Preparació, estudi estructural i aplicabilitat de derivats de Poli-(4R)-hidroxi-L-prolina a la separació d’enantiòmers per tècniques cromatogràfiques o relacionades

La separació d’enantiòmers (isòmers òptics) és molt important en molts diversos camps, com les síntesis quirals, biologia, i en el camp de la farmacologia especialment. És per això, que es fa necessari de disposar de tècniques i mètodes analítics ràpids, fiables i sensibles per a la separació d’enantiòmers. La present tesi s’emmarca en el camp de la separació d’enantiòmers, concretament en la preparació de fases estacionàries quirals per al seu ús en cromatografia liquida. En aquest sentit, s’ha desenvolupat la síntesi i caracterització de molècules polimèriques quirals derivades de l’aminoàcid L-prolina que incorporades en matrius de gel de sílice poden constituïr columnes quirals per a la separació d’enantiòmers per cromatografia liquida. S’han estudiat les característiques enantioselectives d’aquests nous materials en la separació de molècules quirals, trobant-se ésser satisfactòriament enantioselectius. L’interès que suscita l’obtenció d’enantiòmers a gran escala fa que la recerca s’orienti a la recerca de materials amb elevada capacitat de càrrega, és a dir, que puguin donar lloc a la separació d’elevades quantitats d’enantiòmers. Amb aquesta finalitat s’han dut a terme assaigs de capacitat de càrrega, que han posat de manifest la possible aplicació d’aquests materials a la separació preparativa d’enantiòmers. També s’ha parat especial atenció a l’estudi de les característiques de la matriu de gel de sílice, assajant-se altres materials de sílice més porosos i que permeten així treballar amb fluxos més elevats tot reduint-ne el temps d’anàlisi i els costos associats a la separació preparativa d’enantiòmers. L'estudi conformacional d'aquests nous selectors també ha estat contemplat per tal d'explicar l'enantioselectivitat específica que s'observa en certs dissolvents orgànics en els qual es duu a terme la separació dels enantiòmers.

Structural factors impacting carrier transport and electroluminescence from Si nanocluster-sensitized Er ions.

We present an analysis of factors influencing carrier transport and electroluminescence (EL) at 1.5 µm from erbium-doped silicon-rich silica (SiOx) layers. The effects of both the active layer thickness and the Si excess content on the electrical excitation of erbium are studied. We demonstrate that when the thickness is decreased from a few hundred to tens of nanometers the conductivity is greatly enhanced. Carrier transport is well described in all cases by a Poole-Frenkel mechanism, while the thickness-dependent current density suggests an evolution of both density and distribution of trapping states induced by Si nanoinclusions. We ascribe this observation to stress-induced effects prevailing in thin films, which inhibit the agglomeration of Si atoms, resulting in a high density of sub-nm Si inclusions that induce traps much shallower than those generated by Si nanoclusters (Si-ncs) formed in thicker films. There is no direct correlation between high conductivity and optimized EL intensity at 1.5 µm. Our results suggest that the main excitation mechanism governing the EL signal is impact excitation, which gradually becomes more efficient as film thickness increases, thanks to the increased segregation of Si-ncs, which in turn allows more efficient injection of hot electrons into the oxide matrix. Optimization of the EL signal is thus found to be a compromise between conductivity and both number and degree of segregation of Si-ncs, all of which are governed by a combination of excess Si content and sample thickness. This material study has strong implications for many electrically driven devices using Si-ncs or Si-excess mediated EL.

Bulk silica-based luminescent materials by sol-gel processing of non-conventional precursors

The sol-gel synthesis of bulk silica-based luminescent materials using innocuous hexaethoxydisilane and hexamethoxydisilane monomers, followed by one hour thermal annealing in an inert atmosphere at 950oC-1150oC, is reported. As-synthesized hexamethoxydisilane-derived samples exhibit an intense blue photoluminescence band, whereas thermally treated ones emit stronger photoluminescence radiation peaking below 600 nm. For hexaethoxydisilane-based material, annealed at or above 1000oC, a less intense photoluminescence band, peaking between 780 nm and 850 nm that is attributed to nanocrystalline silicon is observed. Mixtures of both precursors lead to composed spectra, thus envisaging the possibility of obtaining pre-designed spectral behaviors by varying the mixture composition.

Preparació de materials híbrids orgànico-inorgànics a partir de sals d'imidazoli

Estudi elaborat a partir d’una estada a l’ Ecole Nationale Supérieure de Chimie de Montpellier, França, durant 2006. S’han sintetitzat materials híbrids orgànico-inorgànics mitjançant el procés sol-gel i altres estratègies sintètiques. En alguns casos, s’ha intentat estructurar aquests materials, ja sigui per autoestructuració o per mitjà de tensioactius. Com a catalitzadors de les reaccions d'hidròlisi i policondensació s’han utilitzat àcids, bases i fluorurs. Els materials obtinguts s’han caracteritzat mitjançant diferents tècniques: BET (Brunauer-Emmett-Teller), TEM (microscopia electrònica de transmissió), SEM (microscòpia electrònica de rastreig), raigs X en pols , IR i RMN (ressonància magnètica nuclear) en estat sòlid. Amb aquests materials es pretén preparar catalitzadors heterogenis de Pd per reaccions d’acoblament creuat, i de Ru per reaccions de metàtesi. També s’han sintetitzat sals d'imidazoli amb cadenes hidrocarbonades llargues amb l'objectiu de preparar gels de sílice amb aquestes molècules atrapades dins la matriu inorgànica. Aquests materials s’utilitzaran com a organocatalitzadors i també es prepararan els corresponents catalitzadors de Pd per reaccions de Heck, Suzuki i Sonogashira. Les sals d’imidazoli s’han utilitzat com a tensioactius en la preparació de gels de sílice estructurats. Aquestes molècules han resultat ser cristalls líquids i s’han caracteritzar mitjançant DSC (differential scanning calorimetry), microscopia òptica i raigs X.

Metallic and nonmetallic shine in luster: An elastic ion backscattering study

Luster is a metal glass nanocomposite layer first produced in the Middle East in early Islamic times ( 9th AD) made of metal copper or silver nanoparticles embedded in a silica-based glassy matrix. These nanoparticles are produced by ion exchange between Cu+ and Ag+ and alkaline ions from the glassy matrix and further growth in a reducing atmosphere. The most striking property of luster is its capability of reflecting light like a continuous metal layer and it was unexpectedly found to be linked to one single production parameter: the presence of lead in the glassy matrix composition. The purpose of this article is to describe the characteristics and differences of the nanoparticle layers developed on lead rich and lead free glasses. Copper luster layers obtained using the ancient recipes and methods are analyzed by means of elastic ion backscattering spectroscopy associated with other analytical techniques. The depth profile of the different elements is determined, showing that the luster layer formed in lead rich glasses is 5–6 times thinner and 3–4 times Cu richer. Therefore, the metal nanoparticles are more densely packed in the layer and this fact is related to its higher reflectivity. It is shown that lead influences the structure of the metal nanoparticle layer through the change of the precipitation kinetics

Proteomic analysis of peach fruit mesocarp softening and chilling injury using difference gel electrophoresis (DIGE)

Background: Peach fruit undergoes a rapid softening process that involves a number of metabolic changes. Storing fruit at low temperatures has been widely used to extend its postharvest life. However, this leads to undesired changes, such as mealiness and browning, which affect the quality of the fruit. In this study, a 2-D DIGE approach was designed to screen for differentially accumulated proteins in peach fruit during normal softening as well as under conditions that led to fruit chilling injury. Results:The analysis allowed us to identify 43 spots -representing about 18% of the total number analyzed- that show statistically significant changes. Thirty-nine of the proteins could be identified by mass spectrometry. Some of the proteins that changed during postharvest had been related to peach fruit ripening and cold stress in the past. However, we identified other proteins that had not been linked to these processes. A graphical display of the relationship between the differentially accumulated proteins was obtained using pairwise average-linkage cluster analysis and principal component analysis. Proteins such as endopolygalacturonase, catalase, NADP-dependent isocitrate dehydrogenase, pectin methylesterase and dehydrins were found to be very important for distinguishing between healthy and chill injured fruit. A categorization of the differentially accumulated proteins was performed using Gene Ontology annotation. The results showed that the 'response to stress', 'cellular homeostasis', 'metabolism of carbohydrates' and 'amino acid metabolism' biological processes were affected the most during the postharvest. Conclusions: Using a comparative proteomic approach with 2-D DIGE allowed us to identify proteins that showed stage-specific changes in their accumulation pattern. Several proteins that are related to response to stress, cellular homeostasis, cellular component organization and carbohydrate metabolism were detected as being differentially accumulated. Finally, a significant proportion of the proteins identified had not been associated with softening, cold storage or chilling injury-altered fruit before; thus, comparative proteomics has proven to be a valuable tool for understanding fruit softening and postharvest.

Estudio comparado de la génesis de espeleotemas silíceos en granitoides de climas semiáridos y templados húmedos

Silica speleothems take differenr forms such as cylindrical stems growing from either the floor or the ceiling in granitic caves. Mineralogically they are opal-A and accumulate in successive layers with a whiskery druse tip formed by gypsum crystals. Initially they are porous but progressively become infilled by opal precipitation. This results in formation of solid speleothems. their size is only a few millimetres long. Bacterial activity accelerate quartz dissolution

Study of the variability in chemical composition of bark layers of Quercus Suber L. from different production areas

Cork is the bark of the cork oak tree (Quercus suber L), a renewable and biodegradable raw bioresource concentrated mainly in the Mediterranean region. Development of its potential uses as a biosorbent will require the investigation of its chemical composition; such information can be of help to understand its interactions with organic pollutants. The present study investigates the summative chemical composition of three bark layers (back, cork, and belly) of five Spanish cork samples and one cork sample from Portugal. Suberin was the main component in all the samples (21.1 to 53.1%), followed by lignin (14.8 to 31%), holocellulose (2.3 to 33.6%), extractives (7.3 to 20.4%), and ash (0.4 to 3.3%). The Kruskal-Wallis test was used to determine whether the variations in chemical composition with respect to the production area and bark layers were significant. The results indicate that, with respect to the bark layer, significant differences were found only for suberin and holocellulose contents: they were higher in the belly and cork than in the back. Based on the results presented, cork is a material with a lot of potential because of its heterogeneity in chemical composition

Nanosized Nb-TiO2 gas sensors derived from alkoxides hydrolization

Nanocrystalline TiO2 modified with Nb has been produced through the sol-gel technique. Nanopowders have been obtained by means of the hydrolysis of pure alkoxides with deionized water and peptization of the resulting hydrolysate with diluted acid nitric at 100 C. The addition of Nb stabilizes the anatase phase to higher temperatures. XRD spectra of the undoped and the Nb-doped samples show that the undoped sample has been almost totally converted to rutile at 600 C, meanwhile the doped samples present still a low percentage of rutile phase. Nanocrystalline powders stabilized at 600 C with grain sizes of about 17 nm have successfully been synthesized by the addition of Nb with a concentration of 2% at., which appears to be an adequate additive concentration to improve the gas sensor performances, such as it is suggested by the catalytic conversion efficiency experiments performed from FTIR measurements. FTIR absorbance spectra show that catalytic conversion of CO occurs at lower temperatures when niobium is introduced. The electrical response of the films to different concentrations of CO and ethanol has been monitored in dry and wet environments in order to test the influence of humidity in the sensor response. The addition of Nb decreases the working temperature and increases the stability of the layers. Also, large enhancement of the response time is obtained even with lower working temperatures. Moreover, humidity effects on the gas sensor response toward CO and ethanol are less important in Nb-doped samples than in the undoped ones.

Analysis of S-rich CuIn(S,Se)2 layers for photovoltaic applications: Influence of the sulfurization temperature on the crystalline properties of electrodeposited and sulfurized CuInSe2 precursors

This paper reports the microstructural analysis of S-rich CuIn(S,Se)2 layers produced by electrodeposition of CuInSe2 precursors and annealing under sulfurizing conditions as a function of the temperature of sulfurization. The characterization of the layers by Raman scattering, scanning electron microscopy, Auger electron spectroscopy, and XRD techniques has allowed observation of the strong dependence of the crystalline quality of these layers on the sulfurization temperature: Higher sulfurization temperatures lead to films with improved crystallinity, larger average grain size, and lower density of structural defects. However, it also favors the formation of a thicker MoS2 interphase layer between the CuInS2 absorber layer and the Mo back contact. Decreasing the temperature of sulfurization leads to a significant decrease in the thickness of this intermediate layer and is also accompanied by significant changes in the composition of the interface region between the absorber and the MoS2 layer, which becomes Cu rich. The characterization of devices fabricated with these absorbers corroborates the significant impact of all these features on device parameters as the open circuit voltage and fill factor that determine the efficiency of the solar cells.

Analysis by optical absorption and transmission electron microscopy of the strain inhomogeneities in InGaAs/InP strained layers

Optical absorption spectra and transmission electron microscopy (TEM) observations on InGaAs/InP layers under compressive strain are reported. From the band¿gap energy dispersion, the magnitude of the strain inhomogeneities. Is quantified and its microscopic origin is analyzed in view of the layer microstructure. TEM observations reveal a dislocation network at the layer interface the density of which correlates with ¿¿. It is concluded that local variations of dislocation density are responsible for the inhomogeneous strain field together with another mechanism that dominates when the dislocation density is very low.

Structural and gas-sensing properties of WO3 nanocrystalline powders obtained by a sol-gel method from tungstic acid

WO3 nanocrystalline powders were obtained from tungstic acid following a sol-gel process. Evolution of structural properties with annealing temperature was studied by X-ray diffraction and Raman spectroscopy. These structural properties were compared with those of WO3 nanopowders obtained by the most common process of pyrolysis of ammonium paratungstate, usually used in gas sensors applications. Sol-gel WO3 showed a high sensor response to NO2 and low response to CO and CH4. The response of these sensor devices was compared with that of WO3 obtained from pyrolysis, showing the latter a worse sensor response to NO2. Influence of operating temperature, humidity, and film thickness on NO2 detection was studied in order to improve the sensing conditions to this gas.