Analytical properties of the amidoxime group. XII

Journal of Thermal Analysis and Calorimetry - The acid-base equilibria of succinediamidoxime (SIDA) were studied by means of potentiometric and thermometric techniques. RefinedpK values (pK...     

Frost heave in argon

The freezing of argon in silica powder is observed to generate bands of pure solid argon in the same manner as in the phenomenon of ice lens formation in the freezing of moist ground. A first principles dynamical theory describes the mechanism of lens formation by the thermomolecular pressure-driven flow of interfacially melted films at the lens-solid boundary.     

Potential of multisyringe flow-based multicommutated systems

This work is aimed at emphasizing the potential of the multicommutated systems based on the multisyringe flow injection analysis (MSFIA) modality. First, the characteristics, advantages and withdraws offered by flow analysis systems based on the different non-segmented modalities are briefly described. In these systems, multicommutation and computer control of the analytical process occupy a predominant place, as in the case of sequential injection analysis (SIA), multicommutated flow injection analysis (MCFIA), MSFIA and multipumping flow systems (MPFS). Next, several examples are given and different aspects of the implementation of analysers based on MSFIA designs for the construction of different analysis systems, including intelligent (smart) systems, use of sample pre-treatment automatic systems, for chromatographic and non-chromatographic determinations as well as use of monolithic or capillary electrophoresis columns are considered.     

Intermolecular interaction potentials for the Ar-C2H2, Kr-C2H2, and Xe-C2H2 weakly bound complexes: information from molecular beam scattering, pressure broadening coefficients, and rovibrational spectroscopy

Integral cross sections and pressure broadening coefficients have been measured for the acetylene-krypton complex, by molecular beam scattering and by high resolution IR spectroscopy, respectively. A new potential energy surface (PES) is proposed to describe structure and dynamical properties of this prototypical weakly bound complex. The PES has been parametrized exploiting a novel atom-bond pairwise additive scheme and has been fitted to the experimental data. A similar PES has been obtained for the acetylene-xenon system by a proper scaling of the interaction parameters of the krypton case, based on empirical considerations. These PESs together with that recently proposed by the same authors [J. Phys. Chem. 109, 8471 (2005)] for the acetylene-argon case have been employed for close coupling calculations of the pressure broadening cross sections and for a characterization of the rovibrational structure of the complexes.     

Nanostructuration of soft hydrogels: synthesis and characterization of saccharidic methacrylate gels

With the tremendous development of biosensors, there is a strong need in new biocompatible materials avoiding possible denaturing of biological species, which can be easily processed with already existing technologies. The scope of this study was to develop new hydrogels which could be nanostructured by common lithographic methods. Therefore, new methacrylate hydrogels are described, which include functionalized monomers bearing either neutral groups, such as saccharidic moieties, anionic, or cationic groups. The gels have been synthesized by redox or photochemical-initiated radical polymerization. Their porosity has been characterized by thermoporometry, AFM, and electronic microscopy. The kinetics of the photocross-linking has been analyzed by piezorheometry on some of the materials and has been shown to be compatible with technological process time range. Although the obtained hydrogels are soft, their nanostructuration into 500-nm patterns could be performed by nanoimprint photolithography process, and these patterns were observed to be stable for several months.     

A membraneless gas-diffusion unit-multisyringe flow injection spectrophotometric method for ammonium determination in untreated environmental samples

A new design of a membraneless gas-diffusion (MGD) unit coupled to a multisyringe flow injection system is proposed. The spectrophotometric determination of ammonium using an acid-base indicator was chosen to show the feasibility of this approach. Hence, in alkaline medium, ammonium ions are transformed into ammonia (donor channel) which diffuses through the headspace into the acceptor stream (bromothymol blue solution), causing a pH change and subsequently a colour change. The exploitation of the enhanced potentialities of this re-designed MGD device was the main purpose of the present work. Hence, several strategies concerning flow management were studied seeking to characterize and improve the analytical features of the methodology and moreover, untreated environmental samples were analysed without previous filtration. Consequently, stopped flow in acceptor channel with continuous flow in donor channel was chosen for the application to wastewater and spiked river water samples. A linear concentration range between 10.0 and 50.0 mg L⁻¹ of NH₄⁺, a limit of detection of 2.20 mg L⁻¹ and a determination frequency of 11 h⁻¹ were obtained.     

Electrochemical Determination of Norepinephrine on Cathodically Pretreated Poly(1,5‐diaminonaphthalene) Modified Electrode

A sensitive and simple electrochemical method for norepinephrine (NE) determination was developed based on a poly(1,5‐diaminonaphthalene) film electrode (PDAN). Cathodically pretreated PDAN presents good selectivity, sensitivity, and reproducibility for NE. The polymer film can be easily electropolymerized onto a platinum electrode by cyclic voltammetry in 1.0 M HClO₄. A cathodic pretreatment, consisting of the application of a potential of ?0.7 V for 3 s (vs. Ag/AgCl) to PDAN before each voltammetric measurement, enhanced the electrochemical activity of NE with no inference of ascorbic acid (AA). In optimized conditions, PDAN presents linear responses for NE in the range of 9.90 to 90.9 µM by differential pulse voltammetry (DPV) with a detection limit of 1.82 µM. A relative standard deviation of 3.0 % was obtained for 10 consecutive measurements of 40.0 µM NE solutions. The cathodically pretreated PDAN was successfully applied for NE determination in pharmaceutical formulation samples.     

The Effects of Grape Polysaccharides Extracted from Grape By-Products on the Chemical Composition and Sensory Characteristics of White Wines

There is an increasing interest in the valorization of wine waste by-products. Grape pomace/marc can be an important source of polyphenols but also of polysaccharides (PSs). Therefore, the aim of this work was to extract PSs from grape pomace and musts and incorporate them into wines to improve their quality and valorize these residues. Two white wines were elaborated and treated with four different PS extracts obtained from white grape pomace, white must, a wine purified extract rich in RG-II, and commercial inactivated yeasts. In general, the use of grape PSs extracted from grape pomace or must improve some characteristics of wine, increasing the polysaccharide and volatile concentrations. These PS extracts can be useful to modulate some taste attributes such as an excess of acidity and bitterness and can also prevent the loss of volatile compounds associated with fruity and floral notes over time. This is the first study that shows the effects of grape polysaccharides on the chemical composition and sensory characteristics of white wines. Considering the obtained results, the grape pomace and surplus of musts can be considered valuable sources to obtain polysaccharide-rich products, opening a new opportunity to take advantage of by-products from the wine industry.