ESR study of aqueous micellar solutions of perfluoropolyether surfactants with the use of fluorinated spin probes

The acid-base properties of synthetically prepared and well-characterized hydroxyapatite (HAP) in contact with KNO3 solutions were investigated at 25 degrees C, through potentiometric titrations, zeta-potential measurements, and surface complex modeling. Aliquots of suspension were withdrawn every 0.5 pH unit during the titration procedure and analyzed for calcium and phosphate. It was found that, even for rapid titration experiments, a remarkable amount of H+ ions (H+dissol.) is consumed in the bulk solution in reacting with species coming from the dissolution of HAP. These H+ ions must be taken into account in the H+ mass balance, in order for true value for the point of zero charge (pzc=6.5+/-0.2) and consequently true value for the surface charge (sigma0) to be obtained. Besides the conventional potentiometric titration technique, it was found that pzc may be determined much more easily as the intersection point of the suspension titration curve and the blank one modified to include the amount of H+dissol. obtained at one ionic strength. Finally, a surface complexation model was proposed for the development of surface charge. Experimental data were satisfactorily fitted by using the value of 4.2 F m-2 for the capacitance.     

A modifier that enables the easy dispersion of alkyl-coated nanoparticles in an epoxy network

Nanoparticles (NPs) coated with alkyl chains cannot be dissolved in diglycidylether of bisphenol A (DGEBA), which is a typical monomer used in the synthesis of epoxy networks. We show that adding small amounts of the linear amphiphilic polymer obtained by reaction of DGEBA with dodecylamine, produced a stable dispersion of dodecanethiol-coated gold NPs in DGEBA. The anionic homopolymerization of this blend initiated by a tertiary amine led to a nanocomposite with a uniform dispersion of gold NPs. The selected crosslinking chemistry allowed covalent bonding of the modifier to the matrix, avoiding phase separation and enabling easy tuning of the thermal properties of the matrix.     

Diesel soot combustion. KNO3 and KOH catalysts supported on zirconia

KNO₃/ZrO₂ and KOH/ZrO₂ catalysts were studied and found active in the catalytic soot combustion. Two equipments were used to carry out the combustion experiments: a thermogravimetric reactor with an O₂/He feed and a fixed bed microreactor with NO/O₂/He feed.     

Cyclic RGD peptidomimetics containing bifunctional diketopiperazine scaffolds as new potent integrin ligands

The synthesis of eight bifunctional diketopiperazine (DKP) scaffolds is described; these were formally derived from 2,3-diaminopropionic acid and aspartic acid (DKP-1-DKP-7) or glutamic acid (DKP-8) and feature an amine and a carboxylic acid functional group. The scaffolds differ in the configuration at the two stereocenters and the substitution at the diketopiperazinic nitrogen atoms. The bifunctional diketopiperazines were introduced into eight cyclic peptidomimetics containing the Arg-Gly-Asp (RGD) sequence. The resulting RGD peptidomimetics were screened for their ability to inhibit biotinylated vitronectin binding to the purified integrins α(v)β(3) and α(v)β(5), which are involved in tumor angiogenesis. Nanomolar IC(50) values were obtained for the RGD peptidomimetics derived from trans DKP scaffolds (DKP-2-DKP-8). Conformational studies of the cyclic RGD peptidomimetics by (1)H?NMR spectroscopy experiments (VT-NMR and NOESY spectroscopy) in aqueous solution and Monte Carlo/Stochastic Dynamics (MC/SD) simulations revealed that the highest affinity ligands display well-defined preferred conformations featuring intramolecular hydrogen-bonded turn motifs and an extended arrangement of the RGD sequence [Cβ(Arg)-Cβ(Asp) average distance ≥8.8??]. Docking studies were performed, starting from the representative conformations obtained from the MC/SD simulations and taking as a reference model the crystal structure of the extracellular segment of integrin α(v)β(3) complexed with the cyclic pentapeptide, Cilengitide. The highest affinity ligands produced top-ranked poses conserving all the important interactions of the X-ray complex.     

Selection of a New Whole Cell Biocatalyst for the Synthesis of 2-Deoxyribose 5-Phosphate

2-Deoxyribose 5-phosphate (DR5P) is a key intermediate in the biocatalyzed preparation of deoxyribonucleosides. Therefore, DR5P production by means of simpler, cleaner, and economic pathways becomes highly interesting. One strategy involves the use of bacterial whole cells containing DR5P aldolase as biocatalyst for the aldol addition between acetaldehyde and d-glyceraldehyde 3-phosphate or glycolytic intermediates that in situ generate the acceptor substrate. In this work, diverse microorganisms capable of synthesizing DR5P were selected by screening several bacteria genera. In particular, Erwinia carotovora ATCC 33260 was identified as a new biocatalyst that afforded 14.1-mM DR5P starting from a cheap raw material like glucose.     

3D analysis of the morphology and spatial distribution of nitrogen in nitrogen-doped carbon nanotubes by energy-filtered transmission electron microscopy tomography

We present here the application of the energy-filtered transmission electron microscopy (EFTEM) in the tomographic mode to determine the precise 3D distribution of nitrogen within nitrogen-doped carbon nanotubes (N-CNTs). Several tilt series of energy-filtered images were acquired on the K ionization edges of carbon and nitrogen on a multiwalled N-CNT containing a high amount of nitrogen. Two tilt series of carbon and nitrogen 2D maps were then calculated from the corresponding energy-filtered images by using a proper extraction procedure of the chemical signals. Applying iterative reconstruction algorithms provided two spatially correlated C and N elemental-selective volumes, which were then simultaneously analyzed with the shape-sensitive reconstruction deduced from Zero-Loss recordings. With respect to the previous findings, crucial information obtained by analyzing the 3D chemical maps was that, among the two different kind of arches formed in these nanotubes (transversal or rounded ones depending on their morphology), the transversal arches contain more nitrogen than do the round ones. In addition, a detailed analysis of the shape-sensitive volume allowed the observation of an unexpected change in morphology along the tube axis: close to the round arches (with less N), the tube is roughly cylindrical, whereas near the transversal ones (with more N), its shape changes to a prism. This relatively new technique is very powerful in the material science because it combines the ability of the classical electron tomography to solve 3D structures and the chemical selectivity of the EFTEM imaging.     

The Dual Action of Epigallocatechin Gallate (EGCG), the Main Constituent of Green Tea, against the Deleterious Effects of Visible Light and Singlet Oxygen-Generating Conditions as Seen in Yeast Cells

Green tea extracts (GTEs) as well as their main component, the polyphenol epigallocatechin gallate (EGCG), are known for their versatile antioxidant, antimicrobial, antitumoral or anti-inflammatory effects. In spite of the huge beneficial action, there is increasing evidence that under certain conditions green tea and its components can be detrimental to living organisms. Using Saccharomyces cerevisiae strains with various defects in the response to oxidative stress, we found that GTEs or EGCG act in synergy with visible light, exhibiting either deleterious or protective effects depending on the solvent employed. Similar synergistic effects could be observed under singlet oxygen-generating conditions, such as light exposure in the presence of photosensitizers or UV-A irradiation, therefore solvent variance may represent a powerful tool to modulate the preparation of green tea extracts, depending on the intended target.     

Sparsity-certifying Graph Decompositions

We describe a new algorithm, the (k, ℓ)-pebble game with colors, and use it to obtain a characterization of the family of (k, ℓ)-sparse graphs and algorithmic solutions to a family of problems concerning tree decompositions of graphs. Special instances of sparse graphs appear in rigidity theory and have received increased attention in recent years. In particular, our colored pebbles generalize and strengthen the previous results of Lee and Streinu [12] and give a new proof of the Tutte-Nash-Williams characterization of arboricity. We also present a new decomposition that certifies sparsity based on the (k, ℓ)-pebble game with colors. Our work also exposes connections between pebble game algorithms and previous sparse graph algorithms by Gabow [5], Gabow and Westermann [6] and Hendrickson [9]. Ileana Streinu; Research of both authors funded by the NSF under grants NSF CCF-0430990 and NSF-DARPA CARGO CCR-0310661 to the first author.     

Sparse hypergraphs and pebble game algorithms

A hypergraph G=(V,E) is (k,ℓ)-sparse if no subset V^′V spans more than k|V^′|−ℓ hyperedges. We characterize (k,ℓ)-sparse hypergraphs in terms of graph theoretic, matroidal and algorithmic properties. We extend several well-known theorems of Haas, Lovász, Nash-Williams, Tutte, and White and Whiteley, linking arboricity of graphs to certain counts on the number of edges. We also address the problem of finding lower-dimensional representations of sparse hypergraphs, and identify a critical behavior in terms of the sparsity parameters k and ℓ. Our constructions extend the pebble games of Lee and Streinu [A. Lee, I. Streinu, Pebble game algorithms and sparse graphs, Discrete Math. 308 (8) (2008) 1425–1437] from graphs to hypergraphs.