Destructive adsorption of CCl4 over lanthanum-based solids: linking activity to acid-base properties

The relative activities of a low-surface crystalline and high-surface amorphous LaOCl, further denoted as S1 and S2, have been compared for the destructive adsorption of CCl4. It was found that the intrinsic activity of S2 is higher than that of S1. Both samples were characterized with X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2-physisorption, and Raman and infrared (IR) spectroscopy. IR was used in combination with CO2, CO, and methanol as probe molecules. The CO2 experiments showed that different carbonate species are formed on both materials. For S1, a high surface concentration of bidentate carbonate species and a lower concentration of monodentate carbonate were observed. In the case of S2, bulk carbonates were present together with bridged carbonates. CO adsorption shows that S2 and S1 have very similar Lewis acid sites. However, methanol adsorption experiments showed that S2 had a higher number of stronger Lewis acid sites than S1 and that twofold coordinated methoxy species were more strongly bound than threefold coordinated methoxy species. Because of the analogy between methanol dissociation and the removal of the first chlorine atom in the destructive adsorption of CCl4, the sites enabling twofold coordination were likely to be the same Lewis acid sites actively involved in the destructive adsorption of CCl4. La2O3 was less active than the two LaOCl materials, and therefore, the intrinsic activity of the catalyst increases as the strength of the Lewis acid sites increases. S2 contains more chlorine at the surface than S1, which is expressed by the higher number of sites enabling twofold coordination. Moreover, this explains the difference in destructive adsorption capacity for CCl4 that was observed for the samples S1 and S2. Since LaCl3, being the most acidic phase, is not active for the destructive adsorption of CCl4, basic oxygen atoms, however, remain needed to stabilize the reaction intermediate CCl3 as La-O-CCl3.     

Detection and characterization of the spatial inhibition potential in electroperforated sheet materials

The spatial distribution of tiny holes in sheet materials generated by means of electrical discharges is investigated using spatial statistics techniques. It is shown that whereas the holes appear to be randomly distributed according to a Poisson point pattern, there is in fact a small region around each hole in which the generation of a new one is statistically inhibited as a consequence of the lower impedance path offered by the already made hole. The resulting pattern is known in spatial statistics as a point process with a soft-core inhibition potential, which can be characterized using the pair correlation function.     

Edge linking and image segmentation by combining optical and digital methods

We present a hybrid method for segmentation of intensity images, which combines an optical contouring technique and digital algorithms for linking edge points or image segmentation. In a first stage, the digital image to be processed is displayed in a twisted-nematic liquid-crystal display (LCD), which is placed between a polarizer–analyzer pair at 45 deg (instead of 90 deg as occurs in standard LCDs). It is not difficult to demonstrate that the proposed setup produces a resultant image with very pronounced dark contours at middle intensity. After the optical preprocessing, two different digital algorithms are applied: an edge linking algorithm (modified chain code) and a simple thresholding technique for image segmentation. The proposed procedure works well with monochromatic and color images. The method could be useful as a robust technique for segmentation of large images in real-time, which presents potential applications in medical and biological imaging.     

Compensation of second-order dispersion in femtosecond pulses after filamentation using volume holographic transmission gratings recorded in dichromated gelatin

We have designed and developed a pulse compressor with volume transmission holographic gratings to be implemented in post-compression experiments based on filamentation in gases. Pulse compression down to 13?fs has been demonstrated. The gratings have been recorded in commercial PFG-04 dichromated gelatin emulsions with a recording wavelength of 532?nm, attaining sufficient index modulation to achieve high efficiency when they are illuminated by an 800-nm laser.     

Polyarginine nanocapsules: a new platform for intracellular drug delivery

This report describes the development of a new nanocarrier, named as polyarginine (PArg) nanocapsules, specifically designed for overcoming cellular barriers. These nanocapsules are composed of an oily core and a PArg corona. The attachment of the PArg corona was mediated by its interaction with the oily core, which was conveniently stabilized with phosphatidylcholine. Hybrid PArg/PEG nanocapsules could also be obtained by introducing PEG-stearate in the nanocapsules formation process. The nanocapsules had an average size in the range of 120–160 nm, and a positive surface charge, which varied between +56 and +28 mV for PArg and PArg/PEG nanocapsules, respectively. They could accommodate significant amounts of lipophilic drugs, i.e., docetaxel, in their core, and also polar negatively charged molecules, i.e., plasmid DNA, on their coating. As a preliminary proof-of-principle, we explored the ability of these nanocarriers to enter cancer cells and to inhibit proliferation in the non-small cell lung cancer NCI-H460 cell line, using flow cytometry and confocal microscopy analysis. The results indicated that PArg nanocapsules are rapidly and massively accumulated into the NCI-H460 cells and that the PArg shell plays a critical role in the internalization process. Moreover, the incubation with docetaxel-loaded nanocapsules with NCI-H460 cells led to an enhanced inhibition of their proliferation, as compared to the free drug. Overall, this is the first report of the potential of PArg nanocapsules as intracellular drug delivery vehicles.

     

An efficient and scalable block parallel algorithm of Neville elimination as a tool for the CMB maps problem

This paper analyses the performance of several versions of a block parallel algorithm in order to apply Neville elimination in a distributed memory parallel computer. Neville elimination is a procedure to transform a square matrix A into an upper triangular one. This analysis must take into account the algorithm behaviour as far as execution time, efficiency and scalability are concerned. Special attention has been paid to the study of the scalability of the algorithms trying to establish the relationship existing between the size of the block and the performance obtained in this metric. It is important to emphasize the high efficiency achieved in the studied cases and that the experimental results confirm the theoretical approximation. Therefore, we have obtained a high predicting ability tool of analysis. Finally, we will present the elimination of Neville as an efficient tool in detecting point sources in cosmic microwave background maps.     

Intramolecular [2+2] Photocycloaddition of 3‐ and 4‐(But‐3‐enyl)oxyquinolones: Influence of the Alkene Substitution Pattern,Photophysical Studies,and Enantioselective Catalysis by a Chiral Sensitizer

The intramolecular [2+2] photocycloaddition of four 4‐(but‐3‐enyl)oxyquinolones (substitution pattern at the terminal alkene carbon atom: CH₂, Z‐CHEt, E‐CHEt, CMe₂) and two 3‐(but‐3‐enyl)oxyquinolones (substitution pattern: CH₂, CMe₂) was studied. Upon direct irradiation at λ=300 nm, the respective cyclobutane products were formed in high yields (83–95 %) and for symmetrically substituted substrates with complete diastereoselectivity. Substrates with a Z‐ or E‐substituted terminal double bond showed a stereoconvergent reaction course leading to mixtures of regio‐ and diastereomers with almost identical composition. The mechanistic course of the photocycloaddition was elucidated by transient absorption spectroscopy. A triplet intermediate was detected for the title compounds, which–in contrast to simple alkoxyquinolones such as 3‐butyloxyquinolone and 4‐methoxyquinolone–decayed rapidly (τ≈1 ns) through cyclization to a triplet 1,4‐diradical. The diradical can evolve through two reaction channels, one leading to the photoproduct and the other leading back to the starting material. When the photocycloaddition was performed in the presence of a chiral sensitizer (10 mol %) upon irradiation at λ=366 nm in trifluorotoluene as the solvent, moderate to high enantioselectivities were achieved. The two 3‐(but‐3‐enyl)oxyquinolones gave enantiomeric excesses (ees) of 60 and 64 % at ?25 °C, presumably because a significant racemic background reaction occurred. The 4‐substituted quinolones showed higher enantioselectivities (92–96 % ee at ?25 °C) and, for the terminally Z‐ and E‐substituted substrates, an improved regio‐ and diastereoselectivity.     

A Chiral Thioxanthone as an Organocatalyst for Enantioselective [2+2] Photocycloaddition Reactions Induced by Visible Light

Thioxanthone 1 , which was synthesized in a concise fashion from methyl thiosalicylate, exhibits a significant absorption in the visible light region. It allows for an efficient enantioselective catalysis of intramolecular [2+2] photocycloaddition reactions presumably by triplet energy transfer.