PubMed Health⌕ Search

Biomedical subjects

Luis A Villaescusa

Publications and source records attributed to Luis A Villaescusa.

11 recordsLinked to original sources
PubMed2006

Anchoring dyes into multidimensional large-pore zeolites: a prospective use as chromogenic sensing materials.

A versatile procedure for anchoring dyes into the pores of multidimensional zeolites by including organic dye precursors in the synthesis gel has been developed. To prove the concept, an aniline-functionalised zeolite Beta was obtained by reaction of triethylorthosilicate (TEOS), tetraethylammonium hydroxide, and N-methyl,N-(propyl-3-trimethoxysilyl)aniline (MPTMSA) in the presence of HF. Further extraction of the structure-directing agents resulted in a highly crystalline, white, functionalised zeolite Beta containing anchored aniline groups. Similar organic functionalised molecular sieves (OFMS) have been explored as novel catalysts, but, as far as we know, OFMS have never been used as precursors for dye-immobilisation or to design new solid-based host systems for selective molecular sensing processes as is reported here. In a second step the solids containing dyes were prepared by reaction of the hybrid material with the appropriate reactives to obtain tricyanovinylbenzene, triphenylpyrylium, azoic, and squaraine derivatives. All these reactions are straightforward and involve electrophilic aromatic substitution or diazotisation reactions at the electron-rich aniline ring. The final dye-functionalised solid materials were isolated by simple filtration and washing procedures and have been characterised by a number of techniques. In all cases the Beta structure of the solid remains unaltered. Among the large number of areas where dye-containing zeolites might be of importance, we were interested in testing their unconventional use as heterosupramolecular hosts in chromogenic protocols. To check their potential use as chemosensors, microporous solids with anchored triphenylpyrilium and squaraine dyes were selected and used as sensors for the chromogenic discrimination of amines. It was found that the response of both solids to amines was basically governed by the three-dimensional (3D) solid architecture that tuned the intrinsic unselective reactivity of the pyrylium dye. By using new solid-state supramolecular chemistry protocols we believe that these, and similar future dye-zeolite hosts, might be promising new sensor materials allowing the visible discrimination of selected target guests by size and/or polarity within families or closely related molecules.

Journal Article↗
PubMed2005

Growth of mesoporous materials within colloidal crystal films by spin-coating.

A combination of colloidal crystal planarization, stabilization, and novel infiltration techniques is used to build a bimodal porous silica film showing order at both the micron and the nanometer length scale. An infiltration method based on the spin-coating of the mesophase precursor onto a three-dimensional polystyrene colloidal crystal film allows a nanometer control tuning of the filling fraction of the mesoporous phase while preserving the optical quality of the template. These materials combine a high specific surface arising from the nanopores with increased mass transport and photonic crystal properties provided by the order of the macropores. Optical Bragg diffraction from these type of hierarchically ordered oxides is observed, allowing performing of optical monitoring of the different processes involved in the formation of the bimodal silica structure.

Journal Article↗
PubMed2004

Toward the development of ionically controlled nanoscopic molecular gates.

An ionically controlled nanoscopic molecular gate has been developed by using functionalized mesoporous materials. The system shows that control of mass transport at nanometric scale can be achieved by using suitable rigid solids and pH-active molecules. The design principle suggests new perspectives in the search of ionically tuned tailored materials and devices with a fine control of mass transport for new applications in fields such as drug delivery, selective removal of toxic species, sensing, or catalysis.

Journal Article↗
PubMed2004

A severely interrupted germanate zeolite framework synthesised from isolated double four-ring units.

A new germanate zeolite framework has been prepared by first determining the reaction conditions required to prepare a molecular analogue of the zeolite double four-ring secondary building unit and then altering the conditions so as to encourage condensation of these units. The resultant material is a severely interrupted solid showing an unusual two dimensional channel system. It is also one of the most open frameworks yet discovered. The material was characterised using single crystal X-ray diffraction at a synchrotron source and solid state magic angle spinning NMR.

Journal Article↗
PubMed2003

An X-ray diffraction and MAS NMR study of the thermal expansion properties of calcined siliceous ferrierite.

Powder and single-crystal X-ray diffraction, combined with MAS NMR measurements, has been used to study the thermal expansion of siliceous zeolite ferrierite as it approaches a second-order displacive phase transition from a low-symmetry (Pnnm) to a high-symmetry (Immm) structure. Below the transition temperature, ferrierite exhibits positive thermal expansivity. However, above the transition temperature a significant change in thermal behavior is seen, and ferrierite becomes a negative thermal expansion material. Accurate variable-temperature single-crystal X-ray diffraction measurements confirm the transition temperature and allow the changes in average atomic position to be followed with temperature. The results from the single-crystal X-ray diffraction study can be correlated with (29)Si MAS NMR chemical shifts for the low-temperature phase. At low temperatures the results show that the positive thermal expansivity is driven by an overall increase in Si[bond]Si distances related to an increase in Si[bond]O[bond]Si bond angles. However, in the high-temperature phase the Si[bond]O[bond]Si angles are approximately invariant with temperature, and the negative thermal expansion in this case is caused by transverse vibrations of the Si[bond]O[bond]Si units.

Journal Article↗
PubMed2002

Combined solid state NMR and X-ray diffraction investigation of the local structure of the five-coordinate silicon in fluoride-containing as-synthesized STF zeolite.

The local structure of the [SiO(4/2)F]- unit in fluoride-containing as-synthesized STF zeolite has been experimentally determined by a combination of solid-state NMR and microcrystal X-ray diffraction to be very close to trigonal bipyramidal. Because the fluoride ions are disordered over two sites, the resulting local structure of the [SiO(4/2)F]- unit from a conventional XRD refinement is an average between tetrahedral SiO(4/2) and five-coordinate [[SiO(4/2)F]-, giving an apparent F-Si distance longer than expected. The correct F-Si distance was determined by slow spinning MAS and fast spinning (19)F/(29)Si CP and REDOR solid-state NMR experiments and found to be between 1.72 and 1.79 A. In light of this, the X-ray structure was re-refined, including the disorder at Si3. The resulting local structure of the [SiO(4/2)F]- unit was very close to trigonal bipyramidal with a F-Si distance of 1.744 (6) A, in agreement with the NMR results and the prediction of Density Functional Theory calculations. In addition, further evidence for the existence of a covalent F-Si bond is provided by a (19)F-->(29)Si refocused INEPT experiment. The resonance for the five-coordinate species at -147.5 ppm in the (29)Si spectrum is a doublet due to the (19)F/(29)Si J-coupling of 165 Hz. The peaks in this doublet have remarkably different effective chemical shift anisotropies due to the interplay of the CSA, dipolar coupling, and J-coupling tensors. The distortions from tetrahedral geometry of the neighboring silicon atoms to the five-coordinate Si3 atom are manifested in increased delta(aniso) values. This information, along with F-Si distances measured by (19)F-->(29)Si CP experiments, makes it possible to assign half of the (29)Si resonances to unique tetrahedral sites. As well as determining the local geometry of the [SiO(4/2)F]- unit, the work presented here demonstrates the complementarity of the solid-state NMR and X-ray diffraction techniques and the advantages of using them together.

Journal Article↗
PubMed2002

Toward inorganic electrides.

Electrides are materials in which alkali metals (Li through Cs) ionize to form bound alkali cations and "excess" electrons. The electrons reside in large cavities or channels or both in the host lattice. We report here the first synthesis of thermally stable inorganic electrides with cation-to-electron ratios of 1:1 as in organic electrides. Although alkali metal adducts to alumino-silicate zeolites are well known, the cation-to-electron ratio is generally 3:1 or greater because these zeolites contain alkali cations prior to incorporation of the alkali metal. In this work, two pure silica zeolites, ITQ-4and ITQ-7, with pore diameters of approximately 7 A, absorb up to 40 wt % cesium from the vapor phase (even at room temperature). The other alkali metals (except Li) can also be introduced at elevated temperatures. The optical and magnetic properties of the cesium-loaded samples suggest ionization to form Cs+ and e- with substantial electron-spin pairing. The metal-loaded samples are stable to at least 100 degrees C and are able to reduce small aromatic molecules such as benzene and naphthalene to the radical anions within the pores of the zeolite.

Journal Article↗