CROMATOGRAFIC ANALYSIS (3)

Author: GARCÍA VILLAR NATIVIDAD.
Year: 2005.
University: BARCELONA [www.ub.es].
Place of defense: FACULTAT DE QUÍMICA DE LA UNIVERSIDAD DE BARCELONA.
Place of preparation: UNIVERSIDAD DE BARCELONA.

Summary: The overall objective of this dissertation is the development of analytical methodology that allows sensitive determination of amino acids and amines biógenas. It has investigated the use of enzyme biosensors, continuous flow methodologies and different separation techniques such as liquid chromatography (HPLC) and capillary electrophoresis (CE), which has used the detection potentiometric, spectrophotometric and spectrometry mass (MS). It has also implemented various methods quimiométricos for the design of experiments and data processing. First, it developed three methods potentiometric using an enzyme biosensor lysine. The biosensor is based on an electrode potenciométrico contact metallic (All-solid-state) selective (ISE) of ammonium ion and consists of a membrane on which immobilizes chemically lysine oxidase enzyme. Lysine is degraded in the biosensor, releasing ammonia that is detected by the ISE ammonium. It provides a method potenciométrico for determining lysine based on the joint analysis of multivariate data generated by a system of sensors in series, which consists of the biosensor lysine and seven ISEs, NH4 +, K +, Na +, Li +, Ca2 +, Mg2 + and H +. Then, it optimizes an HPLC method for the determination of lysine using the biosensor potenciométrico developed as detection system. Lastly, there is a method in flow injection analysis based on a system potenciométrico differential Jan l biosensor that lysine is used as a working electrode, while as reference electrode is used ammonium circular electrode. The methods developed are applicable to the determination of lysine in samples of animal feed supply aminal and pharmaceuticals. Here are three developed analytical methods for determination of amines biogénas. These are based on the derivatization of the analytes with the reagent 1,2-naftoquinona-4-sulfonato sodium (NQS) and chromatographic separation or electroforética of derivatives for subsequent spectrophotometric detection. The first job to determine histamine through a system of derivitzación online (online) coupled with HPLC. It focuses especially on optimizing the reaction conditions continuously, allowing derivatizar histamine in perfectly controlled conditions. In this case, the separation of histamine and other amino acids amines is achieved by injecting the sample derivatizada directly in the chromatographic system. The next work is carried out off-guard column derivatization of the amines biógenas followed by a liquid-liquid extraction step that helps to clear the array of samples and preconcentrar the analytes. Thirdly, there is a growing separation of derivatives of amines biógenas by capillary zone electrophoresis, as an alternative to liquid chromatography. In this case, we have studied various strategies derivatization in-capillary allowing clean matrix samples and preconcentrar the analytes. Thirdly, there is a growing separation of derivatives of amines biógenas by capillary zone electrophoresis, as an alternative to liquid chromatography. In this case, we have studied various strategies derivatization in-capillary enabling automation and simplification of the derivatization process. It was also studying the possibility of improving the sensitivity by injecting electrocinética of samples. The methods developed in this section apply to the determination of amines biógenas in samples of red wine. Finally, there is a method HPLC-ESI-MS for determining 8 stating what 38b s cis-and trans-isomers of hydroxyproline, hidroxilisina and amino acid protein. It is based on the pre derivatization of the analytes with the reagent chiral N2- (5-fluoro-2 ,4-dinitrofenil) -L-valinamida (L-FDVA), and the chromatographic separation of its derivatives by HPLC. The detection of analytes is espectofotométricamente and additionally by mass spectrometry, using an electrospray ionization source and a mass spectrometer to tripo cuadrupolo.

Author: RODRÍGUEZ DIAZ RAFAEL CARLOS.
Year: 2005.
University: CÓRDOBA [www.uco.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: This report has contributed to the development of analytical methods readily applicable to the analysis routine using ion lantánidos as reagents. It is proposed for the first time a method which involves tying up ions terbio (III) and europio (III) in strips of cellulose for use as reagents dry in determining antibiotic ciprofloxacin and tetracycline in biological fluids. The measure of the intensity of both luminescent chelates independently allows resolution of the mixture without the need for complex mathematical treatments to get discrimination against both signals. The usefulness of these ions as analytical reagents in solution has been expanded through the development of various methods and direct derivatization post-columna parla with chromatographic determination of organic compounds. It has been carrying out a systematic study of behavior lumniscente of chelates antibiotic group quinolones with terbio. High levels of sensitivity obtained for the chelate terbio (III) -ciprofloxacina have allowed their determination in milk samples, using the methodology of time resolved. Moreover, similar to the behavior observed luminescent chelates of terbio of these antibiotics difficult to pinpoint one individual in the presence of others, which requires an additional phase chromatographic separation. We compared the results obtained for flumequine, measures and time resolved fluorescence, for the direct and chromatographic methods. The sensitivity and selectivity of chromatographic method with fluorescence detection allow the determination of this antibiotic in samples of animal tissues and milk, with a simple treatment shows for the elimination of proteins. Successes for flumequine served as a basis for the separation cormatográfica with derivatization post-columna eight quinolone antibiotics used in veterinary practice. This method has been applied to the determination of ciprofloxacin, enrofloxacin, danofloxacina and flumequine in milk samples with satisfactory results. It also has extended the applicability analytical terbio (III) as reagent derivatizante for the separation of eight phenolic compounds, specifically acid hidroxibenzoicos and catechins in samples of white wine. It has been demonstrated for the first time the value of ytterbium (III) as analytical reagent for obtaining measures dynamic scattering long wavelength and has been applied to the determination of inorganic ions and phosphate sulfites based on the formation of species Unhealthy for this purpose. The spectral and temporal selectivity are improved through the implementation of measures already kinetic long wavelength due to the elimination of static background signals and other components of the sample that can emit at wavelengths minors. The similarity of the results of the proposed methods with the methods provided by the official confirms its practical utility in the analysis of real samples.

Author: LUCENA RODRÍGUEZ RAFAEL.
Year: 2005.
University: CÓRDOBA [www.uco.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The chromatographic separation techniques are not present in almost all processes of measurement bio (chemical) with different purposes. In the same way his usual presence in configurations based on automatic flow systems. In research reported in this Doctoral Thesis has claimed progress in its implementation methodologies in both injection and continuous flow sequence for designing autoanalizadores multiparamétricos in the food sector and infrared sensors in the contexts of environmental and industrial sectors. The work aims to introduce develop and validate innovative analytical tools to improve determinations based on the measure of total rates. This option is consistent with the trend of analytical information demanded by customers Analytical Laboratory in which embodies the concept of simplification. So they chose, in most cases, by the use of a detector universal response little used in this context as the detector evaporativo light scattering, but also have been used in specific cases spectroscopy UV-vis and fluorescence. Also progress has been made in the design of sensors ATR-FT-IR based on the integration of separation (microextracción liquid) and detection. Also, there has been progress in the definition of autoanalizador adapting to the current trends in relation to demand for information from customers Analytical Laboratory. Thus, in this case the answer is provided by the autoanalizador: A Multiple-identifying up to three parameters using a single aliquot of sample, so that the discrimination between families is carried out by implementing the autoanlizador various techniques separation. B-Global family of compounds in the absence chromatographic separation between the various components of the sample. It has also innovated in the area of separation techniques through: A - The design of a multi-camera perfectly compatible with the flow configurations whose main characteristic is its versatility as it can, with the same basic design, implement various techniques separation with or without the use of membranes. B - The design of an infrared sensor based on the use of a membrane hidrófoba allowing completely automate the analytical process to be docked in line with an injection system with sequential flow (SIA) and significantly simplify the integration of the same stages of separation (microextracción liquid) and detection (ATR-FT-IR). The tools developed have been applied to solving analytical problems related to: A-measure parameters directly related to the quality of foods such as milk, soft drinks, wine, fruit juices and beer. B - The parameter estimation of environmental and industrial interests for determining the degree of depletion of alkali degreasing baths.

Author: SANTOS LUQUE BRICIO.
Year: 2005.
University: CÓRDOBA [www.uco.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: Over the last decade, the Analytical Chemistry has experienced exponential development with the emergence of new tools, new techniques and new tools for treating sample. At this time capillary electrophoresis has become, due to its high power resolution, as an analytical tool essential in many situations. Analysis and industrial controls, clinical analysis, environmental toxicology, analysis quieral or genetic analysis, are clear examples of this. This analytic potential is considerably amplified when this hybrid separation technology to the detection by mass spectrometry as it joins the high resolution power of technology with the sensitivity and selectivity of mass spectrometry. Despite this great potential, the use of computers CE-MS in laboratories routine is restricted, primarily because of the limitations or drawbacks inherent in the technique. These limitations are due on the one hand to the low number of shows that can be introduced into the electrophoretic systems, and on the other hand in diucion suffering from the analytes at the interface of electrospray when mixed with the liquid sheath. Besides the need to analyze complex samples leads to the emergence of matrix effects. In this context is the introduction, in a large number of methodologies, sample processing steps to resolve these limitations. Moreover, laboratories routinely require robust analytical tools and methodologies, fully automated involving minimal involvement of the analyst. It is also desirable that are quick techniques, which involve the use of minimum participation analísta. It is also desirable that are quick techniques, which involve the use of the minimal amount of sample and above all they are simple. Throughout this Doctoral Thesis, progress has been made in the development of analytical tools associated with capillary electrophoreses hibridada to mass spectrometry in a commercial equipment, which have increased the potential analytical technique and facilitate the transfer of this technique the laboratories routine. To that end, we have made use of the system preplnishment for treatment stages shows, specifically in solid phase extraction (SPE), by including minicolumnas in the system itself. Likewise, have carried out a series of amendments have been proposed and instrumental links, which have helped increase the potential analytical equipment business CE-MS. In this regard have been coupled treatment units based on sample flow techniques, FI or SI, in a discontinuous (At-line) through replenishment system on an ongoing basis (online), through the design an interface that has been integrated into the team by conducting a series of simple modifications instrumentals (with appropriate safety standards). Also, within the coupling constant, it has developed an interface that has enabled the integration of microestracción in solid phase (SPME) with the teams hibridados CE-MS. Finally, it has accomplished the transformation of the commercial team of CE-MS in a team that allows us to make two-dimensional separations. The team also proposed to introduce a high robustness and effectiveness, it only requires the inclusion of a modified electrode and a simple switch.

Author: PENSADO GÓMEZ-ULLA LUIS.
Year: 2005.
University: SANTIAGO DE COMPOSTELA [www.usc.es].
Place of defense: FACULTAD DE QUÍMICA DE LA UNIVERSIDAD DE SANTIAGO DE COMPOSTELA.
Place of preparation: FACULTAD DE QUÍMICA DE LA UNIVERSIDAD DE SANTIAGO DE COMPOSTELA.

Summary: The polycyclic aromatic hydrocarbons (PAHs) is one of the families surveyed more historically environmental contaminants in the field of analytical chemistry because of its carcinogenic and mutagenic nature to many international agencies refer such as WHO, the EPA, IARC , and so on. However, in addition to its natural origin, the growing emissions from the industrialization of society, coupled with the continuing advances in science that offers researchers new tools and new techniques, and the continual revisions in the law places the PAHs in a prominent position and current standing in the analytical chemistry must move forward. The work reflected in this report involves the development and optimization of new analytical techniques applied to the analysis of PAHs in various environmental matrices. In addition to application software specifically designed for the optimization of gradient HPLC separations for the ternary composition of samples applied to the analysis of PAHs, work addresses innovative methodologies extraction of these pollutants in different samples of environmental concern.

Author: GARCIA DEL MORAL GARCIA Ma. DEL PILAR.
Year: 2005.
University: LEÓN [www.unileon.es].
Place of defense: FACULTAD DE CIENCIAS BIOLOGICAS Y AMBIENTALES.
Place of preparation: FACULTAD DE CIENCIAS BIOLOGICAS Y AMBIENTALES.

Summary: LIVESTOCK IN THE CURRENT TREND IS LIMITED TO AVOID POLLUTION nitrogen SWALLOWED BY THE ANIMALS OF AN EXCESS OF PROTEÍNA DEGRADABLE. BY THEREFORE BE TIENDE TO BE INCLUDED IN THE DIET OF RUMIANTES SUPPLEMENTS PROTEICOS OF LOW DEGRADABILIDAD THAT COMPLEMENTEN TO PROTEÍNA MICROBIAL SINTETIZADA IN RUMEN. THE ORIGIN OF ANIMAL CHARGES HAVE BEEN BANNED DUE TO THE PROBLEM OF ENCEFALOPATÍA BOVINE AND USE SOME OF VEGETABLE. TO BE AMONG THE HIGHLIGHT TANNINS. SO VERY GENERAL COULD DECIRSE SUCH CONTENT OR LOW BENEFICIOSOS MODERADOS EJERCERÍAN EFFECTS ON ANIMAL AND BUT CONTENT ARE SENIOR NEGATIVE EFFECTS CLEARLY THAT PRODUCIRÍAN DISORDERS KIDNEY AND HEPÁTICAS E IRRITACIONES IN THE DIGESTIVE TRACT. WITHIN THE TANNINS THINK IS THAT HIDROLIZABLES ARE THAT PRODUCED MORE NEGATIVE CONSEQUENCES, AND THAT IS A COMPOSITE FENÓLICOS SINGLES degrading THAT MAY BE THE CAUSANTES ITS TOXICITY. MAJOR IMPACT IS ON THE EXPRESS RUMEN, WHERE ACTÚAN ON MICRO HEREIN, DROP THE SUMMARY OF PROTEÍNA MICROBIAL. RELATED TO IT, IS A SERIES OF SUBSTANCES, AMONG THAT STRESS CREATININA AND DERIVATIVES PÚRICOS, ALANTOÍNA ACID ÚRICO And XANTINAS, TO BE EXCRETAN IN THE URINE FROM RUMIANTES AND THE FOUNDATIONS PÚRICAS, ADENINA And GUANINA, IN PELLETS BACTERIANOS. THE ANALYSIS OF SOME OF THESE METABOLITOS NITROGENOUS NECESSARY TO STUDY THE EFFECT OF TANNINS IN RUMIANTES, BECAUSE APORTAN INFORMATION RUMINAL FERMENTATION PROCESS. THE NEED FOR AN ACCURATE AND RELIABLE ANALYSIS OF THESE FAMILIES OF COMPOUND IN DIFFERENT PARENTS, WE PUT HAS LED TO A POINT ANALYTICAL METHODS SUFICIENTEMENTE SENSITIVE TO DETECT AND CUANTIFICAR, CONCURRENT FORM, THE LARGEST NUMBER OF POSSIBLE COMPOUNDS. BY ANOTHER SIDE IS INTENDED TO THESE METHODS PERMITIESEN, ONLY WITH SOME CHANGES IN THE EXPERIMENTAL CONDITIONS, THE PURPOSE OF THE ANALYSIS OF THE VARIOUS GROUPS ESTUDIADOS, MAINTAINING THE NOT ALWAYS ON INTERFERENCE WITH EACH OTHER COMPOUNDS. HAS CHOSEN THE LIQUID CHROMATOGRAPHIC HIGH EFFICIENCY (HPLC), BECAUSE IT IS USED IN MORE TECHNICAL ANALYSIS OF THIS KIND OF SUBSTANCES ON ANY STAGE IN REVERSE .. IN THIS WORK IS PRESENT AS ALTERNATIVE, CHROMATOGRAPHIC BY PAIR OF ION TO INCREASE THE RETENTION AND IMPROVE THE SEPARATION OF COMPOSITE ESTUDIADOS, SOME OF THEM VERY POLARES, HOW IS THE CASE OF THE ALANTOÍNA. IN SUMMARY, DOCTORAL THESIS ON THIS, HAVE BEEN MADE POINT ANALYTICAL METHODS OF HPLC BY ION TO PAIR WITH LIGHT CHANGES IN EXPERIMENTAL CONDITIONS HAVE ALLOWED THE DETERMINATION OF DIFFERENT FAMILIES OF COMPOUND INTEREST IN THE FIELD OF NUTRITION ANIMAL DIVERSA IN SAMPLES OF NATURE, WHAT HAS THE PROVIDER KEY GOAL OF THIS STUDY.

Author: LEÓN LEAL ANDRÉS GERARDO.
Year: 2005.
University: COMPLUTENSE DE MADRID [www.ucm.es].
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: FACULTAD DE FARMACIA.

Summary: It has studied the influence of the presence of various cyclodextrins (CDs): beta-CD, 2-hidroxipropil-beta-CD, 2,3-dimetil-beta-CD and 2,3,6-trimetil-beta-CD, added the mobile phases on the conditions for the separation of alkaloids derived from beta-carbolina: norharmano, harmano and harmina. These compounds have a great biological significance because, in addition to presenting different pharmacological activity, occurring endogenously in the human organism as a result of the ingestion of alcohol and certain foods. The CDs conveniently added to the mobile phases improve chromatographic separations and chemical compounds structurally closely related (isomers). In this research were used brought two phases of silica stationary amended, C1 (methyl) and as a reference C18 (octadecilo). As mobile phases are optimized proportion organic solvent / buffer aqueous paralas mixing methanol / buffer, ethanol / buffer and n-propanol/tampón. We studied the effect of temperature on the separation process. Likewise, were determined by HPLC association constants of the complex alcaloide-CD, in different experimental conditions described for all alcoloides and various CDs studied. In addition, it marked the inclusion complexes synthesized and isolated by spectroscopic techniques of magnetic resonance imaging and luminescence. The results obtained show that the presence of CDs affects very significantly to the separations, and to obtain efficiencies of separation similar to those obtained by the use of mobile phases without CDs but with a higher proportion of organic solvent in the mobile phase . The presence of CDs can reduce the proportion of organic solvent in the mobile phase, which is called the mobile phases clean majority for their content in water. It has been determined as the presence of increasing concentrations of CD in the mobile phases affects the selectivity of separations. The effectiveness increases with increasing concentration of CDs reaching a peak and then decline to high concentrations. The selectivity ratios are increased when the stationary phase is C1 but not in the case of C18. The values and the constant association obtained vary depending on the type of CD and stage estacionaria-fase mobile employee. In general, increasing the temperature decreases the continuing partnership. Studies show luminescence of spectroscopic techniques including, as it produces a very significant change in the balance of proton transfer from norharmano in excited state. The results obtained by 13C-RMN show the inclusion of alcoloides studied, as the signals for the carbons C-6 and C-7 ring beta-carbolina show significant displacement with respect to the corresponding patterns. Experiments 2D-ROEXU-RMN confirm these results.

Author: ROSALES CONRADO NOELIA.
Year: 2005.
University: COMPLUTENSE DE MADRID [www.ucm.es].
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS, UNIVERSIDAD COMPLUTENSE DE MADRID.

Summary: Due to its high efficiency, and selectivity, herbicides fenoxiácido are widely used in agriculture today for the control of broad-leaf weeds, so their residues are present in a wide variety of matrices. The identification of such herbicides, either in the form of acid esters, has been carried out by capillary liquid chromatography, cLC with ultraviolet detection at different modes of separation: isocrático / isotermo, isocrático / temperature gradient elution and scheduled / isotermo, which I due to the small inner diameter of the column, the heat transfer is very effective and influence of temperature on the retention is significant. For maximum sensitivity in the analysis, it has done an exhaustive study of the conditions of injection, through which it has established the importance of the introduction of large volumes of sample along with the use of techniques location at the head column to avoid loss of resolution. Because of the complexity of the samples treated with the aim of achieving low levels of residues permitted by law, procedures have been developed and re-cleaning, mainly through solid phase extraction. They have evaluated the characteristics of retention and elution of herbicides in various absorbents based silica gel and polymer base, and have selected the most appropriate depending on the type of sample and the compatibility of the stage and preconcentration determination through cLC with methodologies location. Different methods developed have allowed the identification of fenoxiácidos in samples of fresh mint and apple juice to the maximum levels permitted by the Spanish and European regulations, in soils and in human urine, to levels that can establish the degree of contamination of workers using these products regularly. Moreover, efforts are on the verge methods for the resolution enantiomeric those herbicides, as 2,4-DP, MCPP and 2,4,5-TP presented quiralidad and thus only one of the isomers is responsible its activity. Among all studied chiral stationary phases, only the antibiotic vancomycin, has led to appropriate enantioselectividad. Through these methods, not only can you control the waste, but also to determine the purity and amount of each of the isomers in commercial formulations. Ultimately, the studies in this dissertation, has demonstrated the usefulness, efficiency and sensitivity of the pair capillary liquid chromatography analysis of this type of compounds with very low levels of concentration in biological samples, environmental and food, with the additional advantage of lower consumption of organic solvents and amount of waste generated, which have systems capillaries used.

Author: CORDOBÉS MARTÍN SHANDRA.
Year: 2005.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS.

Summary: The conidiación is a process morphogenetic common in filamentous fungi and consists of the production of asexual spores with finilidad the dispersion of the species. This is a complex process that involves environmental stimuli and programs genetically set. Most of the filamentous fungi are capable of conidiar amid air but the ability to replicate the process in submerged crops is also possible under controlled conditions very specific. It has been shown that the induction of conidiación in Penicillium cyclopium is determined for the accumulation within the cells of the conidiogenona a diterpeno endogenous secrets to the media. The induction of conidiación in Aspergillus nidulans is mediated by a metabolite terpenoide similar to the conidiogenona. According to the proposed mechanism of induction, the mycelium constitutively produces the inducer, and once they have reached the threshold concentration triggers indución of conidiación and it has been shown that the fungus has a mechanism inherent in the inactivation of this signal. There have also been found mutant aconidiales pointing to a regulatory system with the participation of more compounds.

Author: ORTIN MARTINEZ NATALIA.
Year: 2005.
University: ZARAGOZA [www.unizar.es].
Place of defense: FACULTAD DE MEDICINA.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The work has dealt with the study of sulfur compounds present in the wine. These odorantes can be of great impact on the aroma of wine because it can provide great strength aromatic but are present in small concentrations. They are characterized primarily by its penetrating aroma and be very reactive and unstable. These factors will influence their determination, as well as the inherent complexity of the wine. The analytes were: 4-mercapto-4-metil-2-pentanona, furfuriltiol, 2-metil-3-furantiol, acetate 3-mercaptohexilo and -mercaptohexanol. We have tried, over the work, four approaches to try this determination: 1. Selective extraction by forming complexes with p-hidroximercuribenzoato using a specific detection by mass spectrometry. 2. Optimization of a specific method for detecting a specific sulfur detector: flame photometric detector press. 3. Coupling solid phase extraction with microextracción in solid phase using non-volatile solvents. 4. Derivatización of thiol into wine with 4-vinilpiridina with subsequent isolation of derivatives with solid phase extraction and detection by mass spectrometry. In the second part of the work was performed characterization of the chemical aroma of high quality wines: 6 wines of the variety Merlot and 6 wines of the variety Chardonnay. This first identified the nature of the odorantes assets and secondly relations were established between the sensory descriptors that allow differentiation between wine and aromatic composition of the same. The proposed strategy is based on an analysis of quantitative sensory descriptive wines selected, which provides descriptors discriminating between wines. Below is analysis olfatométrico starting in extracts representative of the wines. After the quantitative analysis of odorantes wine aroma sets the hierarchy to determine odorantes discriminant, odorantes constituent and irrelevant. Multivariate analysis was performed of wines and introducing a number of assumptions which are verified through testing addition. Following this protocol were studied 6 wines Merlot and 6 wines from Chardonnay door quality from different parts of the world. Tests were performed to restore the aroma of one of the wines from Chardonnay and a rosé of Garnacha quite successfully

Author: SALGADO PETINAL CARMEN.
Year: 2006.
University: SANTIAGO DE COMPOSTELA [www.usc.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: There will always be a study of application of the technique microectracción in solid phase (SPME) for the extraction and identification of different compounds, which are considered environmental pollutants, applied to both aqueous and solid matrices. The compounds studied belong to the following groups: drug-selective inhibitors of the uptake of serotonin-Compounds sulforados volatile: alquiltioles and hydrogen sulfide-synthetic Fragrances: MUSK polycyclic and nitro MUSK - Retardantes flame: Polybrominated biphenyls (PBBs) and Difeniléteres (PBDEs ) - perfluorinated carboxylic acids (PFCAs) In all the studies have been optimized conditions SPME combined, in some complex matrices with other techniques of extraction solvent (MAE, US and UXO). For the final determination of the compounds are extracted emplo the gas chromatography with electron capture detector or coupled with mass spectrometry. All analytical methods proposed in the report presented a good selectivity, allowing reach a detection limit of the order of ng / L. Furthermore, this methodology muestramayor simplicity that other analytical techniques developed for the determination of these compounds.

Author: MACIA I PUIG MARIA ALBA.
Year: 2006.
University: ROVIRA I VIRGILI [www.urv.cat].
Place of defense: FACULTAT DE QUIMICA.
Place of preparation: FACULTAT DE QUIMICA. URV.

Author: SÁNCHEZ PRADO LUCÍA.
Year: 2006.
University: SANTIAGO DE COMPOSTELA [www.usc.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: INSTITUTO DE INVESTIGACIÓN Y ANÁLISIS ALIMENTARIO.

Summary: The main objective of the work done in this thesis is to show that the Microextracción in Solid Phase (SPME) can be applied to carry out studies of photodegradation of various pollutants, but not only as a technique of extraction and concentration, but also as a support or matrix, which produce the photodegradation. The photodegradation fiber, foto-SPME, extraction is a pre-irradiation, contrary to what happens in the rest of existing procedures used in the study of photochemical behavior of various pollutants. It has studied the photodegradation of various types of environmental pollutants "fiber" (foto-SPME) and water. The SPME is a technique very appropriate that simplifies photochemical studies of different organic compounds. In foto-SPME, fiber SPME serves as a support for the photodegradation, while in the photodegradation aqueous only be used as a technique for extracting. In short, foto-SPME allows: -Trazar the kinetic curves of photodegradation of the pollutants studied; -Calcular the kinetic parameters, constant speed and half-life times; - Establecer mechanisms photodegradation according to the fotoproductos detected; - Charting the photochemical behavior of these fotoproductos, as these in turn are likely to fotodegradarse. We have evaluated various factors that may affect the photodegradation fiber as the power of radiation, the wavelength of the same, the initial concentration of contaminant or the presence of dissolved organic matter. To verify whether the conduct in photochemical fiber SPME reproduces what happens in the environment, has also been done in the photodegradation of water all compounds studied, using SPME as a technique for extracting after irradiation, and the results are been compared to those obtained by foto-SPME. Thus, it has been established photochemical behavior of different pesticides, synthetic fragrances, flame retardants and a bactericide. All of them are fotodegradan in a virtually full-time study. Have been detected by foto-SPME, in total, one hundred and fifty nine fotoproductos of all pollutants studied, while by photodegradation water has only been observed training and ninety four of them. The practical application in the real world of foto-SPME has led to the study of photochemical behavior of bactericidal triclosán in samples of actual wastewater contaminated with this compound, without adding to it. It has also demonstrated the validity of foto-SPME to study the photodegradation used as a source of radiation simulator solar radiation and natural sunlight. By using the photodegradation "en-fibra" avoids the use of organic solvents, usually harmful to the environment and humans. Since the photodegradation takes place at the very fiber SPME and fotoproductos are generated "on site" are not necessary stages of extraction after irradiation. Precisely because they are not needed these stages, it is a simple, fast and which also minimizes the possible "loss" of fotoproductos in the stages of extraction. On the other hand, because of the high concentration factor of SPME, the photodegradation studies can be performed at levels of concentration is not as high as required with "classic" or commonplace, and are more representative of the levels found in the environment .

Author: LARRETA ASTOLA JOANA.
Year: 2006.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE CIENCIA Y TECNOLOGÍA.
Place of preparation: FACUTLAD DE CIENCIAS Y TECNOLOGÍA.

Author: MORET SOLÀ SÒNIA.
Year: 2006.
University: GIRONA [www.udg.es].
Place of defense: UNIVERSITAT DE GIRONA.
Place of preparation: UNIVERSITAT DE GIRONA.

Summary: Control of herbicides and other organic analytes present in the environment is a common practice in laboratories since the introduction of laws that put limits on the concentrations of these substances. For this reason, it is necessary to the development of new analytical methodologies for the control of organic compounds in the middle. Often, these analytes are trace levels in water and soil, along with a high content of substances húmicas and fúlvicas. One of the challenges in this type of analysis is the treatment of the sample (extraction, concentration and "clean" of the analytes for a proper quantification). These processes must be complemented by the use of chromatography techniques that allow far end of the analytes. The research is presented in this thesis focuses on the development of a method for the determination of 2,4-D, MCPA and its phenolic metabolites and one for the determination of caffeine. The first of the procedures developed has been applied to the monitoring of herbicides and its phenolic metabolites in soil of a golf course, while the second has been used for the determination of caffeine in natural waters, and subsequently in wastewater. The pair ionic liquid chromatography is a technique used in determining herbicides acídicos and composite clorofenólicos and are not required derivatization of the analytes prior to chromatographic analysis. In Chapter 2 develops a method of ion pair liquid chromatography (IP-HPLC) for the joint determination, water and soil of 2,4-dichlorophenoxy acetic acid (2,4-D), acid 4-cloro-2- metilfenoxiacético (MCPA) and its major metabolite clorofenólicos, 2-metilfenol (2-MP) 2-clorofenol (2-CP) 4-clorofenol (4-CP) 4-cloro-2-metilfenol (4-C-2 - HB) and 2,4-diclorofenol (2,4-DCP). The method developed for the joint analysis of the seven analytes based on the use of a mobile phase of acetonitrile: water (30:70) with 10 mM hydroxide tetrabutilamonio (TBA-OH) at pH = 7.2, setting the length of wave work to 230 nm. The separation of the analytes are consigui in a period of less than 22 minutes and the results obtained show that the method provides an adequate linearity. For the determination of caffeine (Chapter 6) is using the reverse-phase liquid chromatography with a mobile phase of acetonitrile: water (20:80), setting a wavelength of working 272 nm. In most methods for determining organic contaminants is necessary to introduce stages preconcentration and "clean" pre-deteccuón because these are trace levels and chromatography techniques are not sensitive enough to detect these levels . The solid phase extraction technique is the most applied by its simplicity and ease, and by the large number of sound stages available. In Chapter 3 evaluates different solid phases for the enrichment and "clean" of the analytes, in conjunction with a development phase extraction of the analytes soil. The adsorbent SDB-1 is the best choice for the merger of the seven analytes when they are extracted from the soil samples with sodium hydroxide 0.01 M. For cafeïna (Chapter 6), being a neutral compound has been conducted concentration and "clean" with an adsorbent sñilice chain C18 (ACCUBOND), obtaining quantitative recoveries working with sample volumes of 100 mL, levels of 0.1 mg L-1, flows load 25 mL min-1 and eluciones with 2 mL of methanol. Along with the solid phase extraction, in Chapter 4 explores an alternative that aims to improve the conditions of concentration and "clean" to 2,4-D, MCPA and its phenolic metabolites. It has opted for the development of a system of supported liquid membrane coupled to the system IP-HPLC. For studies using SLM have used two types of geometry: Membran 8 as lamin 82f ares and hollow fiber ( "hollow fiber"). The preconcentration technique of mambrana liquid tubular geometry has been compared with the technique of solid phase extraction (SPE). This comparison shows that both provide a high level of "clean" in extracots soil, a high concentration factor and an efficient separation of the analytes in relation to the amteria organic present in the soil sample. However, the liquid membrane system provides better overall performance because the receiving phase aqueous medium is a fully compatible with the method of detection IP-HPLC and all analytes can be extracted and analyzed in a single fraction. Finally, in Chapter 5 the developed analytical methodology has been applied to the study of the processes of adsorption and transport of 2,4-D, MCPA and its phenolic metabolites in soil. In the laboratory study of the adsorption has ealizado through experiments in batch that have identified the corresponding adsorption isotherms, and trials column. In order to study the dynamics of herbicides in real terms, has conducted a field experiment. We conducted a controlled application of herbicide business Bi-Hedonal, which contains as active ingredients 2,4-Dy MCPA and simúltaneamente a plotter, in a plot of 100 m2 located on the golf course Serres de Pals, irrigated with reclaimed water.

Author: PERÉ TREPAT EMMA.
Year: 2006.
University: BARCELONA [www.ub.es].
Place of defense: FACULTAD DE QUÍMICAS.
Place of preparation: FACULTAT DE QUÍMIQUES, UNIVERSITAT DE BARCELONA.

Summary: In this thesis applies Quimiometria two phases of the analytical determination of pollutants in the environment. It has been applied Quimiometria analyzing environmental data tables, where he has studied and analyzed systematically by applying various methods quimiométricos the presence and distribution of pollutants in the environment, whether organic compounds or metals, obtained in follow-up studies (monitoring) and control of various environmental compartments (air, water, sediments, fish…). And where it draws most important sources of pollution, both natural and type of anthropogenic type, and both ad hoc nature of the type of diffuse. It also deducted its geographical distribution and / or its temporal evolution. All this with the aim of contributing to the overall assessment of environmental quality currently available in the various geographic areas under study. At the same time also deepens the understanding, development and widespread use of lso different methods quimiométricos proposed. A second application of Quimiometria has been chromatographic data analysis and specifically, it has been studied and solved problems coelución chromatographic analysis in complex samples using techniques quimiométrica. Traditionally determining bioacidas carried out by liquid chromatography with detection diodes in series (LC-DAD) or by liquid chromatography with detection by mass spectrometry (LC-MS). Here, in this thesis are proposed resolution procedures quimiométrica in cases where possible strategies experimental traditional problems related coelución compound interest, the overlap of their MS spectra or fragmentation ions in common or similar; or if you optimize the parameters of time and / or cost determinations chromatography. The procedure has been applied Resolution Multivariante of Curves by alternating least squares (MCR-ALS), in the resolution, identification and quantification of compounds strongly coeluidos chromatographic in environmental samples and in the presence of strong interference and matrix effects. It has used the procedure MCR-ALS in chromatographic analysis with short columns (fast chromatography), which provide eluciones fastest of the compounds of interest and therefore a considerable saving of time and reagents, but unfortunately coeluciones stronger.

Author: MARTÍNEZ CAÑAS MANUEL ALEJANDRO.
Year: 2006.
University: EXTREMADURA [www.unex.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS - UNIVERSIDAD DE EXTREMADURA.

Summary: This Labor Research aims at the analysis of some antibiotics quinolónicos and fluroquinólonicos for use in medicine and veterinary science, and the development of new analytical methods for determination of the same. The techniques used have been working both electroanalíticas as luminescence molecular and HPLC. Applications post has been made in biological fluids, pharmaceuticals and animal tissues. Various strategies have been used chemical (media micelares) and quimiométricas (techniques derived, multivariate calibration methods) for the development of analytical methods. Among these methods include first order (partial least squares regression, principal component regression and classical least squares regression), second order (PARAFAC, N-PLS, Unfolded-PLS) and non-linear (Artificial Neural Networks) , as well as methods for optimization and design of experiments. The methods developed presented an undeniable interest from him standpoint of their application agrifood and farmacologíca, to allow additional analysis procedures simple and sensitive.

Author: SANCHEZ MARTINEZ MARIA LOURDES.
Year: 2006.
University: CÓRDOBA [www.uco.es].
Place of defense: CAMPUS DE RABANALES.
Place of preparation: CAMPUS DE RABANALES.

Summary: This report has demonstrated the usefulness of fluoróforos long wavelength and / or use of reagents inmunoquímicos in various methodologies determinativas. It has proposed two analytical methods based on chromatography inmunoafinidad detection fluorimétrica indirectly for determining alquibencenosulfonatos chain linear (LASs) in environmental samples. It has compared the characteristics of the measures fluorescence long wavelength with those provided by a fluoróforo conventional. Three methods have been developed based immunoassay for the fluorescence polarization (FPIA) Long-wavelength for determining haptenos low molecular weight, such as amikacin and surfactants LASs and for the determination of macromolecules such as gliadinas. The most important methodological innovations achieved, which pose an advantage over the FPIA conventional, were: 1, Development strips inmunoreactivo through technology dried reagents and polarization measurements of the lfuorescencia in solid applied to the determination of amikacin in serum samples. 2, - Marking of gliadinas with a complex ruteniol (II) for the development of a strip method FPIA long wavelength for the analysis of gluten-free foods. 3 - Utility measures dynamic FPIA long wavelength for determining LASs in environmental samples. Three methods have been proposed kinetic rapid response through measures luminescence long wavelength. It has extended the usefulness of dye green indocianina as analytical reagent for the development of a kinetic method for determining fluorimétrica of amikacin long wavelength in serum samples. It has been described a fluorinmunoensayo homogeneous, using a marker terbio, for the determination of gliadinas in food samples. Finally, it has demonstrated the utility of the measures dynamic polarization of the fluorescence for determining LASs using the FPIA long wavelength above. The implementation of all the methods developed in other research to actual sample analysis has provided satisfactory results, demonstrating its practical usefulness.

Author: EXPOSITO CIMADEVILLA YOANA.
Year: 2006.
University: OVIEDO [www.uniovi.es].
Place of defense: FACULTAD DE QUIMICA.
Place of preparation: FACULTAD DE QUIMICA DE LA UNIVERSIDAD DE OVIEDO.

Summary: In this thesis is a study in produndidad on the behavior of hydrophobic proteins and affect the quality of natural cider Asturian and foaming properties. To that end, it has developed a method for analyzing proteins according to their hydrophobic characteristics by reversed phase liquid chromatography (RP-HPLC), using a column C18 (250 x 4.6 mm, 5 microns and 300 anstrons) and using as mobile phase a mixture of acetonitrile, acid trifluoroacético and water gradient mode. Before carrying chromatographic analysis, it was necessary to consider a procedure for cleaning and concentration, allowing isolate the protein to the appropriate levels for detection. To this end, different treatments were studied sample: Precipitation, ion exchange, ultrafiltration, dialysis and Gel Filtration. Of these, in gel filtration, it was considered the most appropriate for the procedure being able to concentrate and eliminate interfering at the same time, quickly and with greater recovery of protein. In addition it was found that this treatment met the standards of accuracy adequate to characterize the protein profile of a natural cider. The classic electrophoresis confirmed the presence of proteins once completed their treatment and showed us bands of proteins with molecular weights ranging from 20 and 97 KDa. The optimized method has been applied to the analysis of natural Asturian cider fermented in the traditional manner and sparkling ciders produced by the method Champenoise. Their foaming properties have been evaluated, taking into account the characteristics of proteins present and by the determination of its parameters blowing (the maximum height, HM: height stable, HS and stability of the foam, TS). In ciders natural Asturias, the profile of proteins obtained by chromatography, combined with the application of various techniques quimiométricas (ANOVA, PCA) to the results, has allowed the differentiation of cider depending on the sensory attribute espalme of their properties blowing and technology overhaul in the development process. En el intento de determinar qué tipo de proteínas están presentes en la espuma y por tanto determinan su formación y características, se ha llevado a cabo la extracción de la espuma sobre las sidras asturianas, separando así la sidra en dos fracciones: espuma y el resto , called base cider. The fermented cider by the method Champenoise, has done a comparison of the content and features of proteins and the properties of foam samples fermented in two different years and inoculated with two types of yeast. Collected data, it was found that the application of multivariate statistical techniques allow the classification of samples through its chromatographic profile. Using the technique of canonical correlations on the results, has established correlations between the parameters of foam and characteristics of proteins found in ciders studied. From the results obtained, using liquid chromatography as a method of analysis and gel filtration as a technique for cleaning and concentration of the sample, has reached the following conclusions: - There is much protein in ciders natural quality. With only two proteins, one of hydrophobicity and low hydrophobicity of other media, ciders are ranked according to their quality. - In developing natural ciders so industrial there is a higher protein content and in particular of the most hydrophobic. - Proteins hydrophobicity media, which are exerted greater influence on the parameters of foam. The proteins are extracted foam are 8 the most 389 hydrophobic. The protein profile can distinguish between apple cider made from native and foreign, in addition to differentiate the type of yeast used in ciders second fermentation.