Host-guest interactions have been well studied in the new century to obtain fundamental insights into supramolecular chemistry. Most of the pioneering works have been done using techniques such as NMR, X-ray crystallography, IR spectroscopy and so on. However, none of these techniques is universal for the investigation of all types of supramolecules, and usually they have one or more limiting factors such as relatively large sample consumption, matrix effects from solvents, etc. Electrospray mass spectrometry has been widely used to investigate host-guest interactions in the gas phase. A particular advantage of gas phase host-guest research is that the experimental results can be directly compared to computational results because complicating interferences from solvents are not present. Thus electrospray mass spectrometry coupled with high-level computational methods becomes a powerful tool to elucidate binding behavior in host-guest complexes. With rigid, symmetric structures available in a range of sizes, cucurbiturils have been ideal prototypical host molecules in host-guest chemistry since they were characterized in 1980s. Recent research in my group has shown cucurbiturils can form various complexes with positive ions in the gas phase, such as molecular containers trapping small neutral guest molecules inside or wheel-and-axle architectures with linear molecules threaded through. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) is an ideal technique for investigation of host-guest supramolecular complexes due to its ultra-high mass resolving power, ultra-high mass accuracy, and high sensitivity. Moreover it has the capability of trapping ions for ion chemistry, and versatile tandem mass spectrometry capabilities. This dissertation focuses on the characterization of cucurbituril complexes in the gas phase using electrospray ionization FT-ICR mass spectrometry. Chapter 1 describes FTICR mass spectrometry techniques including principles, performance, instrumentation and applications. Electrospray ionization methods are also discussed in this chapter. Chapter 2 introduces structures, properties, synthesis and host-guest chemistry of the cucurbituril family. Chapters 3 investigate cucurbituril complexation behavior with amino acids and peptides. Chapter 4 investigates the alkali metal ions “lids removal” from cucurbit[5]uril molecular box. Chapter 5 characterizes the cucurbit[6]uril pseudorotaxanes in the gas phase. Chapter 6 characterizes the complexes formed by cucurbit[6]uril and α,ω-alkyldiammonium cations in the gas phase, using energy-resolved SORI-CID method. High-level computational methods were also performed to explain the experimental results.

This thesis focuses on using mass spectrometry-based techniques for characterizing the structure and behavior of cucurbituril complexes in the gas phase. Both solvent and counter ion effects can be completely eliminated in the gas phase and the intrinsic interactions in the system are directly shown in the experimental results. Chapter 1 introduces the structures, properties and host-guest chemistry of cucurbituril, and FTICR mass spectrometry including instrumentation, performance and working principles. Two mass spectrometry-based methods for supramolecular characterization, sustained off-resonance irradiation collision induced dissociation (SORI CID) and ion molecule equilibrium measurements, are also discussed in this chapter. Chapter 2 characterizes the dissociation and reaction behaviors of the complexes formed by cucurbit[5]uril (CB5) and primary monoamines [CH3(CH2)nNH2, n = 0-7] as well as similar studies of decamethylcucurbit[5]uril (mc5) in the gas phase. This study probes host-guest interactions between the neutral cucurbituril host and alkyl chains of varying length. All the cucurbit[5]uril and decamethylcucurbit[5]uril complexes have external binding. The dissociation thresholds of the complexes suggest that the optimum monoammonium chain length for binding CB5 in the gas phase occurs for n = 2, whereas for mc5 the optimum is n = 0. Reactivity studies of CB5 and mc5 complexes indicate the highest binding affinity appears at n = 6 for CB5 and n = 5 for mc5. Chapter 3 investigates the complexes formed by cucurbit[6]uril and primary monoamines using energy resolved SORI CID methods and ion molecule equilibrium measurements. The fragmentation data, branching ratios for the various channels, and the reactivities of the complexes suggest the complexes have the monoammonium threaded through the cavity of CB6 forming a pseudorotaxane architecture. Reactivity studies of complexes of cucurbit[7]uril reveal behaviors distinctive from CB5, mc5 or CB6, which suggests both internally-bound and externally-bound structures are present in CB7 complexes.

Orientadores: Marcos Nogueira Eberlin, Eugenio Vaz dos Santos Neto / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T16:54:54Z (GMT). No. of bitstreams: 1 Pereira_RosanaCardosoLopes_D.pdf: 5832219 bytes, checksum: 88820b58f8b6360b78a6aa2f16ceb943 (MD5) Previous issue date: 2012 / Resumo: Este trabalho consistiu na aplicação de tecnologia que se encontra hoje na vanguarda do conhecimento: a Petroleômica via ESI FT-ICR MS, com o objetivo de caracterizar as mais diversas classes de compostos polares ácidos presentes em amostras representativas de óleos de bacias brasileiras. O propósito ambicioso foi o de focalizar aspectos relacionados à toda cadeia de valor da indústria do petróleo, desde a geração do óleo até o seu refino, visando contribuir para novos estudos de interesse às atividades de upstream e downstream da PETROBRAS e, principalmente, fomentar a integração dos conhecimentos das diferentes áreas, o que contribuirá para ganhos de produtividade da empresa. A técnica ESI FT-ICR-MS mostrou-se uma técnica rápida e adequada para acompanhar as alterações verificadas na composição de amostras de petróleo, fornecendo subsídios a partir de uma caracterização única, para estudos diversos, abrangendo toda a cadeia de valor da indústria do petróleo. As alterações composicionais de óleos e extratos obtidos em experimentos de maturação artificial por hidropirólise de matéria orgânica dos tipos I e III foram avaliadas, evidenciando o potencial da técnica para utilização em estudos cinéticos. O estudo de biodegradação utilizando trinta amostras de óleos da Bacia Potiguar evidenciou que a técnica é sensível as variações de composição dos compostos polares que ocorrem em função do processo de biodegradação, e as amostras puderam ser agrupadas de acordo com o grau de biodegradação através da utilização de ferramentas quimiométricas (PCA). A partir dos dados de caracterização obtidos por ESI FT-ICR MS, foi possível agregar informações úteis para o entendimento de comportamentos diferenciados frente à tendência de formação de emulsão/gel durante a produção e frente à corrosão durante o refino / Abstract: This work focuses on the application of a technology that is cutting edge: Petroleomics by ESI FT-ICR MS with the goal of characterizing the large variety of acidic polar compound classes present in representative petroleum samples from Brazilian basins. The ambitious proposal was to focus on aspects related to the whole petroleum industry chain, since crude oil generation up to its processing in refinery units, to contribute to state-of-the-art studies of interest to upstream and downstream activities in PETROBRAS and mostly to encourage the knowledge integration, i.e. to form or blend the information into a whole, to UNITE, accessing high levels of productivity. The ESI FT-ICR MS technique exhibits characteristics like fast response, resolution, selectivity and sensibility, which make it suitable to monitor the changes in composition of petroleum samples and because of its unique and comprehensive characterization attained, to help different studies in the whole petroleum industry chain. The compositional alteration observed in extracts and oils during artificial maturation experiments by hydrouspyrolysis of organic matter types I and III were evaluated showing the potential of the technique to kinetic studies. Biodegradation studies were performed on 30 petroleum samples from Potiguar Basin and the results showed that the technique is sensitive to the variations on the composition of the polar compounds that occur as a result of the biodegradation process, and additionally, that the samples can be grouped according to their biodegradation level by the use of chimiometric tools (PCA). Also from the characterization data from ESI FT-ICR MS analysis it was shown that very useful information can be provided to better understand the differences in the rheological and corrosion behaviors of petroleum samples / Doutorado / Quimica Analitica / Doutora em Ciências

Les pétroles utilisés en raffinage étant de plus en plus lourds et chargés en métaux et hétéroélements, il est d’une grande importance pour les activités de raffinage de connaître la spéciation de ces espèces au sein des produits pétroliers et leurs comportements durant les procédés de raffinage. Afin d’apporter des réponses à cette problématique des techniques de caractérisation élémentaire et moléculaire ont été utilisées notamment par ICP MS Haute Résolution et FT ICR MS respectivement. Ces techniques analytiques sont appliquées à différents échantillons pétroliers provenant parfois de procédés de raffinage et les informations obtenues au niveau élémentaire et moléculaire sont utilisées de manières complémentaires pour améliorer notre compréhension des mécanismes se produisant au sein de nos échantillons durant les activités de raffinage. / The crude oils available for the refining industry are heavier and heavier and more concentrated in metals and heteroelements. It is thus of great importance to study the speciation of these species within the petroleum products and their behavior during the refining processes. To answer that problematic, elemental and molecular characterization techniques have been used, mainly High Resolution ICP MS and FT ICR MS for the elemental and molecular characterization respectively. The analytical techniques quoted are used for the analysis of several petroleum products sometimes originating from refining processes and the information obtained at the elemental and molecular level are combined to improve our understanding of the mechanisms occurring within our samples during refining activities.

La spectrométrie de masse fournit deux types d’informations : la masse moléculaire des molécules présentes dans un mélange, en une première expérience (MS), puis leurs structures après isolation suivie de fragmentation, obtenues une à une (MS/MS). La spectrométrie de masse FT-ICR bidimensionnelle permet d’obtenir toutes ces informations en une seule expérience, sans isolation, quelle que soit la complexité de l’échantillon. Le prix à payer est une faible résolution dans la dimension indirecte, pouvant être améliorée par une augmentation du temps d’analyse, mais qui semblait limiter cette technique à une simple curiosité scientifique.Le premier objectif est d’implémenter l’échantillonnage non uniforme (NUS) en FT-ICR MS 2D. Cette technique consiste en l’acquisition aléatoire du même nombre de points dans la dimension indirecte que lors d’une acquisition uniforme, mais sur une plage de t1max plus grande. Les points manquants sont ensuite reconstruits par des algorithmes, entrainant une augmentation significative de la résolution du signal sans perte de temps sur le spectromètre. La première étape est de créer un algorithme générant un échantillonnage aléatoire de distribution uniforme pour une couverture optimale de la plage de t1max. Les algorithmes de reconstruction ayant des difficultés à reconstituer des signaux de faible intensité quand le nombre de points non échantillonnés augmente, la deuxième étape est de déterminer le facteur de sous-échantillonnage optimal afin d’obtenir le bon compromis entre résolution et signal-sur-bruit. La troisième étape est de réaliser des spectres MS/MS ayant des massifs isotopiques corrects pour des fragments produits à partir des isotopes les plus lourds.Le deuxième objectif est de décrire le comportement des ions dans la cellule ICR en fonction des impulsions RF utilisées à partir des équations de Lorentz. Dans une première partie, le but est d’établir les équations qui régissent le mouvement des ions précurseurs jusqu’à leur détection. Ensuite, il s’agit d’introduire la fragmentation et de déterminer les solutions analytiques décrivant le mouvement des fragments. La dernière étape est de simuler le comportement des ions précurseurs tout au long de la séquence d’impulsions ainsi que celui des nuages de fragments, de leur formation à leur détection. / Mass spectrometry provides two kinds of information: the molecular mass of molecules present in a mixture, obtained all at once (MS), and structure through isolation and fragmentation, obtained one by one (MS/MS). Two-dimensional FT-ICR MS allows simultaneous parallel acquisition of structural information without isolation, regardless of the number of molecules. Nevertheless, the low resolution in the indirect dimension, which could be improved by increasing the acquisition time, seemed to limit this method to a simple curiosity. The first objective is to implement non-uniform-sampling (NUS) in 2D FT-ICR MS. This method consist in the random acquisition of the same number of points in the indirect dimension as in uniform acquisition, but over a wider t1max range. Processing algorithms then reconstruct skipped points, and the result is an increase of signal resolution without wasting analysis time. The first step is to create an algorithm that can generate random sampling with a uniform distribution for an optimal coverage of the t1max range. Processing algorithms may have trouble to reconstruct small peaks when the number of skipped points increases. The second step is to choose the under-sampling ratio for the best compromise between the gain in resolution and the signal-to-noise ratio. The third and last step is to obtain MS/MS spectra with corrects isotopic patterns for fragments produced from heavy isotopes. The second objective is to improve the understanding of ion motions in ICR cells depending on the RF pulses by using Lorentz equations. The first goal is to determine the equations governing precursors motions until their detection. Then the fragmentation will be introduced and analytical solutions describing fragments motions will be established. The last step is to simulate the trajectories of precursors throughout the entire pulse sequence as well as the behavior of fragments clouds, from their formation to detection.

Tout au long du procédé d’élaboration d’un vin, des réactions d’oxydation peuvent se produire y compris au cours du vieillissement en bouteilles. Depuis quelques années, la profession viti-vinicole est confrontée au problème de l’oxydation prématurée des vins blancs.. A ce jour, peu d’études ont pu apporter des explications d’ordre chimique à ce phénomène, et les mécanismes réactionnels intervenant restent peu connus.L’objectif de ce travail de thèse est d’apporter, au travers d’une analyse moléculaire non ciblée en spectrométrie de masse à transformée de Fourier et à résonance cyclotronique des ions (FT-ICR-MS) couplée à une étude chimiométrique, des réponses originales aux questions posées par la problématique actuelle d’oxydation prématurée des vins blancs. Nous avons montré suite à l’étude d’une série de vins oxydés prématurément non seulement la grande diversité chimique des vins, mais aussi la présence d’un ensemble de masses typiques associées à ce phénomène. Pour une meilleure compréhension de l’origine de cette problématique, nous avons considéré deux autres types d’oxydation : une oxydation relative exclusivement à un apport contrôlé en oxygène et une autre relative à l'évolution naturelle de vins en bouteilles. Cette dernière consiste en le suivi de l'évolution des espaces chimiques de séries verticales de vins blancs et rouges en fonction du temps. Sur la série verticale des vins blancs allant de 1979 à 2006, une charnière à l’année 1990 a été observée avec des groupes de masses typiques de chacun des vins jeunes (1979-1990) et des vieux vins (1991-2006).La comparaison entre les espaces chimiques discriminants chacun de ces trois types d’oxydation ne révèle la présence que de trois masses en commun, ce qui appuie l'hypothèse de causes multiparamétriques à l’oxydation prématurée des vins blancs, qui ne serait donc pas un phénomène du exclusivement à une exposition non contrôlée à l'oxygène.Des essais d’élucidation structurale en FT-ICR-MS/MS des masses discriminantes des vins oxydés et de la série verticale ont été effectués et des schémas de fragmentation pour certaines masses sont proposés / During winemaking processes, many oxidation reactions may occur especially during the aging period. Recently, white wines are characterized by a problem of premature oxidation for which few studies have provided chemical explanation. To date, the involved mechanisms in this phenomenon remain poorly understood.The aim of this thesis project is to provide, through an untargeted molecular analysis using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) coupled to chemometric analysis, original clue to understand the premature oxidation of white wines. Based on the study of a series of premature oxidized white wines, we were able to elucidate the high complexity and the chemical diversity of wine, and got out typical masses characterizing the oxidation state. In order to better understand the origin of this phenomenon, we considered two alternative possibilities of oxidation: the first one induced by oxygen, and the second through a natural evolution of wines in bottles. The latter included the monitoring of the chemical evolution of white and red wines as a function of time. A very interesting result was obtained on the vertical series of white wines from 1979 to 2006, where two groups were separated at the 1990 vintage to provide a group of old wines (1979-1990) and a group of new wines (1991-2006). Typical discriminant masses were found for each group.A comparison between the chemical spaces discriminating each of the three types of oxidation (premature oxidation, oxidation with oxygen and natural evolution of wine in bottle) revealed very few common masses that may indicate that the phenomenon of premature oxidation is indeed influenced by multiple factors.Finally, a structural elucidation of the typical masses of the groups of oxidized and aged wines were established using FT-ICR-MS/MS. Possible fragmentations schemes of some of these masses were proposed

Presented in this dissertation are FT-ICR H/D exchange and fragmentation studies of protonated peptides for the purpose of better understanding gas phase conformation and protonation motifs, and their affect on fragmentation patterns. In addition, a new ion activation method is developed to enhance the abundance of higher energy fragmentation pathways, thereby providing additional structural and/or mechanistic information.Studies to probe the relay mechanism of H/D exchange in small, model peptides found that residue position, proline configuration, and availability of the termini have a measurable effect on the H/D exchange behavior reflective of different conformation / protonation motifs.Charge remote cleavage C-terminal to aspartic acid was studied with the fixed charge derivative tris(2,4,6-trimethoxyphenyl) phosphonium (tTMP-P+). Ab initio calculations demonstrate that tTMP-P+ cannot activate the proposed aspartic acid nucleophile, the acidic side chain hydrogen initiates cleavage. Despite the absence of an ionizing proton, the derivatized peptide P+LDIFSDF (where P+ = tTMP-P+) exchanges three acidic hydrogens for deuterium. This supports the proposed aspartic acid cleavage mechanism that occurs without the direct involvement of an ionizing proton because acidic protons are able to participate in H/D exchange in the absence of an added proton. In addition, H/D exchange of P+LDIFSDF analogues provides insight into the sites and mechanisms of H/D exchange.H/D exchange to separate distinct peptide populations with differing rates and their subsequent fragmentation demonstrate that conformation / protonation motif affects the fragmentation spectrum observed. Studies of [P+LDIFSDF + H]2+, [RPPGFSPFR + 2H]2+ (bradykinin), and [RVYIFPF + 2H]2+ show that at least two distinct structures exist with different rates of H/D exchange and different fragmentation patterns. The overall MS/MS spectrum is a linear combination of all conformations and protonation motifs. In addition, fragmentation of labeled populations suggests that complementary bn+ / ym-n+ ion pairs are being formed from doubly-charged precursor by the same mechanism.SORI-RE CID is a new FT-ICR ion activation method based on the combination of sustained off-resonance irradiation (SORI) and on-resonant excitation (RE) with the purpose of enhancing higher energy fragmentation while maintaining low energy processes. The experiments presented serve to illustrate the usefulness of SORI-RE in diverse cases.

Humic substances (HS), the complex mixture of organic molecules produced by microbial and abiotic degradation of plant and animals residues, are the major components of organic matter in soil and natural waters. As such, they are vital to the integrity of soil, play important roles in nutrient biogeochemical cycling and determine the mobility and fate of both nutrients and contaminants. How HS enact their varied roles, however, is largely unknown due to the lack of comprehension of their molecular make-up. What is known is that they contain aromatic (e.g. phenols, condensed aromatics) and aliphatic (e.g. carbohydrates, lipids) molecules with prevailing carboxyl and hydroxyl functionalities. As for other complex chromatographically inseparable mixtures, high-resolution analytical techniques such as Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) as well as Nuclear Magnetic Resonance (NMR) spectroscopy have been applied to study HS composition at the molecular level. While FT-ICR MS can provide molecular formulae, it is only NMR that can unveil structures. Until now, however, very few unambiguous structures of individual molecules have emerged from standard NMR experiments. This is because purposely designed multidimensional NMR experiments are required to achieve ‘spectroscopic separation’ where chromatography fails. In this work, ‘spectroscopic separation’ was accomplished with the aid of chemical modification in the form of 13C methylation of COOH and OH groups. 13C containing tags allow the observation of signals only from molecules carrying these tags. In combination with purposelydesigned isotope-filtered NMR experiments, these tags act as spies reporting on their surrounding structure. This is achieved by utilising scalar and dipolar couplings to transfer the polarisation between protons and carbons of the 13CH3O groups and nuclei of the parent molecules. The necessary spectral resolution is attained using 3D/4D NMR experiments. This approach provides access to an array of correlated chemical shifts of HS molecules and represents a paradigm shift in the use of tags in investigations of complex mixtures: instead of focusing only on the tags, they are used to obtain structural information from the molecules they are attached to. The compounds at the centre of this investigation are the phenols of HS. These molecules are thought to be important in many of the key processes in organic matter rich soils, particularly peat. For example, their accumulation is thought to impair the activity of extracellular enzymes essential for the degradation of peat HS. Understanding the nature and source of phenols would provide a more fundamental framework for rationalising their role in peat, as well as other carbon rich soils. The developed methodology was initially tested on model mixtures containing 3 or 9 phenolic compounds before applying it to a operational fraction of HS, fulvic acid, extracted from a Scottish raised peat bog. For this fulvic acid, over 30 major phenolic molecules/moieties were identified, many of which can be directly traced to the flora prevalent in the vicinity of the sampling site. For the first time in 150 years of HS research, a novel analytical methodology has yielded unambiguous structural information, providing the first steps towards understanding the various roles of HS in natural systems.

This study examines voluntary intellectual capital reporting (ICR) in New Zealand firms' annual reports, with a view to contributing to understanding ICR practice. This study also reflects on content analysis with a view to refining the methodology when applied to investigating ICR.The literature includes widespread claims that intellectual capital (IC) resources are important value drivers and assets, and that IC information should be reported externally. However, complexities relating to identifying IC prevent it from being recognised as an asset under current accounting regulations. Consequently, the traditional financial reporting system is being criticised as out-of-date, giving deficient and irrelevant information, and having lost its value relevance. Numerous scholars have investigated voluntary ICR in several countries, but have presented different results and findings. The literature argues that the results of many ICR studies cannot be meaningfully compared because inconsistent data collection instruments have been applied. To advance ICR research, further refining and developing of the methodology is advocated; problems relating to applying methodological issues need to be resolved. Moreover, to establish consensus about ICR, more research and evidence is needed concerning exactly what and how IC is reported.The 2004 annual reports of the 30 largest (by market capitalisation) New Zealand firms listed on the New Zealand Stock Exchange were analysed. Content analysis was applied to determine what and how IC is reported. Inferences about what IC is communicated were made based on an analysis of the content of texts and visual representations. To determine how IC is reported, voluntary reporting was categorised according to the form, nature and location of the disclosure. Frequencies of mention were recorded. Hence, each incidence of occurrence was coded and counted.This study reflected on content analysis methodology by searching the literature for guidance on how to apply this approach and how to deal with the challenges and problems it poses. The thesis discusses methodological issues that could be applied differently, and hence hinder the replicability and comparability of ICR studies. Moreover, the ICR literature provided limited guidance about how to deal with methodological challenges and problems, and revealed an absence of explicit recording instructions. Therefore, explicating this study's recording instructions should enhance replicability and comparability of future ICR research and hence further refine the methodology.Some results of this content analysis study disconfirm those of prior research: New Zealand firms show high levels of ICR, the most reported IC category is human capital, and the most reported IC item is employees. In line with prior research, this study showed that most ICR is presented in declarative terms. Moreover, more than one-third of New Zealand firms' ICR is disclosed as pictures. This indicates the importance of pictorial information as a means of reporting IC and the need to include graphics when conducting ICR research. This study's findings also indicate a narrative approach, similar to the European notion of story telling, to voluntarily report IC information. This approach suggests that narratives have possible potential for voluntary ICR, as an approach that departs from a measurement and quantification approach.

PARMI LES DIFFERENTES SOURCES NATURELLES DE COMPOSES BIOLOGIQUEMENT ACTIFS, LES VENINS REPRESENTENT, DE PAR LA GRANDE VARIETE DE LEURS CONSTITUANTS, UNE CIBLE DE CHOIX POUR LA RECHERCHE MEDICALE. LES TOXINES QU'ILS CONTIENNENT SONT VARIEES ET COMPRENDRE LEUR MODE D'ACTION DANS LE BUT DE SYNTHETISER DES ANALOGUES D'INTERET PHARMACOLOGIQUE PASSE PAR UNE DETERMINATION PRECISE DE LEUR STRUCTURE CHIMIQUE AVEC LA CONTRAINTE QUE LA FAIBLE QUANTITE DE MATERIEL GENERALEMENT DISPONIBLE REND L'ENSEMBLE DES PROCESSUS DE SEPARATION ET DE CARACTERISATION TRES DELICAT. C'EST DANS CE CONTEXTE QUE SE SITUE CETTE THESE DONT L'OBJECTIF A ETE DE METTRE AU POINT DE NOUVELLES STRATEGIES D'ANALYSE PAR SPECTROMETRIE DE MASSE A HAUTE RESOLUTION DE NOUVELLES TOXINES PEPTIDIQUES. CETTE THESE A PARTICULIEREMENT CIBLE L'ETUDE DE TOXINES PEPTIDIQUES DE CONES (MOLLUSQUES UTILISANT UN HARPON VENIMEUX POUR ATTEINDRE ET PARALYSE! R LEUR PROIE) ET DE SERPENTS. AU FINAL, LA SPECTROMETRIE DE MASSE A HAUTE RESOLUTION S'EST REVELEE COMME UN OUTIL TRES PUISSANT POUR LA CARACTERISATION DE PETITES TOXINES MODIFIEES PAR SES GRANDES CAPACITES EN TERMES DE PRECISION SUR LA MESURE DE MASSE MAIS AUSSI DANS L'ETUDE DE PLUS GROSSES TOXINES POUR LESQUELLES LA RECENTE TECHNIQUE DE DISSOCIATION PAR CAPTURE D'ELECTRON S'EST MONTREE DES PLUS PERFORMANTES.