predictability of the thermodynamic models.     

Experimental analysis of the pressure drop and heat transfer through metal foams used as volumetric receivers under concentrated solar radiation

The main objective of this work was to evaluate the behavior of porous materials, when treated as volumetric receivers under concentrated solar radiation. For this reason various porous metallic and ceramic materials have been tested as potential receivers for concentrated solar radiation. The experimental investigation showed that their efficiency was depending on both materials parameters and flow conditions. In this work, a variety of foam materials such as Ni and Ni alloy, inconel, copper, aluminum and SiC with different open cell porosity were tested as potential media to be used as volumetric receivers and heat exchangers. However, since the results were similar, for space economy, only the results of two of them, nickel and inconel were presented in detail and compared with each other.     

Effect of the peptide secondary structure on the peptide amphiphile supramolecular structure and interactions

Bottom-up fabrication of self-assembled nanomaterials requires control over forces and interactions between building blocks. We report here on the formation and architecture of supramolecular structures constructed from two different peptide amphiphiles. Inclusion of four alanines between a 16-mer peptide and a 16 carbon long aliphatic tail resulted in a secondary structure shift of the peptide headgroups from α helices to β sheets. A concomitant shift in self-assembled morphology from nanoribbons to core-shell worm-like micelles was observed by cryogenic transmission electron microscopy (cryo-TEM) and atomic force microscopy (AFM). In the presence of divalent magnesium ions, these a priori formed supramolecular structures interacted in distinct manners, highlighting the importance of peptide amphiphile design in self-assembly.