MASS SPECTROSCOPY

Author: CHALER FERRER ROSER.
Year: 2004.
University: BARCELONA [www.ub.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA DE LA UNIVERSIDAD DE BARCELONA.

Summary: As part of this thesis has been implemented the concept of biomarcador and have developed analytical methods to study in order to contribute to the resolution of various geochemical problems, which have marked the following objectives: development of methodologies for quantifying alquenonas of interest paleoclimático by gas chromatography coupled with mass spectrometry in positive chemical ionization mode. Comparison with the reference method usually used to measure paleotemperaturas from these alquenonas by gas chromatography with flame ionization detection. And analysis of compounds esterólicos as specific markers of pollution in urban samples from a wastewater treatment plant. And to advance basic knowledge d mechanisms processing organic molecules in different environments depsocionales old, have charted these three objectives: Characterization using biomarkers geochemical rock originating in the watershed Vasco-Cantábrica to establish the origin of the oil found in the zone. Study of sediments in the period Albiense (Cretaceous middle) of the basin Vasco-Cantábrica to ascertain the origin of distributions alcanos linear predominance of long-chain counterparts par. And characterization of resins or ámbares period fossils from Cretaceous deposits of Alava and Cantabria

Author: SENTELLAS MINGUILLÓN SÒNIA.
Year: 2004.
University: BARCELONA [www.ub.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Author: RODRIGUEZ GONZALEZ PABLO.
Year: 2004.
University: OVIEDO [www.uniovi.es].
Place of defense: FACULTAD DE QUIMICA.
Place of preparation: FACULTAD DE QUIMICA.

Author: PISONERO CASTRO JORGE.
Year: 2004.
University: OVIEDO [www.uniovi.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: This Doctoral Thesis has focused the study and development of new instrumentation based on downloads luminescent (GDs) with detection by optical spectroscopy (OES) and mass (MS), and in its application to the direct analysis of solids. It has evaluated the potential of an analytical system GD-OES (using a plasma generated by radio frequency) to conduct an analysis of the concentration profiles in depth material with metallic coatings based Zn. We have used a method of measurement based on the concept of efficiency and emission in particular, has studied the method of operation that leaves the variable parameters such as pressure, and obtained satisfactory results comparable to those obtained using the other methods of operation. In order to improve the sensitivity of the system GD-OES and assess the benefits it provides analytical system GD-MS, has been designed and developed different prototypes of a new luminescent discharge chamber to be coupled with a mass spectrometer time flight (TOFMS), which originally was a sales team ICP (inductively coupled plasma) -TOFMS. The simple design of the chamber allows for easy downloading exchange with the PKI which can be carried out using the same mass spectrometer both the direct analysis of solid (GD) and the analysis of samples dissolved (PKI). There has been studied the different physical and chemical properties of the new system GD-TOFMS for analysis of coated materials: metal and glass materials of different thicknesses, using the latter discharges generated luminescent radiofrequency rather than direct current. The rapid speed of acquiring mass spectra of the system GD-TOFMS has enabled to carry out the analysis of thin coatings of only a few nanometers thick. Moreover, the characteristics of extraction and detection of ions in TOFMS make it a very suitable to be coupled with a pulsed ion source. Therefore, they have been evaluated analytical benefits of a system GD-TOFMS where the discharge is doubly luminescent press. Two consecutive high-voltage pulses with a duration of a few microseconds, to improve the processes of fragmentation and subsequent ionization taking place in the plasma discharge, improving sensitivity and temporal resolution of separating the sign from the ions gas discharge those from the sample. In addition, these features have been compared with those obtained analytical in a pulsed discharge easy way. On the other hand, the use of a mass spectrometer dual approach (high resolution) (DFMS) enhances in several orders of magnitude sensitivity obtained with the system GD-TOFMS although in this case the spectral acquisition speed decreases considerably. However, while systems GD-DFMS exhibit excellent sensitivity most of them show a very poor depth resolution that prevents them from carrying out in-depth analysis of coated materials. In this regard have been improved analytical performance of a system GD-DFMS from changes in the design of the camera and the parameters that control the discharge, so that has finally obtained a system GD-DFMS which presents a high sensitivity at the same time an adequate resolution to carry out deep analysis of coated materials.

Author: NOGAL SANCHEZ MIGUEL DEL.
Year: 2004.
University: SALAMANCA [www.usal.es].
Place of defense: FACULTAD DE CIENCIAS QUIMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUIMICAS.

Summary: The objective of this work is to explore the possibilities of analytical direct coupling of a generator head space of a mass spectrometer (HS-MS) to resolve various problems of environmental pollution. The instrumental configuration used is within the methodologies not separativas. The measurement procedure is simple and just handling of the sample with decreasing errors stages of preparing the same. The coupling HS-MS was used in three specific environmental problems: 1 .- Detection and quantification of contamination by petroleum hydrocarbons. The results show that this methodology is revealed as a powerful tool in the field of pollution of soil and sand beaches. Using techniques quimiométricas represents a simple solution, quickly and efficiently. 2 .- simultaneous quantification of a mixture of compounds. The team used a technique is reliable and fast for the quantification of a mixture of compounds. Specifically good results were obtained in quantifying 6 volatile organic compounds (benzene, toluene, ethylbenzene, m-xileno, methyl tert-butil ether and mesitylene) in drinking water and river. The incorporation of the transfer of calibrated to correct the problems of instability of the signal is an important contribution to the teams with detection by mass spectrometry. 3 .- Overall methyl tert-butil ether in gasoline through three methods of analysis based on mass spectrometry: generation of space head, direct injection and fast gas chromatography. The three developed methodologies have provided similar results in the identification of this compound. Analysis times are reduced significantly when using methods not separativos

Author: HINOJOSA REYES LAURA.
Year: 2005.
University: OVIEDO [www.uniovi.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: Selenium is an essential element that plays a very important role in the human diet. However, the optimal daily intake is in a narrow range (50-200 ug.día-1), out of which can have different clinical disorders both states as deficiency of intoxication. Some studies suggest that the deficiency may increase the risk of heart disease power and some types of cancer. Here, the consumption of different selenium supplementation, including yeast selenizadas, have increased markedly. However, the bioavailability and toxicity of the element depends not only on its total concentration but also the ways in which physico is therefore the aim fundametnal of this Doctoral Thesis is about to put new analytical methodologies for the total determination and the expectation of selenium in biological samples from clinical and nutritional by isotope dilution mass spectrometry and. So, first became a methodology for determining analytical total selenium in biological samples by isotope dilution analysis in a ICP-MC equipped with cell collision / reaction. The methodology was used to study the levels of selenium in serum of healthy people. Subsequently it was pointed an analytical method for the quantitative speciation of selenium in human serum using isotope dilution in the form of addition post-columna comparing two types of chromatographic separation: anion exchange chromatography and affinity chromatography. The methodology was used to study the distribution of selenium in serum protein between healthy individuals and patients with renal efforts to detect possible differences enters both populations. On the other hand, was made unto a method of analysis by isotope dilution for quantifying slenometionina in yeast selenizadas. It summed up the selenomethionine (SeMet) enriched isotópicamentel The SeMet marked the isotope get through the cultivation of the yeast Saccharomyces cervisiae in an environment enriched with 77Se. The isotopic tracer thus obtained was applied to the analysis of SeMEt in yeast selenizadas through IDA-HPLC-ICP-MS comparing different procedimietnos of enzymatic hydrolysis. Finally, we used a model of gastrointestinal digestion in vitro for information on the bioavailability of selenium compounds on yeast selenizadas. To do this, first identified both selenocompuestos posts, in solution with digestion gastrointestinal as those remaining in the non-digested strong (and therefore not biodisponbibles. Lastly, it also obtained quantitative information on the amount of selenomethionine available after digestion gastrointestinal in vitro. It used two-dimensional chromatography and espectormetría of atomic masses (ICP-MS) and molecular (ESI-MS and MALDI-TOF MS).

Author: CENTINEO GIUSEPPE.
Year: 2005.
University: OVIEDO [www.uniovi.es].
Place of defense: FACULTAD DE QUIMICA.
Place of preparation: UNIVERSIDAD DE OVIEDO, FACULTAD DE QUIMICA.

Summary: Analysis of speciation has been defined as the determination of the physicochemical ways in which one can find an element in a sample. Normally these tests focus acoplando a technique of separation powerful, as chromatography or gas chromatography Liquid, a highly sensitive and selective detector as the Mass Spectrometer (MS). The justification for the need for studies of speciation is that the various chemical species in which one can find an element in drastically affects their toxicity, bioavailability and the role it can play this element in the body of the living. Gradually, both domestic and international laws have begun to include priority substances whose analysis requires the use of chemical analytical procedures that call for "elemental speciation." Thus, Directive 2000/60/EC establishing a framework for Community action in the field of water policy. Annex X of this directive, issued as Decision 2455/2001/EC, drawing up a list of priority substances that have been controlling in inland waters and includes the European cation tributyltin within this list. The legislation also includes Spanish expressly compounds butilados tin on the list of controlled substances in discharges to surface waters Continental, Royal Decree 995/2000. The high content of methyl mercury in some fish for human consumption triggered alarms many administrations due to the high toxicity of this compound and its possible effect on the fetus in pregnant women and on the intellectual development of children. Thus, the European Union in its Regulation (EC) 221/2002 (5) includes the methylmercury in the list of compounds to check on fishery products subject to a ceiling of 1 mg / kg fresh weight. All these data confirm the need for routine monitoring of various chemical species much water as food elemental speciation using procedures that are highly reliable and, if possible, fast and economical. Therefore, the overall objective of this PhD thesis is the development of methodologies for routine high quality for the speciation of organometallic compounds that can be used by public or private laboratories under the current Spanish legislation and community both for water as for food. These methodologies routine must offer advantages over the currently used methods in terms of sensitivity, selectivity, accuracy and uncertainty in terms of speed, cost and ease of manejo.Se has perfected and applied a methodology for determination simultaneous organometallic compounds of mercury, lead and tin in water by Gas Chromatography-Mass Spectrometry. We studied the conditions for extraction / preconcentration of organometallic compounds under study in natural waters through technical microextracción in solid phase (SPME), with the objective of minimizing detection limits for organometallic compounds under review. The final determination of all species simultaneously organometallic interest was carried out by GC-MS with impact-mail has been refined and validated a method for the simultaneous determination of compounds butilados of Sn by Gas Chromatography using a detection technical high accuracy and precision as is the Isotope Dilution in combination with Mass Spectrometry. We studied the feasibility of I 8 toward real af2 tions precise isotopic by GC-MS and optimized parameters necessary for measuring isotopic relations with accuracy and precision, such as integration time. As tracer was used mixture of MBT, DBT and TBT enriched in the isotope 119Sn. It identified the most important features of the analytical methodology GC-IDMS developed and validated methodology GC-IDMS through its application to the analysis of certified reference materials. Finally, it validated and proven methodology in accordance with the rules ENAC (National Accreditation Entity). We studied the interpretation of spectra of masses of compounds butilados tin using an algorithm to reconstruct isotopic patterns for measuring isotopic relations exact molecular fragments by GC-MS. An algorithm was used to reconstruct isotopic profiles to study the mass spectra of butilados tin and routes of these compounds using fragmentation patterns with isotopic concentration of Sn and mono-, di-, and tributyltin enriched in 119Sn. To clarify differences in fragmentation, these compounds have been both etilados as propilados and its impact mass spectra of electronic estudiadron in terms of relations isotopic tin for application in dilution isotópica.Se has perfected and validated an Isotope Dilution methodology for the determination of methylmercury in tuna by Gas Chromatography-Mass Spectrometry. We studied different derivatization reactions in the pursuit of molecular fragment most appropriate for measuring isotopic relations mercury. In addition, it carried out the development of methods for extraction and preconcentration of methylmercury by SPME and Liquid-Liquid Extraction. The validation of the methodology developed was done through its application to the analysis of reference materials and participation in an intercomparison exercise organized by the CCQM (Comité Consultatif pour la Matière Quantity).

Author: BALAGUER ARDANUY ELVIRA.
Year: 2005.
University: BARCELONA [www.ub.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: UNIVERSITAT DE BARCELONA.

Summary: The ultimate objective of this thesis has been set different methodologies using capillary electrophoresis coupled to mass spectrometry with electrospray ionization (CE-ESI-MS) applied to the analysis and characterization of peptide hormones and glycoproteins. At first studied the mating of CE-ESI-MS in the separation of a number of peptide hormones of therapeutic interest, optimizing the main parameters that affect the ionization and separation with two different interfaces, a liquid interface Coaxial and other interface without auxiliary liquid, or sheathless. We compared the two interfaces in terms of reproducibility and detection limits in order to assess what interface provides better benefits. Here are developed different methods of analysis of glycoproteins intact by CE-ESI-MS, especially applied to the analysis of a glycoprotein with high interest: recombinant human erythropoietin (r-HuEPO). It also developed methods for analyzing the N-glicanos released from the various glycoproteins, and especially the r-HuEPO to get more information about their carbohydrates. The information was combined analysis of glycoproteins intact with the analysis of glicanos, and thus were able to deduct a certain composition of carbohydrates with high confidence. Finally, we developed a method of separation by CE-UV of glicoformas of the human transferrin under experimental conditions consistent with the detection with mass spectrometry. In this way it was possible to diagnose congenital disorders of glycosylation unequivocally by CE-ESI-MS.

Author: JOVER COMAS ERIC.
Year: 2005.
University: BARCELONA [www.ub.es].
Place of defense: FACULTAT DE QUÍMICA.
Place of preparation: FACULTAT DE QUÍMICA.

Author: RODA NOGUERA ORIOL.
Year: 2005.
University: POMPEU FABRA [www.upf.edu].
Place of defense: DEPARTAMENTO DE CIENCIAS EXPERIMENTALES Y DE LA SALUD.
Place of preparation: DEPARTAMENTO DE CIENCIAS EXPERIMENTALES Y DE LA SALUD.

Summary: Pancreatic cancer is very aggressive and is the fifth leading cause of cancer death in the Western world. The receiver tissue plasminogen (tPA) is expressed on i plays an important role in tumor progression. This thesis has deepened in the study of molecular mechanism of tPA i their receptors in cancer. First we have characterized the interaction between tPA with Annexian A2 (its main receiver in endothelium and highly expressed in the pancreas) demonstrating that the published data on the sequence responsible for such interaction are correct. Secondly, using tools proteómicas, we have identified proteins that interaccinan with tPA in an essay pull down on lisados cellular pancreatic, characterizing a set of potential recipients of tPA. In this study we found the galectina 1, a lectina of which had not been described interaction with tPA. Finally we made the biochemical characterization of the functional i galectina 1 as a novel ligand of tPA and the paper that this interaction plays in pancreatic cancer.

Author: ABAD GARCÍA BEATRIZ.
Year: 2006.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE CIENCIA Y TECNOLOGÍA.
Place of preparation: FACULTAD DE CIENCIA Y TECNOLOGÍA.

Summary: The adulteration of food, in this case fruit juice is a serious economic problem that not only affects the quality of the product but represents an economic fraud, and you can have an impact on the health of consumers. Therefore, specifies methods for the determination of the effective adulteration juices, so as to reduce the number and severity of the economic fraud and incidents of loss of quality. Therefore, the objective of this work is to study the profiles polifenólicos of fruit used in the production of juices, to find chemical markers polifenóicos to detect adulteration in fruit juices. This has been developed and validated a method of analysis for the identification and determination of the compounds in polifenólicos fruit juices, based on the High-Resolution Liquid Chromatography with detection by photodiodes and Mass Spectrometry and Masses in tandem (HPLC - DAD-MS/MS). We have studied and interpreted the mass spectra patterns and polifenólicos deducted mechanisms fragmentation, in search of patterns and methodological rules simple and useful in identifying plifenoles, and finally, we have identified and quantified the different polyphenols in juice fruit. With the large volume of information gathered, has conducted a survey quimiométrico for characterization and differentiation of fruit juices in terms of its profile polyphenolic, using the Principal Component Analysis (PCA), Cluster Analysis (CA) and Discriminante Linear Analysis (LDA). Finally, it has used the technique of Multiple Linear Regression (MLR) for predicting percentage of adulterant in mixtures fraudulent.

Author: SÁNCHEZ ORTEGA ALICIA.
Year: 2006.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: DEPARTAMENTO DE QUÍMICA ANALÍTICA (UPV/EHU).

Summary: The fenitrothion is an organophosphate insecticide contact, but their toxicity was moderate. An overexposure during manufacture or use, and intentional or accidental ingestion may result in severe poisoning. Recently has been very useful in the treatment of forest pests such as the aphid lanígero of poplar (Erisoma lanigerum) or procesionaria pine (Thaumetopea pityocampa). The main objective of this Doctoral Thesis will be the development of analytical methodologies sensitive and selective enabling the determination of fenitrothion and its major metabolites (3-metil-4-nitrofenol and fenitrooxon) in different environmental matrices. These analytical methodologies will be applied to study the persistence of these compounds after the implementation of fenitrothion over an area affected by Aphid lanígero. Due to the complexity of the arrays to analyze the sample preparation will be one of the most critical stages in the analytical procedure. This will develop different extraction techniques as SPME, SPE and SPE-dispersiva for analysis of aqueous samples, soda and leaf. Analytical techniques will arise as the separation of high-resolution liquid chromatography (HPLC) and gas chromatography (GC) with different types of detection. In addition to the detection of very complex matrices such as leaves, the samples were quantified using real isotope dilution.

Author: BARCELÓ BARRACHINA ELENA.
Year: 2006.
University: BARCELONA [www.ub.es].
Place of defense: FACULTAD DE QUÍMICA-FÍSICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: The heterocyclic amines are compounds that are generated during cooking protein food such as meat and fish. Because they are mutagenic and some of them carcinogenic in animals, to study the possible relationship between the intake of these amines with cancer in humans, it is necessary to determine the content of these compounds in cooked food. Therefore, in this thesis have developed different methods of analysis of heterocyclic amines in some meat extracts, based on separation techniques coupled to mass spectrometry. Specifically, it has proposed methods of liquid chromatography and gas chromatography. Using different types of mass analyzers as triple cuadrupolo, ion trap, and tiempo-de-vuelo. It has also been confirmed the elemental composition of the fragments of amines, previously proposed in the study of the routes of fragmentation. And lastly, it has launched a new line of research in the field of capillary electrochromatography, which has carried out the development of monolithic columns methacrylate base for the study of the separation of amines heeterocíclicas.

Author: VIERA ALCAIDE ISABEL.
Year: 2006.
University: SEVILLA [www.us.es].
Place of defense: FACULTAD DE QUIMICA.
Place of preparation: INSTITUTO DE LA GRASA (C.S.I.C.).

Summary: The innovative Doctoral Thesis of this is based on new parameters seek alternative or complementary to the fatty acid (GA) to allow sort of Iberian pig carcasses on the basis of their food (acorn, recebo or bait). In this sense, both triglycerides (TG) and hydrocarbons (HC) can provide information to address more fully the classification of animals according to their food. The ultimate objective is to propose new parameters for greater reliability in the classification of products, both producers to consumers. The study has been done on the subcutaneous fat of the slaughtered animal. The samples, 1,820 in all, come from animals protected under the OJ 'Ham Huelva' and have been supplied by the Control Board for four campaigns (2002 to 2006). As for the dependence of AG regard to the race, food and campaign, it is noted that most of them are significantly affected by the campaign and food, afectándose by race only stearic, at least from one point of statistically. The values of the weight of Cooman calculated for the AG and SG indicate that the first descriptors are worse than the latter, and within these, the greatest values are achieved for OOO, PSO (TG formed by palmítico-esteárico-oleico) and OOL ( TG formed by oleico-oleico-linoleico), the first of all the most discriminating power. Thus, OOO by itself alone is capable of differentiating between feeding acorn and bait. The biggest discriminating power and the best classification is obtained when used as a criterion for classifying mountain, rather than the animal's weight, a time at minimum range of 110 days. The analytical method fractionation hydrocarbon-based HPLC is proposed as a good alternative to splitting based ccromatografía column. Since it shows a great advantage to recover HC terpénicos and also the results are not significantly different from those obtained by chromatography in column. It has conducted a thorough characterization of the HC fraction of subcutaneous fat of the Iberian pig, by mass spectrometry, identíficándose a minority of 2-alquenos chain pair. It also presents a tentative identification of the two isomeric forms (EyZ) of 1-metil-alcanos and have characterized the 1-alquenos Tangled with two methyl groups in the positions n-1 and n-2. It has been shown that the HC previously identified by other authors as neofitadieno is actually a form of isomeric it, 7,11,15-trimetil-heptadeca-1 ,4-dieno. In addition, the ent-kaureno has been identified for the first time in this type of samples. Lastly was detected a relationship between the level of n-alquenos chain pair and the time of slaughter of animals fed on a bait, with a very low level when animals lacked grass in their food.