Biocompatible polymers for antibody support on gold surfaces

The elimination or minimization of non-specific protein adsorption from serum is critical for the use of surface plasmon resonance (SPR) sensors for in vitro and in vivo analysis of complex biological solutions. The ultimate goals in this application are to minimize non-specific adsorption of protein and to maximize analyte signal. A reduction of the non-specific protein adsorption from serum of up to 73% compared to carboxymethylated-dextran 500 kDa (CM-dextran) was achieved following a survey of eight biocompatible polymers and 10 molecular weights of CM-dextran. These coatings minimize non-specific adsorption on the sensor while also serving as immobilization matrices for antibody fixation to the probes. Polymers including polysaccharides: CM-dextrans, CM-hyaluronic acid, hyaluronic acid, and alginic acid were investigated. Humic acid, polylactic acid, polyacrylic acid, orthopyridyldisuldfide–polyethyleneglycol–N-hydroxysuccinimide (OPSS–PEG–NHS), and a synthesized polymer; polymethacrylic-acid-co-vinyl-acetate (PMAVA) were also used. The non-specific protein adsorption reduction was measured over a 14 day period at 0 °C for each polymer. Calibration curves using some of these polymers were constructed to show the performance and low detection limit possibilities of these new antibody supports. For many of the polymers, this is the first demonstration of employment as an antibody support for an optical or surface active sensor. CM-dextran is the polymer offering the largest signal for the antigen detection. However, the biocompatible polymers demonstrate a greater stability to non-specific binding in serum. These biocompatible polymers offer different alternatives for CM-dextran.     

Half-sandwich and mixed-ring uranium complexes

The monocyclooctatetraene uranium complex [U(COT)(I)₂(THF)₂] (COT=η-C₈H₈; THF=tetrahydrofuran), isolated from the reaction of bis(cyclooctatetraene)uranium with iodine, is a precursor for the synthesis of the alkyl derivatives [U(COT)(CH₂Ph)₂i (HMPA) ₂], [U(COT)(CH₂SiMe₃)₂(HMPA)] (HMPA=hexamethyl phosphorous triamide) and [U(COT)CH₂SiMe₃)₃] [Li(THF)₃] and of the mixed-ring compounds [U(COT)(η-C₅R₅)(I)] (R=H or Me). The last were used to prepare the amide and alkyl complexes [U(COT)(η-C₅H₅)(N{SiMe₃}₂)] and [U(COT)(η-C₅Me₅)(CH₂SiMe₃)].     

Gas-Phase Lithium Cation Basicity: Revisiting the High Basicity Range by Experiment and Theory

According to high level calculations, the upper part of the previously published FT-ICR lithium cation basicity (LiCB at 373 K) scale appeared to be biased by a systematic downward shift. The purpose of this work was to determine the source of this systematic difference. New experimental LiCB values at 373 K have been measured for 31 ligands by proton-transfer equilibrium techniques, ranging from tetrahydrofuran (137.2 kJ mol^?1) to 1,2-dimethoxyethane (202.7 kJ mol^?1). The relative basicities (ΔLiCB) were included in a single self-consistent ladder anchored to the absolute LiCB value of pyridine (146.7 kJ mol^?1). This new LiCB scale exhibits a good agreement with theoretical values obtained at G2(MP2) level. By means of kinetic modeling, it was also shown that equilibrium measurements can be performed in spite of the formation of Li⁺ bound dimers. The key feature for achieving accurate equilibrium measurements is the ion trapping time. The potential causes of discrepancies between the new data and previous experimental measurements were analyzed. It was concluded that the disagreement essentially finds its origin in the estimation of temperature and the calibration of Cook’s kinetic method. Graphical Abstract

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2-Groupe des classes positives d'un corps de nombres et noyau sauvage de la K-théorie

We compute the 2-rank of the wild kernel WK₂(F) of a number field by constructing a 2-class group ad hoc. The main result generalizes in the more intricate case the canonical isomorphism established for odd primes under the assumption in a previous article (cf. (Acta. Arith. 67 (1994) 335; Math. Z. 238 (2001) 335)). It involves a criterium of triviality for the 2-part of the wild kernel of Galois number fields and, in the particular case of quadratic fields, it leads to a logarithmic interpretation of the diophantine conditions obtained by other authors.     

Concentration of sodium ion as the determining factor for the association of dansyl amino acids with the teicoplanin molecule in reversed-phase liquid chromatography

The mechanism of the binding of D,L dansyl amino acids to teicoplanin was investigated. Na+ was used as an indicator of the interactions between the solutes and teicoplanin. The number (n) of sodium ions, Na+, excluded from the solute-teicoplanin interface when analyte transfer occurred was determined. A thermodynamic study and enthalpy-entropy compensation were performed to further explore the interaction mechanism. From these results, it was shown that teicoplanin was balanced between 2 conformational states characterized by distinct enantioselective properties. This approach indicates that liquid chromatography (LC) is a useful tool to extract physicochemical and molecular information from retention data. Thus, LC can be used as a complementary technique with the conventional techniques of molecular interaction analysis.     

A Two-Dimensional Network Model to Simulate Permeability Decrease Under Hydrodynamic Effect of Particle Release and Capture

A model was developed to simulate permeability decrease induced by hydrodynamic effects when injecting a fluid in a reservoir with respect to particle release and capture mechanisms and the parameters of the fluid–rock system. The kinetics of particle release and capture were integrated after computing the initial permeability of the porous medium with a square lattice of a two–dimensional network model. The rate of particle release is related to the difference between a microscopic velocity of the fluid and a critical velocity. The permeability decrease shows a direct link to the reduction of pore throat radii by three mechanisms of particle capture: straining and particle accumulation through direct interception or diffusion. Comparison between the simulations and the experimental results shows that the model reproduces the physics of the permeability decrease phenomenon, although the values are overestimated. The difference between the two sets of results can be explained by the fact that the simulations are realized at constant pressure whereas the experiments are realized at constant flow rate, and that re–entrainment of the trapped particles was not taken into account in the model.     

Influence of the Grain Boundaries on the Heat Transfer in Laser Ceramics

Grain boundaries play a key role in determining several key properties of polycrystalline laser ceramics. Heat transfer measurements at low temperature constitute a good tool to probe grain boundaries. We review the results of heat transfer measurements in polycrystalline Y₃Al₅O₁₂ garnets as well as Y₂O₃ and Lu₂O₃ sesquioxide materials obtained by self-energy-driven sintering of nano-particles. The average phonon mean free path in Y₃Al₅O₁₂ was found to be significantly larger than the average grain size and to scale with temperature as T ⁻² at low temperature. Existing models describing the interaction between phonons and grain boundaries are reviewed. Correct temperature dependence of the mean free path and order of magnitude of scattering rates were found by assuming the existence of a grain boundary layer having acoustic properties different from those of the bulk. A different temperature dependence of phonon mean free path was found for the sesquioxides and was ascribed to the stronger elastic anisotropy of these materials. The thermal resistance associated to the grain boundaries of laser ceramics was found to be lower than in other dense polycrystalline ceramic materials reported in the literature.