Quantitative determination of hexavalent chromium in aqueous solutions by UV-Vis spectrophotometer

In the last decade, different methods have been developed for the determination of chromium(VI) concentration in water. These methods use high cost equipment or they require a long preparation time. Because of their drawbacks, this paper describes an on-line, rapid and sensitive procedure for the determination of Cr(VI) concentrations in aqueous solutions via pH and absorption measurements. Only four Cr(VI) species are considered. The effects of pH and of total amount of chromium on the Cr(VI) speciation are investigated. The molar absorptivities of four chromium species at 371 nm are determined by minimising an objective function. The knowledge of these molar absorptivities and the measurements of pH and absorption at 371 nm lead to a rapid determination of total Cr(VI) concentration. The reliability and applicability of the method were confirmed using synthetic water samples.      

Total synthesis,isolation, surfactant properties,and biological evaluation of ananatosides and related macrodilactone-containing rhamnolipids

Rhamnolipids are a specific class of microbial surfactants, which hold great biotechnological and therapeutic potential. However, their exploitation at the industrial level is hampered because they are mainly produced by the opportunistic pathogen Pseudomonas aeruginosa. The non-human pathogenic bacterium Pantoea ananatis is an alternative producer of rhamnolipid-like metabolites containing glucose instead of rhamnose residues. Herein, we present the isolation, structural characterization, and total synthesis of ananatoside A, a 15-membered macrodilactone-containing glucolipid, and ananatoside B, its open-chain congener, from organic extracts of P. ananatis. Ananatoside A was synthesized through three alternative pathways involving either an intramolecular glycosylation, a chemical macrolactonization or a direct enzymatic transformation from ananatoside B. A series of diasteroisomerically pure (1→2), (1→3), and (1→4)-macrolactonized rhamnolipids were also synthesized through intramolecular glycosylation and their anomeric configurations as well as ring conformations were solved using molecular modeling in tandem with NMR studies. We show that ananatoside B is a more potent surfactant than its macrolide counterpart. We present evidence that macrolactonization of rhamnolipids enhances their cytotoxic and hemolytic potential, pointing towards a mechanism involving the formation of pores into the lipidic cell membrane. Lastly, we demonstrate that ananatoside A and ananatoside B as well as synthetic macrolactonized rhamnolipids can be perceived by the plant immune system, and that this sensing is more pronounced for a macrolide featuring a rhamnose moiety in its native ¹C₄ conformation. Altogether our results suggest that macrolactonization of glycolipids can dramatically interfere with their surfactant properties and biological activity.

We show that macrolactonization of gluco- and rhamnolipids dramatically interfere with their surfactant properties and biological activity.     

Simple ion chromatographic method for the determination of chlormequat residues in pears

Current methods for quantitative determination of chlormequat residues in food crops are characterized by rather low recoveries and the need for derivatization (in case of gas chromatography, GC), or by high capital investment (in case of liquid chromatography–mass spectrometry, LC–MS). We propose a cation-exchange chromatography method for the analysis of chlormequat in pears. The method is based on extraction of the target compound with 40 mM HCl, followed by centrifugation and filtration. The filtrate is directly injected into an ion chromatograph equipped with a commercially available cation-exchange column and a suppressed conductivity detection system. While the limit of detection (LOD) (0.5 mg/kg) may not be small enough to allow dietary analysis, the method meets all validation requirements and is an alternative for the existing GC and LC–MS methods in quality control.     

Non-adiabatic interactions in charge transfer collisions

An analysis of the charge transfer mechanism in the collision of multiply charged ions with molecular and biomolecular targets is performed, considering the non-adiabatic interactions between the molecular states involved. Collisions of doubly charged C ²⁺ ions on small molecular targets, CO and OH, have been investigated, together with the analysis of charge transfer between C ⁴⁺ ions on uracil and halouracil biomolecular targets. The process is studied theoretically by means of ab-initio molecular calculations followed by a semi-classical treatment of the collision dynamics. The influence of rotational couplings is discussed with regard to the collision energy. Strong anisotropic and vibration effects are pointed out.     

The wave-particle dualism in 1992: A summary

We review the past and present theoretical and experimental situations relating to wave-particle dualism. New tests aimed at enlightening the individual behavior as awave, then as aparticle, of asingle quantum mechanical system in the same experimental run are presented. The related epistemological, philosophical, and historical backgrounds are presented in a twofold exposition taking into account thepositivistic standard Copenhagen interpretation as well as therealist de Broglian point of view.     

Bounds and Heuristics for the Shortest Capacitated Paths Problem

Given a graph G, the Shortest Capacitated Paths Problem (SCPP) consists of determining a set of paths of least total length, linking given pairs of vertices in G, and satisfying capacity constraints on the arcs of G.We formulate the SCPP as a 0-1 linear program and study two Lagrangian relaxations for getting lower bounds on the optimal value. We then propose two heuristic methods. The first one is based on a greedy approach, while the second one is an adaptation of the tabu search meta-heuristic.     

Viscosity of aqueous mixtures of silver and thallium nitrates with calcium or cadmium nitrates from pure fused salt to pure water

Fused salt-water systems extending from pure fused salt to pure water have been less studied than dilute aqueous solutions, despite their practical and theoretical importance. Even fewer studies have been made regarding the influence of the temperature upon transport properties. The present publication brings new interesting information on the viscous flow properties of the following two fused nitrate-water systems containing monovalent and divalent cations: AgNO₃–TINO₃–M(NO₃)₂–H₂O where M=Ca or Cd, with the TINO₃ and M(NO₃)₂ mole fractions in the anhydrous salt fixed at 0.436 and 0.100, respectively. The parameters in the Arrhenius, Eyring, Batschinski and the Abraham and Abraham equations are found to be well correlated with the properties of the components of the melts. The temperature effect allows a discussion to be made in terms of structural features such as holes and free volumes.     

Pyrene-sensitised near-IR luminescence from ytterbium and neodymium complexes

Ytterbium and neodymium have been shown to exhibit sensitised emission following excitation of pyrene chromophores. Sensitised emission is demonstrated in self-assembled complexes and in azamacrocycle derivatives bearing pendent pyrene groups. Energy transfer in these systems is dependent on the nature of the link between the ligand and the complex.     

Fragmentation characteristics of permethylated oligosaccharides using a matrix-assisted laser desorption/ionization two-stage time-of-flight (TOF/TOF) tandem mass spectrometer

Matrix-assisted laser desorption/ionization two-stage time-of-flight (MALDI-TOF/TOF) tandem mass spectrometry (MS/MS) was applied to characterize permethylated oligosaccharides. Under these ionization conditions such derivatives yield intense signals corresponding to sodium-cationized molecular species. A systematic study was conducted on a series of neutral and sialylated permethylated oligosaccharides to allow rationalization of the fragmentation processes. The major fragments observed in the MALDI-TOF/TOF-MS/MS spectra result from cleavage of glycosidic bonds, preferentially at N-acetylhexosamine and sialic acid residues. The fragments originating from both the reducing and the non-reducing ends of the glycan yield information on sequence and branching. Cross-ring cleavages, which are very informative of the linkages of the monosaccharide residues constituting these oligosaccharides, and 'internal' cleavage ions which are derived from elimination of substituents from around the pyranose ring, were also observed. This extensive fragmentation was shown to be useful for the structural characterization of oligosaccharides. MALDI-TOF/TOF-MS/MS of permethylated oligosaccharides appears to be a powerful tool for carbohydrate structural analysis.