Platinum Electrodeposition in an Ionic Liquid Analogue. Solvent Stability Monitoring

The use of ionic liquid analogues as solvents has increased in order to substitute the aqueous solvents in some applications in which the side reactions are undesirable. However these solvents prepared from the mixture in the eutectic proportion of species establishing hydrogen bonds are susceptible of electrochemical reactions. The study of platinum deposition on vitreous carbon in an ionic liquid analogue (2 urea: choli ne chloride) is presented; the electrochemical study has permitted to interpret the sequence of the metal deposition process and simultaneously to analyze the behavior of the ionic liquid analogue along the process. Reduction reactions of the solvent relat ed both to the electronation of choline and hydrogen formation have been detected. Different substrata have been used in order to test the possibility and the extent of these reactions depending on the nature of material. The results indicate that the feas ible electrochemical window of the substrate/solvent is highly dependent of the kind of substrate; the negative limit is tied by the massive hydrogen reaction, reaction enhanced by the electrocatalytic character of the substrate.

Electrochemical synthesis of mesoporous CoPt nanowires for methanol oxidation

A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W) microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane"s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter) dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

[BMIM][PF6] Promotes the synthesis of halohydrin esters from diols using potassium halides

Haloesterification of diverse diols with various carboxylic acids was achieved using potassium halides (KX) as the only halide source in ionic liquids. The best yield was obtained in [BMIM][PF6] when 1,2-octanediol, palmitic acid and KBr were used. This yield was 85% and the regioisomer with the bromine in primary position was present in a 75:25 ratio. The regioisomeric ratio could be improved using either KCl or some phenylcarboxylic acids. [BMIM][PF6] acts as both reaction media and catalyst of the reaction. To the best of our knowledge, this type of combined reaction using an ionic liquid is unprecedented. The other solvents tested did not lead either to the same yield or to the same regioisomeric ratio.

Electrochemical synthesis of mesoporous CoPt nanowires for methanol oxidation

A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W) microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane"s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter) dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

Simple and fast methods based on solid-phase extraction coupled to liquid chromatography with UV detection for the monitoring of caffeine in natural and waste waters as marker of anthropogenic impact

Two concentration methods for fast and routine determination of caffeine (using HPLC-UV detection) in surface, and wastewater are evaluated. Both methods are based on solid-phase extraction (SPE) concentration with octadecyl silica sorbents. A common “offline” SPE procedure shows that quantitative recovery of caffeine is obtained with 2 mL of an elution mixture solvent methanol-water containing at least 60% methanol. The method detection limit is 0.1 μg L−1 when percolating 1 L samples through the cartridge. The development of an “online” SPE method based on a mini-SPE column, containing 100 mg of the same sorbent, directly connected to the HPLC system allows the method detection limit to be decreased to 10 ng L−1 with a sample volume of 100 mL. The “offline” SPE method is applied to the analysis of caffeine in wastewater samples, whereas the “on-line” method is used for analysis in natural waters from streams receiving significant water intakes from local wastewater treatment plants

Tailored Jeffamine molecular tools for ordering mesoporous Silica

Herein, we report the formation of organized mesoporous silica materials prepared from a novel nonionic gemini surfactant, myristoyl-end capped Jeffamine, synthesized from a polyoxyalkyleneamine (ED900). The behavior of the modified Jeffamine in water was first investigated. A direct micellar phase (L1) and a hexagonal (H1) liquid crystal were found. The structure of the micelles was investigated from the SAXS and the analysis by Generalized Indirect Fourier Transformation (GIFT), which show that the particles are globular of coreshell type. The myristoyl chains, located at the ends of the amphiphile molecule are assembled to form the core of the micelles and, as a consequence, the molecules are folded over on themselves. Mesoporous materials were then synthesized from the self-assembly mechanism. The recovered materials were characterized by SAXS measurements, nitrogen adsorptiondesorption analysis, transmission and scanning electron microscopy. The results clearly evidence that by modifying the synthesis parameters, such as the surfactant/silica precursor molar ratio and the hydrothermal conditions, one can control the size and the nanostructuring of the resulting material. It was observed that, the lower the temperature of the hydrothermal treatment, the better the mesopore ordering.

Dynamic electrostatic force microscopy in liquid media

We present the implementation of dynamic electrostatic force microscopy in liquid media. This implementation enables the quantitative imaging of local dielectric properties of materials in electrolyte solutions with nanoscale spatial resolution. Local imaging capabilities are obtained by probing the frequency-dependent and ionic concentration-dependent electrostatic forces at high frequency (>1 MHz), while quantification of the interaction forces is obtained with finite-element numerical calculations. The results presented open a wide range of possibilities in a number of fields where the dielectric properties of materials need to be probed at the nanoscale and in a liquid environment.

Dynamic electrostatic force microscopy in liquid media

We present the implementation of dynamic electrostatic force microscopy in liquid media. This implementation enables the quantitative imaging of local dielectric properties of materials in electrolyte solutions with nanoscale spatial resolution. Local imaging capabilities are obtained by probing the frequency-dependent and ionic concentration-dependent electrostatic forces at high frequency (>1 MHz), while quantification of the interaction forces is obtained with finite-element numerical calculations. The results presented open a wide range of possibilities in a number of fields where the dielectric properties of materials need to be probed at the nanoscale and in a liquid environment.

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.

Preparació i caracterització de materials mesoporosos en sistemes tensioactius

Estudi elaborat a partir d’una estada a la Universitat Nacional de Yokohama des de maig fins a mitjans de juny del 2006. S'ha estudiat el comportament fàssic i la preparació de sílica mesoporosa pels nous tensioactius fluorats d'estructura C8F17SO2(C3H7)N(C2H4O)nH (abreujat C8F17(EO)n. El tensioactiu C8F17(EO)n forma micel•les allargades i cristalls líquids en aigua, i per tant pot ser adequat per a la preparació de materials mesoporosos. Sílica mesoestructurada es va preparar pel mètode de precipitació per autoagregació cooperativa. Un estudi sistemàtic es va realitzar, investigant la influència de les concentracions de tensioactiu i precursor (TEOS), l’efecte del pH i de la longitud de cadena de poliòxid d’etilè. Els materials es van caracteritzar per raigs X a angle petit (SAXS), sorció de nitrògen i TEM. Els materials obtinguts presenten diàmetres de por petits i parets de por gruixudes. A més, aquests materials posseeixen altes superfícies específiques, que s’han obtingut emprant concentracions de tensioactiu petites, produint parets de por robustes sense microporositat significativa. La superfície específica es manté durant el procés de calcinació, malgrat un petit encongiment degut a l’entrecreuament de la sílica. Els materials de sílica obtinguts han mostrat ser significativament més robustos que altres materials similars descrits a la bibliografia, com la sílica MCM-41.

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.

Estudi de la desadsorció del pirè amb diferents surfactants en tres sòls artificials

Un dels problemes associats a la remeiació de contaminants hidròfobs és la seva poca disponibilitat. Es considera que un contaminant està disponible quan roman a la fase líquida del medi, ja sigui solubilitzat o en forma d’emulsió. Els surfactants són substàncies anfifíliques que promouen la transferència de compostos hidròfobs de la fase sòlida a la líquida. En aquest estudi s’escull el pirè com a representant dels hidrocarburs aromàtics policíclics i tres surfactants no iònics: un àmpliament citat a la bibliografia científica (Tween 80) i dos comercials (Gold Crew, BS-400). L’estudi es fa amb tres mescles d’argila i sorra amb diferents proporcions. La concentració micel·lar crítica (CMC) s’assoleix abans en sòls amb poc contingut en argila. L’eficiència dels surfactants està estretament relacionada amb la proporció d’argila i sorra. A concentracions molt per sobre de la CMC no s’observa una relació entre l’eficiència i la quantitat d’argila. El Tween 80 ha donat millors resultats que el Gold Crew i el BS-400, sense que aquest darrer no hagi presentat desadsorció de pirè.

An approximate mathematical model for solidification of a flowing liquid in a microchannel

A mathematical model is developed to analyse the combined flow and solidification of a liquid in a small pipe or two-dimensional channel. In either case the problem reduces to solving a single equation for the position of the solidification front. Results show that for a large range of flow rates the closure time is approximately constant, and the value depends primarily on the wall temperature and channel width. However, the ice shape at closure will be very different for low and high fluxes. As the flow rate increases the closure time starts to depend on the flow rate until the closure time increases dramatically, subsequently the pipe will never close.

Extensional flow of nematic liquid crystal under electric field gradient

Systematic asymptotic methods are used to formulate a model for the extensional flow of a thin sheet of nematic liquid crystal. With no external body forces applied, the model is found to be equivalent to the so-called Trouton model for Newtonian sheets (and fi bers), albeit with a modi fied "Trouton ratio". However, with a symmetry-breaking electric field gradient applied, behavior deviates from the Newtonian case, and the sheet can undergo fi nite-time breakup if a suitable destabilizing field is applied. Some simple exact solutions are presented to illustrate the results in certain idealized limits, as well as sample numerical results to the full model equations.

The implementation of liquid chromatography tandem mass spectrometry for the official control of lipophilic toxins in seafood: Single-laboratory validation under four chromatographic conditions

We performed a comprehensive study to assess the fit for purpose of four chromatographic conditions for the determination of six groups of marine lipophilic toxins (okadaic acid and dinophysistoxins, pectenotoxins, azaspiracids, yessotoxins, gymnodimine and spirolides) by LC-MS/MS to select the most suitable conditions as stated by the European Union Reference Laboratory for Marine Biotoxins (EURLMB). For every case, the elution gradient has been optimized to achieve a total run-time cycle of 12 min. We performed a single-laboratory validation for the analysis of three relevant matrices for the seafood aquaculture industry (mussels, pacific oysters and clams), and for sea urchins for which no data about lipophilic toxins have been reported before. Moreover, we have compared the method performance under alkaline conditions using two quantification strategies: the external standard calibration (EXS) and the matrix-matched standard calibration (MMS). Alkaline conditions were the only scenario that allowed detection windows with polarity switching in a 3200 QTrap mass spectrometer, thus the analysis of all toxins can be accomplished in a single run, increasing sample throughput. The limits of quantification under alkaline conditions met the validation requirements established by the EURLMB for all toxins and matrices, while the remaining conditions failed in some cases. The accuracy of the method and the matrix effects where generally dependent on the mobile phases and the seafood species. The MMS had a moderate positive impact on method accuracy for crude extracts, but it showed poor trueness for seafood species other than mussels when analyzing hydrolyzed extracts. Alkaline conditions with EXS and recovery correction for OA were selected as the most proper conditions in the context of our laboratory. This comparative study can help other laboratories to choose the best conditions for the implementation of LC-MS/MS according to their own necessities.