Curvature Effects in the Analysis of Pendant Bubble Data: Comparison of Numerical Solutions, Asymptotic Arguments, and Data

The pendant bubble method is commonly used to measure the evolution of the surface tension of surfactant solutions. Initially, the bubble interface is free of adsorbed surfactant. As time progresses, surfactant diffuses to the interface, adsorbs, and reduces the surface tension. The surface tension is assumed to be in equilibrium with the instantaneous surface concentration. Therefore, surface tension data are analyzed in terms of interfacial thermodynamics and mass transfer models in order to infer the mechanisms which determine the surfactant transport. Diffusion from the bulk solution to the bubble can be approximated as diffusion to a spherical interface. Approximating this process as diffusion to a plane introduces significant errors into the data analysis. Mass transfer to a sphere differs from that to a plane; the equilibration of the spherical interface is more rapid simply because of geometry. The failure to account for this effect in the interpretation of pendant bubble data can lead to serious errors in the transport coefficients for the surfactants. In the diffusion-controlled limit, surfactant diffuses to the sublayer immediately adjacent to the interface and adsorbs in local equilibrium according to the adsorption isotherm. There is a closed-form solution for Fick's law describing adsorption to a sphere in an infinite solution which reduces to the Ward and Tordai solution when the bubble radius is large. This equation, along with the adsorption isotherm relating the surface concentration and the sublayer concentration, must be solved numerically in order to solve for the time evolution of the surface concentration. At early times, the adsorption isotherm can be expanded about the clean interface state. At long times, small departures from the equilibrium state can be assumed. In these limits, asymptotic expansions can be obtained. The short- and long-time expansions are found in this study for adsorption to a sphere and compared to those obtained previously for adsorption to a planar interface. In particular, the long-time asymptote for adsorption to a sphere is proportional to t(-3/2); this asymptote differs significantly from that for adsorption to a plane, which goes as t(-1/2). The full solution for adsorption to a sphere is compared to the Ward and Tordai solution for adsorption to a planar interface. From a comparison of the full solutions, it is established that curvature cannot be neglected unless the ratio of the adsorption depth to the bubble radius is negligible. This ratio can be calculated a priori from equilibrium isotherm parameters. Using constants which describe the surfactant C(12)E(8), for which curvature plays a strong role in the surfactant adsorption dynamics, the short- and long-time solutions for adsorption to the interface are compared to the full solutions and to dynamic surface tension data to infer the range of validity of the approximations. Copyright 2001 Academic Press.     

Bioluminescent flow sensor for L-phenylalanine determination in serum

A highly sensitive and rapid bioluminescent flow sensor was developed for the determination of the content of L-phenylalanine (Phe) in serum by monitoring the reduced form of nicotinamide adenine dinucleotide (NADH), produced by immobilized phenylalanine dehydrogenase (PheDH), with bacterial bioluminescent enzymes immobilized on a separate nylon coil. The L-PheDHs extracted from Bacillus badius, Bacillus sphaericus and Rhodococcus sp. M 4 were investigated and the performances of the three immobilized L-PheDH's were analysed. The B. badius reactor was found to give higher transformation rate and better sensitivity; the response was linear from 1 to 100 microM at 25 degrees , with a detection limit of 10 pmoles (0.5 microM). The intra- and inter-assay coefficients of variation were less than 5% and recoveries ranged from 90 to 101%. The results agreed well with those obtained with a chromatographic method for the Phe determination in serum and with the normal reference values.     

Physical peculiarities of divergences emerging in q-deformed statistics

It was found in [A. Plastino, M.C. Rocca, Europhys. Lett. 104, 60003 (2013)]that classical Tsallis theory exhibits poles in the partition function ?? and the mean energy <??>. These occur at a countably set of the q-line. We give here, via asimple procedure, a mathematical account of them. Further, by focusing attention upon thepole-physics, we encounter interesting effects. In particular, for the specific heat, weuncover hidden gravitational effects.     

Bioactive polymeric materials for targeted administration of active agents: synthesis and evaluation

Bioerodible polymers displaying both stealth and targeting properties for the preparation of nanosystems for targeted and controlled delivery of fibrinolytic drugs to the thrombus were prepared by straightforward synthetic routes and characterized. Poly[(maleic anhydride)-alt-(butylvinyl ether)]s were synthesized in the presence of dodecyl mercaptan as chain transfer agent allowing for the preparation of copolymers with tunable molecular weight. 2-Methoxyethanol hemiesters containing antiopsonizing molecules of poly(ethylene glycol) were prepared and further biofunctionalized with a Fab fragment by a two-step reaction. In vitro biocompatibility investigation of the prepared materials supported their suitability for biomedical applications.     

General one-step synthesis of free hexofuranosyl 1-phosphates using unprotected 1-thioimidoyl hexofuranosides

A general one-step strategy is developed for the synthesis of hexofuranosyl 1-phosphates starting from new unprotected glycofuranosyl donors. It required first the preparation of new 1-thiohexofuranosides bearing a thioimidoyl heterocycle as a leaving group. The presence of sulfur and/or nitrogen atom(s) on the aglycon allowed remote activation of these thioglycofuranosides by anhydrous phosphoric acid and led to the target phosphates 9, 27, 29, and 30 in good to excellent selectivities and, more importantly, with very limited or no ring expansion. Moreover, this one-step phosphorylation reaction could be significantly improved by avoiding any tedious protecting group manipulations on negatively charged compounds and by focusing on a simple but general procedure of purification. This approach was applied to the diastereocontrolled synthesis of d-galacto- and d-glucofuranosyl 1-phosphates and also to the preparation of rare epimer and/or deoxy counterparts, that is, d-manno- and d-fucofuranosyl derivatives.     

Classical molecular dynamics model for coupled two component plasmas

This work is an improved continuation of a previous attempt to use classical molecular dynamics (MD) as a tool for the investigation of hot and dense “real” plasmas. “Real” in this context refers to ions and electrons interacting through Coulomb forces and undergoing ionization/recombination. The objective of designing such a non standard approach to plasma equilibrium is to explore a new way to discuss warm and dense matter with a method able to deal with the whole complexity of a N-body system of ions and electrons. Plasma relaxation times can be investigated up to a picosecond. The resulting equilibrium ion populations, built self consistently, are comparable to those found in literature and, potentially validate access to all the statistical data usually derived from MD simulations.     

Elementaranalyse

Ohne Zusammenfassung     

Rheology of carbon nanofiber-reinforced polypropylene

The rheological properties of two different nanocomposite systems consisting in the dispersion of carbon nanofibers (CNFs) in polypropylene are investigated. The nanoreinforced systems were identically prepared with two CNFs that differ only in the length of the fibers being otherwise identical to analyze the effect of fiber aspect ratio. Linear dynamic viscoelasticity and the steady-state rheology of the two different nanocomposites are presented. The system reinforced with CNFs with larger aspect ratio shows several rheological features that resemble peculiarities of rodlike polymers in the nematic liquid crystalline phase.     

Impact of glycosylation on physico–chemical and biological properties of nitrification inhibitors

The lipophilic 2-mercaptobenzothiazole (MBT), known for its nitrification inhibition properties, was derivatized thanks to direct glycosylation reactions. Similar transformations were also performed starting from 2-mercaptobenzimidazole (MBI), structurally close to MBT. The resulting S-linked mono- or disaccharides derived from d-glucose or l-arabinose, and cellobiose, gentiobiose or lactose, respectively, were subsequently studied as novel nitrification inhibitors without any further formulation or physical processes, except dilution in water. Along with ecotoxicity measurements, inhibition properties of the synthesized water soluble glycoconjugates were studied in a model reactor containing nitrification bacteria. The best results were obtained for the gentiobiosyl derivatives simply dissolved in water.