Synthesis and structural characterization of a liquid polyisoprene bearing amidoxime end groups

Azo-bis(isobutyroamidoxime) was synthesized and used as functionalized initiator to prepare a liquid isoprene bearing amidoxime end groups via radical polymerization. The polymer was characterized by FT-IR, Gel Permeation Chromatography and NMR. In particular, the structure of the polymer was investigated using 1D and 2D NMR techniques. The distribution of the different isoprene units (1,4-trans, 1,4-cis, 1,2 and 3,4), as well as the structure of the amidoxime end-groups was determined. It was found that the structure of the end groups was governed by the steric hindrance of the initiator. Only 1,4 and 4,1 functionalized end units were evidenced, with a majority of 4,1 end units.     

High-throughput approach to the catalytic combustion of diesel soot II: Screening of oxide-based catalysts

Following the development of a high-throughput (HT) methodology for the evaluation of diesel soot oxidation catalysts in a 16 parallel channels reactor, a library of over 60 catalysts was tested under optimized conditions. The catalyst compositions were chosen to include solids which specific properties like oxygen storage capacity, oxygen mobility and ionic conductivity. The key parameters for high activity appear related to the presence of active and mobile surface oxygen species, and to an appropriate catalyst particle size in order to favour the number of contacts with the soot. In contrast, high oxygen storage capacity and bulk oxygen ion mobility do not appear as relevant properties for high catalytic activity. Nine new formulations were found to perform better than the reference catalyst “high surface area (HSA) ceria” (Rhodia).     

Near-Field Electron Energy Loss Spectroscopy in Porous Silicon

First results of an Electron Energy Loss Spectroscopy in the Near Field (NFEELS) mode of n⁺ porous silicon are described here. Sequences of EELS spectra in the low loss energy range (0–30 eV) were recorded, using a scanning transmission electron microscope, as the e-beam was scanned across a nano-hole surrounded by Si platelets. This technique is shown to be very sensitive to spectral and spatial changes in the electromagnetic field distribution outside the surface of nanoparticles, governed by their local nature and shape.     

Concomitant use of liquid–liquid batch and continuous plug flow reactors for kinetic model discrimination. Application to the Rh/TPPTS catalysed reduction of the C–C double bond in dimethylitaconate

The biphasic catalytic reduction of the C–C double bond of dimethylitaconate with a water soluble rhodium/triphenylphosphinetrisulphonated sodium salt (TPPTS) complex is investigated. Kinetic studies in a well-mixed batch reactor provide kinetics parameters and an activation energy of 71 kJ mol⁻¹ but cannot discriminate between a first order or a complex kinetic model within the range of substrate concentration where the approximation of linear liquid/liquid partition is respected. Catalytic tests in the centrifugal partition chromatograph (CPC) reactor under steady-state operations in chemical regime and plug flow mode allow discriminating the kinetic models, the complex kinetic rate law being preferred.     

Silicon Substitution for Aluminum in Calcium Silicate Hydrates

²⁷Al MAS and multiquantum (MQ) MASNMR (magic-angle spinning nuclear magnetic resonance) spectroscopy were used to study the substitution of silicon by aluminum in calcium silicate hydrates (C-S-H), which are the main component of hydrated portland cement. Synthetic C-S-H samples were prepared, and their chemical stability was studied. Two-dimensional 3Q-MASNMR spectra revealed the chemical shift and quadrupolar parameters (delta_iso, nu_Q) that labeled aluminum sites in the C-S-H. Tetrahedral aluminum was observed in the bridging and nonbridging sites of the silicate chains.     

Modeling of the Low-Frequency Noise in Thermal Lens Spectrometry

The low-frequency noise observed in thermal lens spectrometry (TLS) can be modeled by assuming that the heated region, constituted by the thermal lens gradient and associated convective stream, behaves as a weakly damped harmonic oscillator with a natural frequency, v_o, which is forced to move at an externally imposed pump frequency, v_p. Out-of-phase lower-frequency oscillations of the TLS signal can be produced both by transient events, such as the beginning of the TLS experiment and small changes in the pump beam stability, and by drift of boundary conditions, such as the temperature of the surroundings. A model is developed and checked using 1-(2-pyridylazo)-2-napthol (PAN) solutions in silicone oil. Consequences of analytical interest are drawn; e.g., the signal-to-noise ratio of the TLS experiments is improved by pumping at the resonance frequency, where v_p = v_o.     

Behavior of Paramagnetic Iron during the Thermal Transformations of Kaolinite

Kaolinites with various degrees of structural order and iron content were heated and subsequently analyzed via electron paramagnetic resonance. Iron was present in two different states in the heated materials, either as dilute structural Fe³⁺ ions or in concentrated Fe³⁺ phases. During metakaolinization, the environment of dilute Fe³⁺ ions changed, following modifications of the Al³⁺ coordination, and the Fe³⁺ concentration increased. With the breakdown of metakaolinite, the diffusion of Fe³⁺ ions induced their exsolution in superparamagnetic iron-rich domains (Fe³⁺ clusters in γ-Al₂O₃ and/or Fe³⁺ oxide nanophases), which produced a decrease in the dilute Fe³⁺ concentration. The subsequent breakdown of γ-Al₂O₃ and the formation of mullite made the dilute Fe³⁺ concentration increase again, because of the incorporation of Fe³⁺ ions in the mullite structure.     

Atmospheric pollution for trace elements in the remote high-altitude atmosphere in central Asia as recorded in snow from Mt. Qomolangma (Everest) of the Himalayas

A series of 42 snow samples covering over a one-year period from the fall of 2004 to the summer of 2005 were collected from a 2.1-m snow pit at a high-altitude site on the northeastern slope of Mt. Everest. These samples were analyzed for Al, V, Cr, Mn, Co, Ni, Cu, Zn, As, Rb, Sr, Cd, Sb, Pb, and Bi in order to characterize the relative contributions from anthropogenic and natural sources to the fallout of these elements in central Himalayas. Our data were also considered in the context of monsoon versus non-monsoon seasons. The mean concentrations of the majority of the elements were determined to be at the pg g(-1) level with a strong variation in concentration with snow depth. While the mean concentrations of most of the elements were significantly higher during the non-monsoon season than during the monsoon season, considerable variability in the trace element inputs to the snow was observed during both periods. Cu, Zn, As, Cd, Sb, and Bi displayed high crustal enrichment factors (EF(c)) in most samples, while Cr, Ni, Rb, and Pb show high EF(c) values in some of the samples. Our data indicate that anthropogenic inputs are potentially important for these elements in the remote high-altitude atmosphere in the central Himalayas. The relationship between the EF(c) of each element and the Al concentration indicates that a dominant input of anthropogenic trace elements occurs during both the monsoon and non-monsoon seasons, when crustal contribution is relatively minor. Finally, a comparison of the trace element fallout fluxes calculated in our samples with those recently obtained at Mont Blanc, Greenland, and Antarctica provides direct evidence for a geographical gradient of the atmospheric pollution with trace elements on a global scale.     

Positive sliding mode control for blood glucose regulation

Biological systems involving positive variables as concentrations are some examples of so-called positive systems. This is the case of the glycemia–insulinemia system considered in this paper. To cope with these physical constraints, it is shown that a positive sliding mode control (SMC) can be designed for glycemia regulation. The largest positive invariant set (PIS) is obtained for the insulinemia subsystem in open and closed loop. The existence of a positive SMC for glycemia regulation is shown here for the first time. Necessary conditions to design the sliding surface and the discontinuity gain are derived to guarantee a positive SMC for the insulin dynamics. SMC is designed to be positive everywhere in the largest closed-loop PIS of plasma insulin system. Two-stage SMC is employed; the last stage SMC2 block uses the glycemia error to design the desired insulin trajectory. Then the plasma insulin state is forced to track the reference via SMC1. The resulting desired insulin trajectory is the required virtual control input of the glycemia system to eliminate blood glucose (BG) error. The positive control is tested in silico on type-1 diabetic patients model derived from real-life clinical data.