Cyanide sensing with organic dyes: studies in solution and on nanostructured Al2O3 surfaces

The synthesis of two new azo phenyl thiourea compounds and their optical response to different anions is reported herein. Solution studies in methanol indicate that cyanide induces a colour change in these dyes (whereas no changes are observed in the presence of other anions, such as F(-), Cl(-), Br(-), CH(3)COO(-), H(2)PO(4) (-), HSO(4) (-)). Interestingly, in DMSO these dyes are responsive not only to cyanide, but also to fluoride, acetate and dihydrogen phosphate. Each of these anions induces a different colour change. In the second part of the paper, we report the attachment of one of these dyes onto nanostructured TiO(2) and Al(2)O(3) films. The stability of these sensitised films to pH was studied and we concluded that the sensitised Al(2)O(3) films are more robust, and hence, better than the TiO(2) for anion sensing. The dye-sensitised Al(2)O(3) films were immersed in solutions of different anions and their response studied. The films can detect cyanide down to 3 ppm in aqueous solution with relatively good selectivity over other anions.     

Magnetic structure and electronic study of complex oxygen-deficient manganites

Neutron diffraction and X-ray absorption near-edge structure (XANES) studies have been performed in La0.5Ca0.5MnO2.5, La0.5Sr0.5MnO2.5 and Nd0.5Sr0.5MnO2.5 oxygen-deficient perovskite compounds obtained by topotactic reduction. They all exhibit a brownmillerite structure with G-type antiferromagnetic ordering. Mn2+, Mn3+ and Mn4+ coexist at the octahedral sites, whereas only Mn2+ is placed in the tetrahedral positions. A magnetic moment of 1.6 microB has been detected at the tetrahedral layers, which can be explained by assuming Mn2+ is in a low-spin configuration.     

Raman spectroscopy shows interchain through space charge delocalization in a mixed valence oligothiophene cation and in its pi-dimeric biradicaloid dication

The vibrational Raman spectra of a decathiophene are provided in three relevant oxidations states: for the radical cation, its class III mixed valence system and its "frozen, -170 degrees C" class II MV analogue; for the dication, its singlet biradical pi-dimer and its "hot, +70 degrees C" magnetically active triplet excited state. Everything is compatible with interpentathiophene charge delocalization occurring at distances of 4-5 A similar to those found in the crystals of pi-stacked oligothiophenes. This stresses the interest of this spectroscopic tool for the analyses of electronic processes in crystals or in thin films of conjugated organic molecules.     

Synthesis and self-association properties of functionalized C3-symmetric hexakis(p-substituted-phenylethynyl)triindoles

A number of differently substituted phenylethynyl triindoles has been synthesized by 6-fold Sonogashira coupling in a key step. This new series of hexaalkynyl triindoles self-associate through arene-arene interactions in solution. The electronic communication of the external substituents with the central electron-rich triindole core has been demonstrated by means of cyclic voltammetry and optical absorption. A study of the effect of the electronic character of peripheral substituents on their self-association behavior is presented in an effort to shed light on the nature of the pi-stacking interactions.     

Lanthanide complexes based on a 1,7-diaza-12-crown-4 platform containing picolinate pendants: a new structural entry for the design of magnetic resonance imaging contrast agents

We have synthesized a new macrocyclic ligand, N,N'-Bis[(6-carboxy-2-pyridyl)methyl]-1,7-diaza-12-crown-4 (H 2bp12c4), designed for complexation of lanthanide ions in aqueous solution. The X-ray crystal structure of the Gd (III) complex shows that the metal ion is directly bound to the eight donor atoms of the bp12c4 ligand, the ninth coordination site being occupied by an oxygen atom of a carboxylate group of a neighboring [Gd(bp12c4)] (+) unit, while the structure of the Lu (III) analogue shows the metal ion being only eight-coordinate. The hydration numbers obtained from luminescence lifetime measurements in aqueous solution of the Eu (III) and Tb (III) complexes suggest an equilibrium in aqueous solution between a dihydrated ( q = 2), ten-coordinate and a monohydrated ( q = 1), nine-coordinate species. This has been confirmed by a variable temperature UV-vis spectrophotometric study on the Eu (III) complex. The structure of the complexes in solution has been investigated by (1)H and (13)C NMR spectroscopy, as well as by theoretical calculations performed at the DFT (B3LYP) level. The results indicate that the change in hydration number occurring around the middle of the lanthanide series is accompanied by a change in the conformation adopted by the complexes in solution [Delta(lambdalambdalambdalambda) for q = 2 and Lambda(deltalambdadeltalambda) for q = 1]. The structure calculated for the Yb (III) complex (Lambda(deltalambdadeltalambda)) is in good agreement with the experimental structure in solution, as demonstrated by the analysis of the Yb (III)-induced paramagnetic (1)H shifts.     

Spontaneous magnetization in Ni-Al and Ni-Fe layered double hydroxides

Layered double hydroxides containing paramagnetic Ni (II) and diamagnetic/paramagnetic Al (III)/Fe (III) ions have been prepared and characterized. Ni 2Al(OH) 6(NO 3). nH 2O ( 1), Ni 2Fe(OH) 6(NO 3). nH 2O ( 2), Ni 2Fe(OH) 6(C 6H 8O 4) 0.5. nH 2O ( 3), and Ni 2Fe(OH) 6(C 10H 16O 4) 0.5. nH 2O ( 4) were prepared by coprecipitation at controlled pH as polycrystalline materials with the typical brucite-like structure, with alternating layers of hydroxide and the corresponding anions, which determine the interlayer separation. Magnetic studies show the appearance of spontaneous magnetization between 2 and 15 K for these compounds. Interestingly, the onset temperature for spontaneous magnetization follows a direct relationship with interlayer separation, since this is the only magnetic difference between compounds 2, 3, and 4. Magnetic and calorimetric data indicate that long-range magnetic ordering is not occurring in any of these materials, but rather a freezing of the magnetic system in 3D due to the magnetic disorder and competing intra- and interlayer interactions. Thus, these hydrotalcite-like magnetic materials can be regarded as spin glasses.     

On the spectral and modulational stability of periodic wavetrains for nonlinear Klein-Gordon equations

In this contribution, we summarize recent results [8, 9] on the stability analysis of periodicwavetrains for the sine-Gordon and general nonlinearKlein-Gordon equations. Stability is considered both from the point of view of spectral analysis of the linearized problem and from the point of view of the formal modulation theory of Whitham [12]. The connection between these two approaches is made through a modulational instability index [9], which arises from a detailed analysis of the Floquet spectrum of the linearized perturbation equation around the wave near the origin. We analyze waves of both subluminal and superluminal propagation velocities, as well as waves of both librational and rotational types. Our general results imply in particular that for the sine-Gordon case only subluminal rotationalwaves are spectrally stable. Our proof of this fact corrects a frequently cited one given by Scott [11].