Mononuclear and Dinuclear Copper Complexes of Tridentate Redox-active Ligands with Tunable H-bonding Donors: Structure,Spectroscopy and H+/e− Reactivity

In this research article, we describe the synthesis and characterization of mononuclear and dinuclear Cu complexes bound by a family of tridentate redox-active ligands with tunable H-bonding donors. The mononuclear Cu-anion complexes were oxidized to the corresponding “high-valent” intermediates by oxidation of the redox-active ligand. These species were capable of oxidizing phenols with weak O−H bonds via H-atom abstraction. Thermodynamic analysis of the H-atom abstractions, which included reduction potential measurements, pK_a determination and kinetic studies, revealed that modification of the anion coordinated to the Cu and changes in the H-bonding donor did not lead to major differences in the reactivity of the “high-valent” CuY complexes (Y: hydroxide, phenolate and acetate), which indicated that the tridentate ligand scaffold acts as the H⁺ and e⁻ acceptor.     

New water-soluble calix[4]arene-based bipyridyl podands incorporating carboxylate groups

New calixarene-based bis-bipyridyl podands incorporating two sodium (4-oxo)-butanoate or four sodium carboxymethyl groups at the upper rim were synthesised and fully characterised. The (4-oxo)-butanoate derivative bearing unsubstituted bipyridyl arms was not soluble in water at neutral pH, while its 4,4′-dicarboxylate analogue was perfectly soluble, as were the carboxymethyl derivatives. The association of water solubility to the chelating behaviour of the bipyridyl subunits resulted in the ability to complex the unstable copper(I) cation in water, even in the presence of bovine serum albumin.     

On the polarization of non-paraxial transverse fields

On the basis of a plane-wave spectrum representation, the polarization features of a transverse quasimonochromatic non-paraxial field have been studied. A relationship has been established between the polarization characteristics in the near field and the coherence and symmetry properties of the beam in the far field.     

Construction d'une paramétrixe pour des opérateurs différentiels hypoelliptiques marimaux sur un espace homogéne d'un groupe de Lie nilpotent gradué de rang 2

Soient G une alébre de Lie nilpotente stratifée de rang 2, une sous-algébre de G, _0, la représentation de G dans l'espace L ²( \ G) indiute par le caractére trivial C, P un opérateur homogène appartenant à l'algébre universelle enveloppante (complexifiée) U(G) tel que l'opérateur _0, (P) soit hypoelliptique maximal. Cet opérateur peut s'exprimer par une intégrale dépendant de la restriction du symbole p de P au sousensemble = G · décrit par les orbites des éléments de dans la représentation contragrédiente de G dans G ^*.Une algèbre de symboles définis sur est construite et permet de déterminer une paramétrixe de _0, (P); des résultats de réguralité de cet opérateur dans des espaces de Sobolev adaptés sont ensuite obtenus.     

Application of time-of-flight mass spectrometry to the analysis of phototransformation products of diclofenac in water under natural sunlight

Exact mass capabilities of time-of-flight (TOF) mass spectrometry along with other mass spectrometric techniques have been evaluated to elucidate a complete range of dichlofenac phototransformation products. Photolysis experiments with diclofenac in water under direct solar irradiation were performed to characterise the main phototransformation products generated and to determine their stability. Photolysis experiments were performed in both demineralised water and reconstructed standard freshwater. Samples were extracted before analysis by solid phase extraction (SPE) with Oasis HLB and MAX cartridges. Separation and identification of the transformation products were accomplished by the combined use of gas chromatography-mass spectrometry (GC/MS) and liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOFMS). Both techniques provided complementary information that enabled the identification of 13 phototransformation products. Six of them were identified by GC/MS through the structural information provided by the full scan mass spectra obtained under electron impact (EI) ionisation and the confirmation of the molecular mass provided by positive chemical ionisation (PCI) analyses. Accurate mass measurements obtained by LC/TOFMS provided the elucidation of seven polar transformation products. The low mass error observed (<2 ppm) enabled the assignment of highly probable empirical formulas as well as identification of a process dimerisation route. The photoproducts identified demonstrated that photolysis of diclofenac occurs by two main routes. One is the consequence of the initial photocyclisation of diclofenac into carbazole derivatives. The other route goes through the initial decarboxilation of diclofenac and further oxidation of the alkyl-chain, which are typical photolytic process reactions. The main photoproduct identified was 8-chloro-9H-carbazole-1yl-acetic acid.     

Modelisation of the Electric Field Linear Response of an Infinite Aggregate of All-Trans Hexatriene Chains by Electrostatic Interaction Model

A classical electrostatic polarization scheme using the additive distribution procedure has been applied to determine the longitudinal polarizability of an all-trans hexatriene molecule in an infinite stretched fiber. The parameters have been derived from ab initio CPHF/6-31G calculations and the electrostatic scheme has been validated via comparison with ab initio results on small clusters. Upon packing the polarizability of all-trans hexatriene increases by 7%. This small increase results from the balance between the enhancement of the polarizability due to collinear packing and the reduction associated with lateral packing.     

Algebras of sets generating non-barrelled spaces

IfA is a -algebra on setX, thenl ₀ (X,A) is a barrelled space of class ₀. IfA is an algebra, there are conditions which imply thatl ₀ (X,A) is suprabarelled. Here, wheneverA is an algebra, we give conditions forl ₀ (X,A) to be not barrelled which are related with the existence of non-trivial convergent sequences.Supported in part by DGICYT, project PB91-0407 and by the Institució Valenciana d'Estudis i Investigació, project 023.     

Flow-through optical fiber sensor for automatic sulfide determination in waters by multisyringe flow injection analysis using solid-phase reflectometry

A software-controlled flow-through optical fiber diffuse reflectance sensor capitalized on the implementation of disk-based solid-phase pre-concentration schemes in a multisyringe flow injection analysis (MSFIA) set-up is proposed for the trace determination of sulfide in environmental waters and wastewaters. The fully automated flowing methodology is based on Fischer's coupling reaction of sulfide with N,N-dimethyl-p-phenylenediamine (DMPD) in the presence of Fe(iii) as oxidizing reagent in a 0.5 M HCl medium. The on-line generated methylene blue dye is subsequently delivered downstream to a dedicated optode cell furnished with an octadecyl-chemically modified (C(18)) disk, while continuously recording the diffuse reflectance spectrum of the pre-concentrated compound. A double regeneration protocol is finally executed to warrant minimum background noise and negligible baseline. Under the optimized chemical and hydrodynamic conditions, the optosensing MSFIA method features coefficients of variation better than 0.7%(n= 10) at 50 microg l(-1) concentration, a linear working range of 20-200 microg l(-1) sulfide, a 3sigma(blank) detection limit of 2.9 microg l(-1) sulfide and an injection throughput of 8 h(-1) for a pre-concentration sample volume of 2.9 ml. The interfacing of the robust and versatile multisyringe flow injection-based optode with a plug-in spectrophotometer furnished with a light emitting diode assures the miniaturization of the overall flow analyzer, which is, thus, readily adaptable to real-time monitoring schemes. The potential of the multisyringe flow method was assessed via the determination of sulfide traces in water samples of different complexity (namely, freshwater, seawater and wastewater).