Pseudolattice theory of charge transport in ionic solutions: Corresponding states law for the electric conductivity

A statistical mechanical framework for charge transport in ionic liquid–solvent mixtures based on the existence of a statistical lattice structure (pseudolattice) throughout the whole range of concentration is reported. The ion distribution is treated in a mean-field Bragg–Williams-like fashion, and the ionic motion is assumed to take place through hops between cells of two different types separated by non-random-energy barriers of different heights depending on the cell type. Assuming non-correlated ion transport, the electrical conductivity is shown to have a maximum, arising from the competition between the concentration of charge carriers in the bulk medium and their mobilities in the pseudolattice. An explicit expression for the concentration at which this maximum occurs is given in terms of microscopic parameters, and the electrical conductivity normalized by its maximum value (κ/κ_max) is shown to follow rather closely a universal corresponding states law in concentration space when represented against the ionic concentration scaled by its value at the conductivity maximum (?_α/?_max). Ion–ion and ion–solvent interactions are explicitly considered combining the path probability method for charge transport in solid electrolytes and the Bragg–Williams approximation for interparticle interactions, and their impact on the deviations of experimental data from the universal behavior of non-correlated transport analyzed. The theoretical predictions are shown to satisfactorily predict experimental values of electrical conductivity of aqueous solutions of conventional electrolytes and of mixtures of room temperature molten salts with typical solvents.     

Synthesis of new luminescent supramolecular assemblies from fluorenyl porphyrins and polypyridyl isocyanurate-based spacers

Two new dendrimeric supramolecular assemblies bearing twelve and twenty-four fluorenyl peripheral donor groups surrounding an organic core have been prepared and studied. These assemblies are composed of three zinc porphyrins possessing each four (ZnTFP) and eight fluorenyl chromophores (ZnOOFP) linked together by a central tris-pyridyl organic ligand. Due to efficient energy transfer between the fluorenyl arms, which act as antennas, and the Zn centres, which act as emitters; these assemblies behave as red emitters after selective UV or visible irradiation. The kinetic stability of these supramolecular assemblies and its impact on their photophysical properties are discussed.     

Synthesis and photophysical properties of new conjugated fluorophores designed for two-photon-excited fluorescence

[structure: see text] Novel elongated push-push fluorophores (e.g., 9) were synthesized by 2-fold Sonogashira or Wittigminus signHorner reactions. Modulation of the length and topology of the conjugated connectors allows tuning of their photophysical properties. In addition, their photoluminescence can be adjusted by playing on polarity. Derivatives combining enhanced two-photon absorption cross section (sigma2) in the visible red and high fluorescence quantum yield (Phi) have been obtained. Such fluorophores hold promise for nonlinear imaging of biological systems.     

New cyclen-cored dendrimers functionalized with pyrene: Synthesis characterization,optical and photophysical properties

New cyclen (1,4,7,10-teraazacyclododecane) cored dendrimers up to the second generation, functionalized with 4, 8 and 16 pyrene units, respectively, were synthesized following a convergent procedure. All new compounds were characterized by NMR spectroscopies and ESI or MALDI TOF mass spectrometry. The optical and photophysical properties of the new dendrimers were studied in THF solution. Absorption spectra showed the typical absorption bands of pyrene moieties. In the fluorescence spectra, monomer as well as excimer emission were observed for all compounds. An increased proportion of excimer emission was observed in the dendrimer of the highest generation.     

Synthesis of cycloalkenyl geminal bisphosphonates by ring closing metathesis

Five‐ and six‐membered cycloalkenyl bisphosphonates were obtained by ring closing metathesis (RCM) reactions of diethyl bis(alkenyl)methylene bisphosphonates using ruthenium alkylidene catalysts. The substitution pattern on the double bonds involved in the reaction greatly influences the reaction rate. The synthesis of the starting materials was carried out by dialkylation of tetraethyl methylene bisphosphonate or through a Michael addition of Grignard reagents to tetraethyl vinylidene bisphosphonate followed by alkylation, depending on the structure of the required substrate. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:332–338, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20622     

An investigation of the structural aspects of the tomato fruit by means of quantitative nuclear magnetic resonance imaging

In this study, magnetic resonance imaging (MRI) was applied to study the structural aspects of the tomato fruit. The main study was performed on tomatoes (cv. Tradiro) using a 0.2-T electromagnet scanner. Spin-echo images were acquired to visualize the tomato macrostructure. The air bubble content in tissues was evaluated by exploiting susceptibility effects using multiple gradient echo images. The microstructure was further studied by measuring spin–spin (T₂) and spin–lattice (T₁) relaxation time distributions. Nuclear magnetic resonance relaxometry, macro vision imaging and chemical analysis were used as complementary and independent experimental methods in order to emphasize the MRI results. MRI images showed that the air bubble content varied between tissues. The presence of gas was attested by macro vision images. Quantitative imaging showed that T₂ and T₁ maps obtained by MRI reflected the structural differences between tomato tissues and made it possible to distinguish between them. The results indicated that cell size and chemical composition contribute to the relaxation mechanism.