Excitation processes leading to ruby emission

We excited the ²T₁-levels in ruby by tunable laser light, pumped bya pulsed YAG:Nd³⁺ laser, and observed the low temperature emissions from the 2$\text{A}$ and $\text{E}$ sublevels of ²E in the mild bottlenecking regime. The R₂-line decay time was about five-fold longer and the ratio of intensities R₂/R₁ higher (by up to a factor 10) than after pumping into ⁴T₂. It is suggested that when ⁴T₂ is pumped the relaxation is nonadiabatic, so that transitions between the sublevels occur while the ²E state relaxes to its normal (trigonal) configuration. The time-development of the relaxing state is studied. It is shown that its coherence between the 2$\text{A}$ and $\text{E}$ sublevels leads to a narrowing of the spectral width in transition between the sublevels.     

Some aspects on thermodynamic properties, phase diagram and alloy formation in the ternary system BAs–GaAs—Part II: BGaAs alloy formation

We present a detailed analysis of the thermodynamics of the BGaAs alloy formation taking into account the question of boron solubility and Gibbs free energy change. We also predict a Gibbs free energy change for the gas phase formation of BAs to be compared to for GaAs. We show that the experimental boron solubility is actually an open question both theoretically and experimentally, while the maximum concentration obtained up to date is reaching 6–7%. It thus follows that despite the low boron solubility, the Gibbs free energy change for the alloy formation is dominated by the chemical term over the mixing energy change. We could deduce order of magnitude for the ratio of the boron partial pressure and that of gallium. P_B could be estimated as being always much lower than P_Ga; it is shown that the alloy content is probably controlled by the Ga equilibrium partial pressure.     

Controlled Radical Polymerization of Ethylene Using Organotellurium Compounds

The first successfully controlled radical polymerization (CRP) of ethylene is reported using several organotellurium chain‐transfer agents (CTAs) under mild conditions (70 °C, 200 bar of ethylene) within the concept of organotellurium‐mediated radical polymerization (TERP). In contrast to preceding works on CRPs of ethylene applying reversible addition–fragmentation chain‐transfer (RAFT), the TERP system provided a high livingness and chain‐end functionalization of polyethylene chains. Molar‐mass distributions with dispersities between 1.3 and 2.1 were obtained up to average molar masses of 5000 g mol^?1. As in the RAFT system, the high reactivity of the growing polyethylenyl radical led to an inherent side reaction. For the presented TERP systems, however, this side reaction did not result in dead chains, while it could even be effectively suppressed by a good choice of the CTA.     

Behaviour of vicinal InP surfaces grown by MOVPE: exploitation of AFM images

InP substrates and epilayers grown by MOVPE have been studied by AFM. For different misorientation angles, we observed the surface of the substrate after annealing under phosphine (PH₃) and of the epilayers under different growth conditions such as growth temperature T_g and trimethylindium (TMI) partial pressure. After annealing the terrace width corresponds to the nominal value of misorientation angle measured by X-ray diffraction. We observed different topographies and roughnesses for the grown layers corresponding to different growth modes. We propose, taking into account the roughness of the surface, a calculation of the step height and terrace width. For 2D nucleation (θ ≤ 0.2° and T_g = 500°C) and step flow mode, the roughness is low while it is increased by step bunching (θ ≥ 0.5° and T_g ≥ 580°C). Moreover we have examined the surface morphology for different misorientation angles and determined the influence of growth conditions (growth temperature, indium partial pressure) on the growth mechanism. At T_g = 580°C the increase of the TMI partial pressure in the reactor enhances the step bunching and leads to larger terraces.     

Local order around rare earth ions during the devitrification of oxyfluoride glasses

Erbium L(3)-edge extended x-ray absorption fine structure (EXAFS) measurements were performed on rare earth doped fluorosilicate and fluoroborate glasses and glass ceramics. The well known nucleating effects of erbium ions for the crystallization of cubic lead fluoride (based on x-ray diffraction measurements) and the fact that the rare earth ions are present in the crystalline phase (as indicated by Er(3+) emission spectra) seem in contradiction with the present EXAFS analysis, which indicates a lack of medium range structural ordering around the Er(3+) ions and suggests that the lead fluoride crystallization does not occur in the nearest neighbor distance of the rare earth ion. Molecular dynamics simulations of the devitrification process of a lead fluoride glass doped with Er(3+) ions were performed, and results indicate that Er(3+) ions lower the devitrification temperature of PbF(2), in good agreement with the experimental results. The genuine role of Er(3+) ions in the devitrification process of PbF(2) has been investigated. Although Er(3+) ions could indeed act as seeds for crystallization, as experiments suggest, molecular dynamics simulation results corroborate the experimental EXAFS observation that the devitrification does not occur at its nearest neighbor distance.     

One-Pot Synthesis of Phosphinylphosphonate Derivatives and Their Anti-Tumor Evaluations

This paper reports on the synthesis of new hydroxymethylene-(phosphinyl)phosphonates (HMPPs). A methodology has been developed to propose an optimized one-pot procedure without any intermediate purifications. Various aliphatic and (hetero)aromatic HMPPs were synthesized in good to excellent yields (53–98%) and the influence of electron withdrawing/donating group substitution on aromatic substrates was studied. In addition, the one-pot synthesis of HMPP was monitored by ³¹P NMR spectroscopy, allowing effective control of the end of the reaction and identification of all phosphorylated intermediate species, which enabled us to propose a reaction mechanism. Optimized experimental conditions were applied to the preparation of biological relevant aminoalkyl-HMPPs. A preliminary study of the complexation to hydroxyapatite (bone matrix) was carried out in order to verify its lower affinity towards bone compared to bisphosphonate molecules. Moreover, in vitro anti-tumor activity study revealed encouraging antiproliferative activities on three human cancer cell lines (breast, pancreas and lung).     

Tracking the interfacial dynamics of PNiPAM soft microgels particles adsorbed at the air–water interface and in thin liquid films

We report the behavior of thermosensitive soft microgel particles adsorbed at the air–water interface. We study the effect of temperature on the adsorption, interfacial diffusion, and surface rheology of pure N-isopropylacrylamide (NiPAM) microgel particles at the air–water interface. We find that the surface tensions of the solutions are the same as those of polyNiPAM solution; hence, their adsorption properties are dominated by the surface activity of the NiPAM repeat units of the particles. Particle-tracking experiments show that the particles adsorb irreversibly at the interface and form stable clusters at very low concentrations, e.g., 5.10^-3 wt%. We suggest that attractions between dangling arms or capillary interaction may be responsible for the formation of these clusters. For concentrations above 10^-2 wt%, the interface is filled with particles, and their Brownian diffusivity is arrested. The compression elastic moduli—measured using the pendant drop method—are one or two orders of magnitude below those obtained for hard particles and NiPAM chains, and their value is probably dominated by the intrinsic compressibility of the particles. The thin liquid films made from microgels exhibit a symmetric drainage, consistent with a high surface viscosity, but their lifetime is surprisingly short, illustrating the fragility of the films. We observed the formation of a monolayer of microgels bridging the two interfaces of the film outside the dimple. This zone grows and thins over time to a point where the microgels are highly compressed and stretched, resulting in the rupture of the film.     

Dynamical processes in sol-gel derived rare-earth doped glasses

We have investigated the dynamical processes of rare-earth photoluminescence in silica glasses produced by the sol-gel method. Generally, static spectroscopic properties are used as a tool to probe the local structure near dopants as well as for the study of glass formation. Rare earth ions are preferred structural probes, especially the Eu³⁺ ion for its sensitivity to local structural modifications and its spectroscopic simplicity. By an analysis of the decaying emission that follows a pulsed laser excitation, we have studied several dynamical processes. Importance of a distribution of different environments for the dopant is clearly seen even for the wet gels. The evolution of the lifetimes allow to study the densification process.     

Bisphosphonate prodrugs: synthesis of new aromatic and aliphatic 1-hydroxy-1,1-bisphosphonate partial esters

Methods for the preparation of various 1-hydroxy-1,1-bisphosphonate partial esters were developed. They were obtained from (alkyl or phenyl) bis(trimethylsilyl) phosphite and aromatic or aliphatic acid chlorides, followed by methanolysis.