Javier Alarcón

Anion detection by fluorescent Zn(II) complexes of functionalized polyamine ligands.

The Zn(2+) coordination chemistry and luminescent behavior of two ligands constituted by an open 1,4,7-triazaheptane chain functionalized at both ends with 2-picolyl units and either a methylnaphthyl (L1) or a dansyl (L2) fluorescent unit attached to the central amino nitrogen are reported. The fluorescent properties of the ZnL1(2+) and ZnL2(2+) complexes are then exploited toward detection of anions. L1 in the pH range of study has four protonation constants. The fluorescence emission from the naphthalene fluorophore is quenched either at low or at high pH values leading to an emissive pH window centered around pH = 5. In contrast, in L2 the fluorescence emission from the dansyl unit occurs only at basic pH values. In the case of L1, a red-shifted band appearing in the visible region was assigned to an exciplex emission involving the naphthalene and the tertiary amine of the polyamine chain. L1 forms Zn(2+) mononuclear complexes of ZnH(p)L1((p+2)+) stoichiometry with p = 1, 0, -1. Formation of the ZnL1(2+)species produces a strong enhancement of the L1 luminescence leading to an extended emissive pH window from pH = 5 to pH = 9. Addition of several anions to this last complex leads to a partial quenching effect. On the contrary, the fluorescence emission of L2 is partially quenched upon complexation with Zn(2+) in the same pH window (5 < pH < 9). The lower stability of ZnL2(2+) with respect to ZnL1(2+) suggests a lack of involvement of the sulfonamide group in the first coordination sphere. However, there is spectral evidence for an interesting photoinduced binding of the sulfonamide nitrogen to Zn(2+). While addition of diphosphate, triphosphate, citrate, and D,L-isocitrate to a solution of ZnL2(2+) restores the fluorescence emission of the system (lambda max ca. 600 nm), addition of phosphate, chloride, iodide, and cyanurate do not produce any significant change in fluorescence. Moreover, this system would permit one to differentiate diphosphate and triphosphate over citrate and d, l-isocitrate because the fluorescence enhancement observed upon addition of the first anions is much sharper. The ZnL2(2+) complex and its mixed complexes with diphosphate, triphosphate, citrate, and D,L-isocitrate have been characterized by (1)H, (31)P NMR, and Electrospray Mass Spectrometry.

Synthesis and phase transformations of mullites obtained from SiO2Al2O3 gels

Abstract Synthesis and structural characterization of mullite phases obtained from three nominal compositions in the SiO2Al2O3 system is reported and comparisons between them are established. Monosized gels with Al Si atomic ratios of 2:3, 3:1 and 9:1 were obtained and thermally treated at temperatures between 700 and 1500 °C. The thermal evolution of amorphous gels was followed by thermal analysis, X-ray diffraction and infra-red spectroscopy. The microstructural changes were studied by scanning electron microscopy and transmission electron microscopy. The formation of Al2O3-rich mullite started around 1000 °C for all samples and was fully developed at 1400 °C. The chemical composition of mullites changed as a function of calcining temperature. An anomalous low value of the lattice parameter a was obtained for the sample with Al Si atomic ratio of 9:1 compared with the 3:1 sample at 1400 °C, which may be due to the slow reaction rate of Al2O3 with SiO2-rich glassy phase during mullite formation.

Synthesis and characterization of vanadium-containing ZrSiO4 solid solutions from gels

A procedure is reported for the preparation of vanadium-doped zircon pigmenting system with different vanadia loadings which enabled their complete formation and further characterization. Vanadium-zircon solid solutions were prepared by gelling mixtures of ZrO2 and V2O5 colloidal sols and tetraethylorthosilicate and studied over the temperature range up to the formation of zircon. The reaction sequence of gels was evaluated by X-ray powder diffraction (XRD) and ultraviolet-visible (UV-Vis) diffuse reflectance. It was found that the first crystalline phase detected was a vanadium-containing tetragonal ZrO2 solid solution where vanadium was stabilized in the reduced V+4 state. The formation of the V-ZrSiO4 solid solution occurred by the reaction between the monoclinic form of V+4-ZrO2 solid solution and the amorphous silica phase. Energy dispersive X-ray microanalysis (SEM/EDX) data, measurements of lattice parameters and UV-Vis diffuse reflectance of V-ZrSiO4 solid solutions revealed that vanadium was dissolved as V+4 replacing Si+4 in tetrahedral sites in the crystal structure of zircon. The solubility limit of vanadium in ZrSiO4 was about 0.01 mole of vanadium per mole of zircon (0.5 wt% as V2O5).

Crystallization behaviour and microstructural development in ZrSiO4 and V-ZrSiO4 solid solutions from colloidal gels

Abstract Zircon and vanadium-doped zircon blue pigments were prepared by heat treatment of gel precursors. Gels with nominal compositions Vx-ZrSiO4 with x=0.0, 0.002, 0.004, 0.02 and 0.2 were prepared by formation of a silica coating on zirconia colloidal particles previously obtained. The crystallization behavior and microstructural evolution were studied using X-ray powder diffraction (XRD), energy dispersive X-rays microanalysis (EDX), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). The results indicated that the vanadia loading in the precursor gels speeds up the crystallization of the vanadium-containing tetragonal zirconia solid solutions and their transformation to the monoclinic form. The overall conversion rate of gel precursors to pigmenting powders increased when the vanadia content was higher. Microstructural data revealed that the used procedure for the preparation of vanadium-zircon pigments allowed high-purity and non-agglomerated powders with controlled particle size to be obtained.

Grafted squaramide monoamine nanoparticles as simple systems for sulfate recognition in pure water

New simple systems formed by a chain containing a squaramide function and a quaternised amine group attached to boehmite or silica-coated boehmite nanoparticles are able to discriminate anions in pure water.

New sensing devices part 1: indole-containing polyamines supported in nanosized boehmite particles

The synthesis, characterisation and optical properties of new sensing systems made by attaching different polyamine chains functionalised with an indole fluorophore to a boehmite matrix is reported for the first time. Firstly, a family of tri(alkoxy)alkylpolyaminosilanes have been reacted with indole-3-carboxaldehyde to form the corresponding Schiff bases which were reduced with sodium borohydride. The anchoring to the surface of the boehmite nanoparticles was carried out by reacting the precursors with the hydroxyl groups available in the surface of the support. The characterisation of the materials by elemental microanalysis, X-ray powder diffraction, CP-MAS 29Si NMR and electron microscopy unambiguously proved that covalent anchorage had occurred. Steady-state fluorescence emission studies showed that these materials present a very efficient sensing behaviour for hydrogen ions, metal ions such as Cu2+ and Zn2+ and for the anionic nucleotides ATP, ADP and AMP.

Mechanism of crystallization of Co-cordierites from stoichiometric powdered glasses

Abstract The influence of cobalt, as a divalent cation, on the crystallization behaviour of the cordierite based glasses was studied. Powdered glass specimens of stoichiometric composition 2MO 2Al 2 O 3 5SiO 2 (M=Co and/or Mg) were obtained and thermally treated at several temperatures and times, and the sequence of crystallization and their microstructural evolution were analysed by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). Results on the crystallization sequence showed that the steps in the crystallization path are independent of the nature of the divalent cation. The first crystalline phase detected displayed the μ-cordierite structure, i.e. a solid solution with β-quartz structure. After further thermal treatment a phase with α-cordierite structure was formed. Cobalt μ- and α-cordierites were further characterized by infrared (IR) and UV–vis diffuse reflectance spectroscopies. The final morphology of cobalt-containing hexagonal cordierites depended on the densification degree of the precursor glass.

Cobalt aluminate spinel-mullite composites synthesized by sol-gel method

Abstract CoAl 2 O 4 spinel-mullite composites were prepared by double substitution of Al by Ti and Ni in stoichiometric 3:2 mullite. Gels with compositions 3(Al 2 − 2 x Co x Ti x O 3 )·2SiO 2 (x = 0.025, 0.05 and 0.2) and 3(Al 2 − 2 x M x O 3 )·2SiO 2 (x = 0.05; M = Co 2+ or Ti 4+ ) were synthesized by sol-gel techniques. The structure of the gels was investigated by infra-red spectroscopy. Heating gels at 750 °C produced an amorphous silicoaluminate network. The reaction sequence was investigated by differential thermal analysis, X-ray diffraction and ultraviolet-visible spectroscopy. All samples crystallized at temperatures lower than 1000 °C from the amorphous state. Al-Si spinel and/or CoAl 2 O 4 were the first crystalline phases detected, which appeared almost simultaneously. This finding indicated the important role played by Co 2+ and Ti 4+ in phase development and crystallization kinetics, even for compositions very close to the stoichiometric 3:2. The reaction sequence can understood by assuming that CoAl 2 O 4 spinel was developed by epitaxial growth on Al-Si spinel. This fact permitted direct control of the final microstructure of the CoAl 2 O 4 spinel-mullite composite as revealed by scanning and transmission electron microscopies.

Preparation of Hg2+ selective fluorescent chemosensors based on surface modified core–shell aluminosilicate nanoparticles

A synthetic procedure for the preparation of functional structured inorganic–organic hybrid materials consisting of boehmite-silica core–shell nanoparticles and anthracene-containing amines covalently attached to the nanoparticles surface is reported. The system functionalised with the monoamine chain shows a very high sensing performance for Hg2+ detection in pure water reaching a detection limit of 0.2 ppb. Two additional advantages of these systems are their stability over a wide pH window and the feasibility to be recovered by a simple procedure.

Low-temperature metastabilization of tetragonal V+4-containing ZrO2 solid solutions

Abstract The formation and characterization of tetragonal vanadium–zirconia solid solutions with different vanadium contents have been investigated. Vanadium–zirconia precursors were prepared by gelling mixtures of zirconium n-propoxide and vanadyl acetylacetonate, and studied over the range of temperature up to the tetragonal–monoclinic phase transformation. The formation of the tetragonal phase has been investigated by X-ray powder diffraction (XRD). It was found that it took place after annealing around 450°C for all specimens independently of the vanadium loading. In contrast, the temperature for the subsequent tetragonal to monoclinic transformation was dependent on the nominal vanadium content. Further characterization of the tetragonal–vanadium zirconia solid solutions by measurements of lattice parameters, ultraviolet-visible (UV-Vis) diffuse reflectance spectroscopy and electron paramagnetic resonance (EPR) revealed that vanadium was dissolved as V +4 replacing Zr +4 in octacoordinated sites in the crystal structure of tetragonal zirconia. The solubility limit of V +4 in tetragonal ZrO 2 was about 5 mol% of vanadium. The EPR and diffuse reflectance spectroscopy results provided new evidence for the presence of V +4 in the tetragonal zirconia phase, which confirmed previous results in the V 2 O 5 –ZrO 2 –SiO 2 ternary system.