The use of temporary tethers in the meta photocycloaddition reaction

The use of temporary tethers in facilitating meta photocycloaddition reactions between phenol and allyl alcohol derivatives has been investigated. The merits of silicon, carbonate and methylene acetal tethers were assessed, whilst considering strategies for the preparation of the natural products gymnomitrol and gelsemine. The photoadducts were epoxidised, and then subjected to acid catalysed fragmentation with concomitant cleavage of the tether. Depending on whether water or methanol was used during the fragmentation stage of the methylene tethers, the methylene group was either removed altogether or transformed into a MOM group.     

Effect of Ga doping on magneto-transport properties in colossal magnetoresistive La0.7Ca0.3Mn1−xGaxO3 (0<x<0.1)

Samples of La_0.7Ca_0.3Mn_1−xGa_xO₃ with x=0, 0.025, 0.05 and 0.10 were prepared by standard solid-state reaction. They were first characterized chemically, including the microstructure. The magnetic properties and various transport properties, i.e. the electrical resistivity, magnetoresistivity (for a field below 8 T), thermoelectric power and thermal conductivity measured each time on the same sample, are reported. The markedly different behaviour of the x=0.1 sample from those with a smaller Ga content, is discussed. The dilution of the Mn³⁺/Mn⁴⁺ interactions with Ga doping considerably reduces the ferromagnetic double exchange interaction within the manganese lattice leading to a decrease of the Curie temperature. The polaron binding energy varies from 224 to 243 meV with increased Ga doping.     

How homogeneous are the trehalose, maltose, and sucrose water solutions? An insight from molecular dynamics simulations

The structural properties resulting from the reciprocal influence between water and three well-known homologous disaccharides, namely, trehalose, maltose, and sucrose, in aqueous solutions have been investigated in the 4-66 wt % concentration range by means of molecular dynamics computer simulations. Hydration numbers clearly show that trehalose binds to a larger number of water molecules than do maltose or sucrose, thus affecting the water structure to a deeper extent. Two-dimensional radial distribution functions of trehalose solutions definitely reveal that water is preferentially localized at the hydration sites found in the trehalose dihydrate crystal, this tendency being enhanced when increasing trehalose concentration. Over a rather wide concentration range (4-49 wt %), the fluctuations of the radius of gyration and of the glycosidic dihedral angles of trehalose indicate a higher flexibility with respect to maltose and sucrose. At sugar concentrations between 33 and 66 wt %, the mean sugar cluster size and the number of sugar-sugar hydrogen bonds formed within sugar clusters reveal that trehalose is able to form larger clusters than sucrose but smaller than maltose. These features suggest that trehalose-water mixtures would be more homogeneous than the two others, thus reducing both desiccation stresses and ice formation.     

Series expansion calculation of the elastic neutron diffuse scattering: Ice Ih

A theoretical systematic method for the evaluation of the neutron elastic, coherent, diffuse scattering intensity of ice Ih is presented. For each Q vector, the latter is expressed directly as a series expansion of graphs. This technique is analogous to the Ising susceptibility calculation and avoids the explicit use of individual correlation functions. Therefore the series can be easily and exactly expanded to rather high orders. For the computation of the scattering intensity, the correlation model used is based on the ice rules and the normalized probability is written according to Nagle's formulation. The resulting series is convergent and theoretical isodiffusion patterns have been drawn by extending the series up to the 8th order; the accordance with experiment is good.     

Dynamics of the rotational degrees of freedom in an undercooled crystal of cyanoadamantane

Results of molecular dynamics are presented for a simple model of cyanoadamantane crystal. Rotator cubic phase was simulated over a wide range of temperatures. In this system, glass formation is not induced by quenched diluted disorder, but it occurs similarly to conventional glasses. Simulations have shown that the system evolves from free small-step rotational diffusion to jump like motion. The results obtained with this model are used to discuss the validity of the Mode Coupling Theory (MCT) predictions.     

Method development and inter-laboratory comparison about the determination of titanium from titanium dioxide nanoparticles in tissues by inductively coupled plasma mass spectrometry

Nanosized titanium dioxide (TiO₂) is one of the most interesting and valuable nanomaterials for the construction industry but also in health care applications, food, and consumer goods, e.g., cosmetics. Therefore, the properties associated with this material are described in detail. Despite its widespread use, the analytical determination and characterization of nanosized metal oxides is not as straightforward as the comparatively easy-to-detect metallic nanoparticles (e.g., silver or gold). This study presents the method development and the results of the determination of tissue titanium (Ti) levels after treatment of rats with the nanosized TiO₂. Total Ti levels were chosen to evaluate the presence and distribution of TiO₂ nanoparticles. A procedure consisting of incubation with a mixture of nitric acid (HNO₃) and hydrofluoric acid (HF), and heating was developed to digest tissues and TiO₂ nanomaterials in order to determine the total Ti content by inductively coupled plasma mass spectrometry (ICPMS). For the inter-laboratory comparison, altogether four laboratories analyzed the same samples upon digestion using the available ICPMS equipment. A major premise for any toxicokinetic study is the possibility to detect the chemical under investigation in biological samples (tissues). So, the study has to be performed with a dose high enough to allow for subsequent tissue level measurement of the chemical under investigation. On the other hand, dose of the chemical applied should not induce over toxicity in the animal as this may affect its absorption, distribution, metabolism, and excretion. To determine a non-toxic TiO₂ dosage, an acute toxicity study in rats was performed, and the organs obtained were evaluated for the presence of Ti by ICPMS. Despite the differences in methodology and independent of the sample preparation and the ICPMS equipment used, the results obtained for samples with Ti concentrations >4 μg Ti/g tissue agreed well.

Bipolar Electrochemiluminescence Imaging: A Way to Investigate the Passivation of Silicon Surfaces

This work depicts the original combination of electrochemiluminescence (ECL) and bipolar electrochemistry (BPE) to map in real-time the oxidation of silicon in microchannels. We fabricated model silicon-PDMS microfluidic chips, optionally containing a restriction, and monitored the evolution of the surface reactivity using ECL. BPE was used to remotely promote ECL at the silicon surface inside microfluidic channels. The effects of the fluidic design, the applied potential and the resistance of the channel (controlled by the fluidic configuration) on the silicon polarization and oxide formation were investigated. A potential difference down to 6 V was sufficient to induce ECL, which is two orders of magnitude less than in classical BPE configurations. Increasing the resistance of the channel led to an increase in the current passing through the silicon and boosted the intensity of ECL signals. Finally, the possibility of achieving electrochemical reactions at predetermined locations on the microfluidic chip was investigated using a patterning of the silicon oxide surface by etched micrometric squares. This ECL imaging approach opens exciting perspectives for the precise understanding and implementation of electrochemical functionalization on passivating materials. In addition, it may help the development and the design of fully integrated microfluidic biochips paving the way for development of original bioanalytical applications.     

Applications of high-order harmonics

We review applications of high-order harmonic generation in different fields of physics, from spectroscopic studies of atoms and molecules, to interferometry and plasma diagnostics and nonlinear optics.Received: 11 December 2002, Published online: 24 April 2003PACS: 32.80.Fb Photoionization of atoms and ions - 42.65.Ky Frequency conversion; harmonic generation, including higher-order harmonic generationD. Descamps: Present address: CEA/DRECAM/SPAM, CEN Saclay, 91105 Gif-sur-Yvette, France.     

High-gain amplification in Yb:CaF2 crystals pumped by a high-brightness Yb-doped 976 nm fiber laser

We report on high single-pass gain in Yb:CaF₂ crystal longitudinally pumped with a 40 W high-brightness fiber laser source based on an ytterbium-doped ultra-large core photonic crystal rod-type fiber operating at 976 nm. A single-pass small-signal gain of 3.2 has been achieved in a 6 % Yb-doped 10-mm-long CaF₂ crystal at room temperature, outperforming any CW-diode-pumped scheme and paving the way towards very promising innovative lasers and amplifiers schemes merging the Yb-doped solid-state and fiber technologies.     

Phase characterization of the reflection on an extreme UV multilayer: comparison between attosecond metrology and standing wave measurements

We characterize the phase shift induced by reflection on a multilayer mirror in the extreme UV range (80-93?eV) using two techniques: one based on high order harmonic generation and attosecond metrology (reconstruction of attosecond beating by interference of two-photon transitions), and a second based on synchrotron radiation and measurements of standing waves (total electron yield). We find an excellent agreement between the results from the two measurements and a flat group delay shift (±40?as) over the main reflectivity peak of the mirror.