High‐performance liquid chromatography/electrospray ionization tandem mass spectrometric investigation of stilbenoids in cell cultures of Vitis vinifera L., cv. Malvasia

Cell suspension cultures of Vitis vinifera L., particularly after elicitation, have shown the ability to biosynthesize several stilbenoids. In this work the application of specific tandem mass spectrometry (MS/MS) experiments and the integration with data from UV‐vis spectra, available only for the main compounds of the extract, allowed the detection of over 20 different stilbenoids. Up to eight monoglicosides, both monomers and dimers, a high number of dimer forms (up to 17), belonging to the group of viniferins and to their oxidized derivatives, were identified in the extract of Malvasia cell cultures. Moreover, the selectivity and sensitivity of the method allowed detection also of a few cis derivatives (up to 3) present in very low concentrations and presumably produced by the light exposure during treatment of the sample. To the best of the authors' knowledge, there are no literature data on MS/MS experiments targeted to simultaneously study monomeric and dimeric stilbenoids, both as free and glycosilated forms, in a complex mixture from V. vinifera cell suspension cultures. Copyright © 2010 John Wiley & Sons, Ltd.     

A sensor based on silver nanoparticles synthesized on carbon graphite sheets for the electrochemical detection of nitrofurazone: Application: Tap water,commercial milk and human urine

Nitrofurazone is a nitrofuran-family synthetic chemical that has been used to treat bacterial infections since 1993. Silver nanoparticles synthesized by the thermal technique on graphite carbon sheets under optimal conditions were used to develop a highly sensitive electrochemical sensor. The main experimental characteristics are optimized to assure that this sensor functions correctly. Scanning electron microscope, X-ray diffraction, infrared spectroscopy were used to determine the chemical composition and morphology of the prepared pastes. With a maximal reduction peak of La nitrofurazone observed at ?0.57V/Ag-NPs@CPE versus Ag/AgCl, this sensor demonstrated good electrocatalytic activity for the reduction of La nitrofurazone. The influence of phosphate buffer solution pH indicates that the numbers of protons and electrons in the reaction at the surface of our constructed sensor were the same. The LOD and LOQ were calculated to be 1.2 × 10^?8 M and 1.3 × 10^?7 M, respectively. Using the differential pulse voltammetry technique, the calibration curve was established in the concentration range of 10^?4 M to 2 × 10^?7 M. Our Ag-NPs@CPE sensors were evaluated in order to detect nitrofurazone in real contaminated samples tap water, commercial milk, and human urine, in particular. The electroanalysis results show a very high recovery rate of more than 96% on average, permitting us to determine that our sensors are functional under optimum working conditions.     

The Richest Collection of Tautomeric Polymorphs: The Case of 2‐Thiobarbituric Acid

Five new polymorphs and one hydrated form of 2‐thiobarbituric acid have been isolated and characterised by solid‐state methods. In both the crystalline form II and in the hydrate form, the 2‐thiobarbituric molecules are present in the enol form, whereas only the keto isomer is present in crystalline forms I (reported in 1967 by Calas and Martinex), III , V and VI . In form IV , on the other hand, a 50:50 ordered mixture of enol/keto molecules is present. All new forms have been characterised by single‐crystal X‐ray diffraction, 1D and 2D (¹H, ¹³C, and ¹⁵N) solid‐state NMR spectroscopy, Raman spectroscopy and X‐ray powder diffraction at variable temperature. It has been possible to induce keto–enol conversion between the forms by mechanical methods. The role of hydrogen‐bond interactions in determining the relative stability of the polymorphs and as a driving force in the conversions has been ascertained. To the best of the authors’ knowledge, the 2‐thiobarbituric family of crystal forms represents the richest collection of examples of tautomeric polymorphism so far reported in the literature.     

Systematic Variation of Length Ratio and the Formation of Smectic A and Smectic C Phases

The phase diagrams of four binary mixtures of chemically similar smectogenic mesogens differing only in molecular length are investigated. In these bidisperse systems the length ratio varies systematically. The phase diagrams show the stabilization of the smectic A and the destabilization of the smectic C phase with increasing length ratio as a general trend. Detailed small‐angle X‐ray diffraction and electro‐optic measurements revealed a decrease in smectic translational order and a continuous reduction of the tilt angle with increasing length difference. These surprising results are of general interest for the understanding of the structure and dynamics of smectic phases. The remarkably strong impact of the length difference on the smectic layer structure and the phase behavior is discussed from a mechanistic point of view taking into account sterical interactions. For the observed structural changes in these bidisperse smectics we propose pronounced out‐of‐layer fluctuations with increasing length difference as driving force, causing neighboring molecules within nearest layer into a smectic A‐like packing.     

Regularities of latex filtration through microfiltration membranes

Filtration of suspensions of emulsifier-free monodisperse polystyrene latexes with particle sizes of 0.25, 0.3, and 0.4 μm through acetylcellulose microfilters is studied as depending on the composition of liquid phases, the rate and time of filtration, and the particle-to-pore size ratios. The effect of particle-membrane interactions, which are governed by the electrostatic repulsion and molecular attraction forces, on particle rejection by membranes is considered. It is shown that, when analyzing the mechanism for the rejection, it is necessary to take into account the electrophoretic motion of particles in the field of the streaming potential arising in the course of suspension filtration.     

Atom states and interatomic interactions in perovskite-like oxides: XXV. Magnetic dilution in the La(Sr)MnO<Subscript>3</Subscript>-LaGaO<Subscript>3</Subscript> system

Magnetic susceptibility of lanthanum gallates doped with manganese and also with manganese and strontium was studied. The calculation of manganese distribution in the solid solutions and a comparison with magnetic data for lanthanum aluminate showed that in gallate the clustering of manganese is higher, and the introduction of strontium results in clusters not destructed even at infinite dilution.     

Isolation and structure determination of the biologically active sphingolipids from marine sponge Haliclona species

In a continuation to our study on the marine sponge Haliclona species we have isolated three new cytotoxic components of sphingolipids (1-3). Methanolysis of the sphingolipid 1a-d in methanol produces fatty acid methyl ester. GC/MS was used to determine the length. The structure of each isolated compound has been determined on the basis of spectroscopic data and chemical evidence.     

A quantum mechanical/molecular dynamics/mean field study of acrolein in aqueous solution: analysis of H bonding and bulk effects on spectroscopic properties

A novel molecular dynamics methodology recently proposed by our group [Rega et al., Chem. Phys. Lett. 422, 367 (2006)], which is based on an integrated hybrid potential rooted in high level quantum mechanical methods using localized basis functions and nonperiodic boundary conditions, has been applied to study acrolein in aqueous solution. The solute structural rearrangement and its hydrogen-bonding pattern due to the interactions with water have been analyzed in some detail. Moreover, the solvent effects on the UV n-->pi* vertical transition and on the NMR 13C and 17O shielding constants of acrolein have been investigated theoretically by performing a posteriori quantum mechanical calculations on a statistically significant number of snapshots extracted from both gas-phase and aqueous solution simulations. Results show that such effective computational strategy can be successfully used to improve our understanding, at atomic level, of important spectroscopic observables.     

s-Triazine and tri-s-triazine based organic-inorganic hybrid gels prepared from chlorosilanes by exchange reactions

Hybrid polymers [(DeltaO3)4Si3]n and [(DeltaO3)SiMe]n (where Delta = C6N7 or C3N3) have been prepared by a novel sol-gel process based on exchange reactions of MeSiCl3 or SiCl4 with C6N7(OSiMe3)3 and C3N3(OSiMe3)3.