Anomalous dispersion in nanocomposite films at the surface plasmon resonance

Nanocomposite thin films formed by Cu nanocrystals (NCs) embedded in an amorphous aluminium oxide (Al₂O₃) host have been prepared by alternate pulsed laser deposition. Spectroscopic ellipsometry is used to determine the effective refractive index (n=n+ik). The extinction coefficient is non-negligible and shows a broad absorption band related to the surface plasmon resonance. In the neighbourhood of this wavelength, the real part of the refractive index undergoes an anomalous dispersion, leading to a significant increase of the n value of the composite compared to that of the host. When the Cu content is low enough, about 2 at. %, the use of an effective medium approach combined with a regression method allows us to determine the metal content and film thickness from the ellipsometric measurements. For larger concentrations this approach is no longer valid. Received: 31 July 2001 / Revised version: 21 September 2001 / Published online: 15 October 2001     

Replacing the Rhamnose-Xylose Moiety of QS-21 with Simpler Terminal Disaccharide Units Attenuates Adjuvant Activity in Truncated Saponin Variants

Adjuvants are key immunostimulatory components in vaccine formulations, which improve the immune response to the co-administered antigen. The saponin natural product QS-21 is one of the most promising immunoadjuvants in the development of vaccines against cancer and infectious diseases but suffers from limitations that have hampered its widespread human use. Previous structure–activity relationship studies have identified simplified saponin variants with truncated carbohydrate chains, but have not focused on the influence of the linear oligosaccharide domain of QS-21 in adjuvant activity. Herein, an expeditious 15-step synthesis of new linear trisaccharide variants of simplified QS-21-derived adjuvants is reported, in which the complex terminal xylose-rhamnose moiety has been replaced with commercially available, simpler lactose and cellobiose disaccharides in a β-anomeric configuration. In vivo immunological evaluation of the synthetic saponins showed attenuated antibody responses, highlighting the negative impact of such carbohydrate modifications on adjuvant activity, which could be associated with higher saponin conformational flexibility.     

Ultraviolet Erythematic Radiation Dose Received by Golfers in Winter,in Valencia

This article analyzes Ultraviolet Erythematic Radiation (UVER) dose received by several golf players in winter in Valencia. Playing golf involves spending several hours outdoors because of the length of golf matches and training. Moreover, in Valencia there are many golf players coming from northern Europe, with a phototype very sensitive (I–II). For that reason, these people have an increasing risk while playing. This article shows that harmful effects coming from UVER radiation may occur not only in summer time but also in winter, especially at these latitudes. VioSpor dosimeters have been used to develop this analysis over several golf players on January 2013 between 10:00 h and 15:00 h, local time.     

Methoxycarbonylation of olefins catalyzed by palladium(II) complexes containing naphthyl(diphenyl)phosphine ligands

Palladium(II) complexes containing phosphine donor ligands derived from naphthyl(diphenyl)phosphine were synthesized and characterized by NMR and elemental analysis. The complexes were studied as catalyst precursors in the methoxycarbonylation reaction of several aromatic and aliphatic olefins under mild conditions. The catalysts reported high chemoselectivities (over 96%) and regioselectivities between 44% and 93% for different olefins. The best results were obtained over a styrene substrate with 97% of conversion after 6 h of reaction, with high regioselectivity (93%). Kinetic studies permitted the determination of the rate law (v = k [substrate]^1.21±0.02 [catalyst]^0.94±0.11 [acid]^0.52±0.03 [MeOH]^0.53±0.05 [CO]^0.65±0.03) for methoxycarbonylation of styrene. Copyright © 2014 John Wiley & Sons, Ltd.     

Formation and synchronization of autocatalytic noise-sustained structures under Poiseuille flow

The formation and synchronization of 2D noise-sustained structures are investigated for Gray–Scott kinetics in packed-bed reactors under Poiseuille flows, when identical systems are submitted to independent spatiotemporal Gaussian white noise sources. A finite-wavelength instability is theoretically predicted and numerically confirmed for uncoupled reactors. In particular, noise-sustained structures that flow with viscous boundary conditions are numerically observed above threshold. When the systems are coupled in master–slave configuration, the numerical simulations show that the slave system replicates to a very high degree of precision the convective patterns arising in the master one due to the selective amplification of noise. The nature of the synchronization and the stability of the synchronization manifold are elucidated.     

Carbon Monoxide Oxidation on Pt Single Crystal Electrodes: Understanding the Catalysis for Low Temperature Fuel Cells

Herein the general concepts of fuel cells are discussed, with special attention to low temperature fuel cells working in alkaline media. Alkaline low temperature fuel cells could well be one of the energy sources in the next future. This technology has the potential to provide power to portable devices, transportation and stationary sectors. With the aim to solve the principal catalytic problems at the anode of low temperature fuel cells, a fundamental study of the mechanism and kinetics of carbon monoxide as well as water dissociation on stepped platinum surfaces in alkaline medium is discussed and compared with those in acidic media. Furthermore, cations involved as promoters for catalytic surface reactions are also considered. Therefore, the aim of the present work is not only to provide the new fundamental advances in the electrocatalysis field, but also to understand the reactions occurring at fuel cell catalysts, which may help to improve the fabrication of novel electrodes in order to enhance the performance and to decrease the cost of low temperature fuel cells.