Methodische Entwicklung der MALDI-TOF-Massenspektrometrie für Grenzbereiche der Polymeranalytik

Zusammenfassung der DoktorarbeitDie MALDI-TOF-Massenspektrometrie (Matrix Assisted Laser Desorption and Ionisation–Time Of Flight) ist in der Lage, Moleküle mit einem Molekulargewicht bis zu mehreren Hunderttausend Da intakt in die Gasphase zu überführen. Dabei wird die Fragmentierung des Analyten stark eingeschränkt bzw. gänzlich vermieden. Diese Methode findet daher zunehmend Verwendung für die Charakterisierung von Biopolymeren und synthetischen Polymeren. Ziel dieser Arbeit war, die MALDI-TOF-Massenspektrometrie zur Charakterisierung von Makromolekülen einzusetzen, bei denen die konventionellen polymeranalytischen Methoden nur unzureichende Informationen oder gar falsche bzw. gar keine Ergebnisse liefern. Mittels einer methodischen Entwicklung der MALDI-TOF-Massenspektrometrie gelang es, die bisherigen Grenzen der Methode zu erweitern und neue Anwendungsbereiche der Polymeranalytik aufzuzeigen. Anhand der erzielten Ergebnisse wurden darüber hinaus neue Erklärungsansätze formuliert, die zu einem besseren Verständnis des noch immer ungeklärten MALDI-Prozesses beitragen können. Besonders vielversprechend sind zum einen die Ergebnisse der Fragmentionenanalyse synthetischer Polymere und zum anderen die Charakterisierung von unlöslichen PAHs (Polycyclic Aromatic Hydrocarbons). Die Möglichkeiten und Aussagekraft der Fragmentionenanalyse wurde an synthetischen Polymeren getestet. Mit Hilfe dieser neuen Technik konnte die komplizierte Endgruppenverteilung einer Polycarbonat-Probe sowie die Zusammensetzung eines Poly-para-phenylenethynylen-b-Polyethylenoxid-Diblock-Copolymers eindeutig bestimmen werden, während die konventionellen MALDI-Massenspektren nur über einen wesentlich geringeren Informationsgehalt verfügten. Auf dem Gebiet der Analytik von unlöslichen PAHs wurde mit der Entwicklung einer neuen MALDI-Probenvorbereitung eine Methode gefunden, die über die PAH Analytik hinaus von großem Nutzen ist. Diese erstmalig angewendete Probenvorbereitung unterscheidet sich von den üblichen MALDI-Probenpräparationen, indem sie auf die Beteiligung eines Lösungsmittels vollkommen verzichtet. Damit konnte speziell ein unlöslicher, zuvor nicht nachweisbarer PAH von ca. 2700 Da mit MALDI eindeutig charakterisiert werden.

Zu Problemen der Flüssigszintillationsspektroskopie bei Transactiniden-Experimenten

Die vorliegende Arbeit beschäftigt sich vorwiegend mit Detektionsproblemen, die bei Experimenten zur Chemie der Transactiniden mit dem schnellen Flüssig-Flüssig-Extraktionssystem SISAK auftraten. Bei diesen Experimenten wird als Detektionsmethode die Flüssigszintillationsspektroskopie (LSC) eingesetzt. Es werden Szintillationspulse registriert, die für das verursachende Teilchen charakteristische Formen zeigen, die unterschieden werden müssen. Am Beispiel der Auswertung des SISAK-Experimentes zur Chemie des Rutherfordiums vom November 1998 wurde gezeigt, dass es mit den herkömmlichen Verfahren zur Pulsformdiskriminierung nicht möglich ist, die aus dem Zerfall der Transactiniden stammenden alpha-Ereignisse herauszufiltern. Ursache dafür ist ein hoher Untergrund, der in erster Linie von beta/gamma-Teilchen, Spaltfragmenten und pile ups verursacht wird. Durch die Verfügbarkeit von Transientenrecordern ergeben sich neue Möglichkeiten für eine digitale Pulsformdiskriminierung. In dieser Arbeit wird erstmals die Methode der digitalen Pulsformdiskriminierung mit künstlichen neuronalen Netzen (PSD-NN) vorgestellt. Es wurde im Zuge der Auswertung des SISAK-Experimentes vom Februar 2000 gezeigt, dass neuronale Netze in der Lage sind, Pulsformen automatisch richtig zu klassifizieren. Es ergeben sich nahezu untergrundfreie alpha-Flüssigszintillationsspektren. Es werden Vor- und Nachteile der neuen Methode diskutiert. Es ist dadurch möglich geworden, in SISAK-Experimenten Transactinidenatome anhand ihres Zerfalls eindeutig zu charakterisieren. Das SISAK-System kann somit bei Experimenten zum Studium des chemischen Verhaltens von Transactiniden in flüssiger Phase eingesetzt werden.____

Evoluzioni e tendenze dei consumi alimentari delle famiglie italiane - Analisi delle decisioni di consumo attraverso il modello Almost Ideal

Il problema affrontato nel lavoro riguarda l'allocazione della spesa tra gruppi di beni alimentari (domestici ed extra-domestici) e le modificazioni che tale allocazione ha subito nell’arco dell’ultimo decennio. L’obiettivo principale dell'analisi proposta è, quindi, di spiegare come variazioni della quota di spesa destinata alle componenti del consumo alimentare siano attribuibili a fattori strettamente economici, oltre che alle caratteristiche struttura socio-demografiche dei consumatori. Allo scopo di valutare l’allocazione inter-temporale della spesa individuale viene proposto come schema di analisi il sistema di domanda Almost Ideal di Deaton e Muellbauer (AIDS).

Existence of solutions and asymtptotic limits of the Euler-Poisson and the quantum drift-diffusion systems

My work concerns two different systems of equations used in the mathematical modeling of semiconductors and plasmas: the Euler-Poisson system and the quantum drift-diffusion system. The first is given by the Euler equations for the conservation of mass and momentum, with a Poisson equation for the electrostatic potential. The second one takes into account the physical effects due to the smallness of the devices (quantum effects). It is a simple extension of the classical drift-diffusion model which consists of two continuity equations for the charge densities, with a Poisson equation for the electrostatic potential. Using an asymptotic expansion method, we study (in the steady-state case for a potential flow) the limit to zero of the three physical parameters which arise in the Euler-Poisson system: the electron mass, the relaxation time and the Debye length. For each limit, we prove the existence and uniqueness of profiles to the asymptotic expansion and some error estimates. For a vanishing electron mass or a vanishing relaxation time, this method gives us a new approach in the convergence of the Euler-Poisson system to the incompressible Euler equations. For a vanishing Debye length (also called quasineutral limit), we obtain a new approach in the existence of solutions when boundary layers can appear (i.e. when no compatibility condition is assumed). Moreover, using an iterative method, and a finite volume scheme or a penalized mixed finite volume scheme, we numerically show the smallness condition on the electron mass needed in the existence of solutions to the system, condition which has already been shown in the literature. In the quantum drift-diffusion model for the transient bipolar case in one-space dimension, we show, by using a time discretization and energy estimates, the existence of solutions (for a general doping profile). We also prove rigorously the quasineutral limit (for a vanishing doping profile). Finally, using a new time discretization and an algorithmic construction of entropies, we prove some regularity properties for the solutions of the equation obtained in the quasineutral limit (for a vanishing pressure). This new regularity permits us to prove the positivity of solutions to this equation for at least times large enough.

Synthesis and characterization of Poly(vinylphosphonic acid) for proton exchange membranes in fuel cells

Vinylphosphonic acid (VPA) was polymerized at 80 ºC by free radical polymerization to give polymers (PVPA) of different molecular weight depending on the initiator concentration. The highest molecular weight, Mw, achieved was 6.2 x 104 g/mol as determined by static light scattering. High resolution nuclear magnetic resonance (NMR) spectroscopy was used to gain microstructure information about the polymer chain. Information based on tetrad probabilities was utilized to deduce an almost atactic configuration. In addition, 13C-NMR gave evidence for the presence of head-head and tail-tail links. Refined analysis of the 1H NMR spectra allowed for the quantitative determination of the fraction of these links (23.5 percent of all links). Experimental evidence suggested that the polymerization proceeded via cyclopolymerization of the vinylphosphonic acid anhydride as an intermediate. Titration curves indicated that high molecular weight poly(vinylphosphonic acid) PVPA behaved as a monoprotic acid. Proton conductors with phosphonic acid moieties as protogenic groups are promising due to their high charge carrier concentration, thermal stability, and oxidation resistivity. Blends and copolymers of PVPA have already been reported, but PVPA has not been characterized sufficiently with respect to its polymer properties. Therefore, we also studied the proton conductivity behaviour of a well-characterized PVPA. PVPA is a conductor; however, the conductivity depends strongly on the water content of the material. The phosphonic acid functionality in the resulting polymer, PVPA, undergoes condensation leading to the formation of phosphonic anhydride groups at elevated temperature. Anhydride formation was found to be temperature dependent by solid state NMR. Anhydride formation affects the proton conductivity to a large extent because not only the number of charge carriers but also the mobility of the charge carriers seems to change.

Development and application of a GC system for NMHC analyses of air samples from the CARIBIC aircraft project

The subject of this thesis is the development of a Gaschromatography (GC) system for non-methane hydrocarbons (NMHCs) and measurement of samples within the project CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container, www.caribic-atmospheric.com). Air samples collected at cruising altitude from the upper troposphere and lowermost stratosphere contain hydrocarbons at low levels (ppt range), which imposes substantial demands on detection limits. Full automation enabled to maintain constant conditions during the sample processing and analyses. Additionally, automation allows overnight operation thus saving time. A gas chromatography using flame ionization detection (FID) together with the dual column approach enables simultaneous detection with almost equal carbon atom response for all hydrocarbons except for ethyne. The first part of this thesis presents the technical descriptions of individual parts of the analytical system. Apart from the sample treatment and calibration procedures, the sample collector is described. The second part deals with analytical performance of the GC system by discussing tests that had been made. Finally, results for measurement flight are assessed in terms of quality of the data and two flights are discussed in detail. Analytical performance is characterized using detection limits for each compound, using uncertainties for each compound, using tests of calibration mixture conditioning and carbon dioxide trap to find out their influence on analyses, and finally by comparing the responses of calibrated substances during period when analyses of the flights were made. Comparison of both systems shows good agreement. However, because of insufficient capacity of the CO2 trap the signal of one column was suppressed due to breakthroughed carbon dioxide so much that its results appeared to be unreliable. Plausibility tests for the internal consistency of the given data sets are based on common patterns exhibited by tropospheric NMHCs. All tests show that samples from the first flights do not comply with the expected pattern. Additionally, detected alkene artefacts suggest potential problems with storing or contamination within all measurement flights. Two last flights # 130-133 and # 166-169 comply with the tests therefore their detailed analysis is made. Samples were analyzed in terms of their origin (troposphere vs. stratosphere, backward trajectories), their aging (NMHCs ratios) and detected plumes were compared to chemical signatures of Asian outflows. In the last chapter a future development of the presented system with focus on separation is drawn. An extensive appendix documents all important aspects of the dissertation from theoretical introduction through illustration of sample treatment to overview diagrams for the measured flights.

La responsabilità del vettore terrestre nel trasporto di cose per conto terzi: riflessi assicurativi.

La ricerca ha ad oggetto l’analisi della disciplina della responsabilità del vettore terrestre di merci per conto terzi ed i riflessi che detta disciplina ha avuto modo di svilupparsi nel mercato assicurativo. L’attenzione è stata rivolta al contratto di trasporto di cose in generale, seguendone la disciplina codicistica e le evoluzioni legislative intervenute. Particolare rilievo assume la novella apportata all’art. 1696 c.c., introdotta dall’art. 10 del Dlgs. 286/2005, grazie alla quale l’ordinamento italiano ha potuto codificare il limite di indennizzo dovuto dal vettore nell’ipotesi di colpa lieve, L’introduzione del limite legale di indennizzo per le ipotesi di responsabilità per perdita o avaria della merce trasportata ha generato nel mondo assicurativo interessanti reazioni. L’elaborato esamina anche l’evoluzione giurisprudenziale formatisi in tema di responsabilità vettoriale, evidenziando il crescente rigore imposto dalla giurisprudenza fondato sul principio del receptum. Tale fenomeno ha visto immediata reazione nel mercato assicurativo il quale, sulla base di testi contrattuali non dissimili tra le diverse compagnie di assicurazioni operanti sul mercato domestico e che traevano origine dai formulari approvati dall’ANIA, ha seguito l’evoluzione giurisprudenziale apportando significative restrizioni al rischio tipico previsto dalle coperture della responsabilità civile vettoriale. La ricerca si è poi focalizzata sull’esame delle più comuni clausole contemplate dalle polizze di assicurazioni di responsabilità civile e sul loro significato alla luce delle disposizioni di legge in materia. Tale analisi riveste preminente interesse poiché consente di verificare in concreto come l’assicurazione possa effettivamente costituire per l’impresa di trasporto non tanto un costo bensì una opportunità di risparmio da un lato ed un modello comportamentale, sebbene indotto, dall’altro lato per il raggiungimento di quei canoni di diligenza che qualsiasi operatore del settore dovrebbe tenere durante l’esecuzione del trasporto ed il cui venir meno determina, come detto, sensibili effetti pregiudizievoli di carattere economico.

Measurement of the ZZ production cross section and limits on anomalous neutral triple gauge couplings with ATLAS

The main work of this thesis concerns the measurement of the production cross section using LHC 2011 data collected at a center-of-mass energy equal to 7 TeV by the ATLAS detector and resulting in a total integrated luminosity of 4.6 inverse fb. The ZZ total cross section is finally compared with the NLO prediction calculated with modern Monte Carlo generators. In addition, the three differential distributions (∆φ(l,l), ZpT and M4l) are shown unfolded back to the underlying distributions using a Bayesian iterative algorithm. Finally, the transverse momentum of the leading Z is used to provide limits on anoumalus triple gauge couplings forbidden in the Standard Model.

The collapse of linear polyelectrolyte chains in a poor solvent: When does a collapsing polyelectrolyte collect its counter ions?

The collapse of linear polyelectrolyte chains in a poor solvent: When does a collapsing polyelectrolyte collect its counter ions? The collapse of polyions in a poor solvent is a complex system and is an active research subject in the theoretical polyelectrolyte community. The complexity is due to the subtle interplay between hydrophobic effects, electrostatic interactions, entropy elasticity, intrinsic excluded volume as well as specific counter-ion and co-ion properties. Long range Coulomb forces can obscure single molecule properties. The here presented approach is to use just a small amount of screening salt in combination with a very high sample dilution in order to screen intermolecular interaction whereas keeping intramolecular interaction as much as possible (polyelectrolyte concentration cp ≤ 12 mg/L, salt concentration; Cs = 10^-5 mol/L). This is so far not described in literature. During collapse, the polyion is subject to a drastic change in size along with strong reduction of free counterions in solution. Therefore light scattering was utilized to obtain the size of the polyion whereas a conductivity setup was developed to monitor the proceeding of counterion collection by the polyion. Partially quaternized PVP’s below and above the Manning limit were investigated and compared to the collapse of their uncharged precursor. The collapses were induced by an isorefractive solvent/non-solvent mixture consisting of 1-propanol and 2-pentanone, with nearly constant dielectric constant. The solvent quality for the uncharged polyion could be quantified which, for the first time, allowed the experimental investigation of the effect of electrostatic interaction prior and during polyion collapse. Given that the Manning parameter M for QPVP4.3 is as low as lB / c = 0.6 (lB the Bjerrum length and c the mean contour distance between two charges), no counterion binding should occur. However the Walden product reduces with first addition of non solvent and accelerates when the structural collapse sets in. Since the dielectric constant of the solvent remains virtually constant during the chain collapse, the counterion binding is entirely caused by the reduction in the polyion chain dimension. The collapse is shifted to lower wns with higher degrees of quaternization as the samples QPVP20 and QPVP35 show (M = 2.8 respectively 4.9). The combination of light scattering and conductivity measurement revealed for the first time that polyion chains already collect their counter ions well above the theta-dimension when the dimensions start to shrink. Due to only small amounts of screening salt, strong electrostatic interactions bias dynamic as well as static light scattering measurements. An extended Zimm formula was derived to account for this interaction and to obtain the real chain dimensions. The effective degree of dissociation g could be obtained semi quantitatively using this extrapolated static in combination with conductivity measurements. One can conclude the expansion factor a and the effective degree of ionization of the polyion to be mutually dependent. In the good solvent regime g of QPVP4.3, QPVP20 and QPVP35 exhibited a decreasing value in the order 1 > g4.3 > g20 > g35. The low values of g for QPVP20 and QPVP35 are assumed to be responsible for the prior collapse of the higher quaternized samples. Collapse theory predicts dipole-dipole attraction to increase accordingly and even predicts a collapse in the good solvent regime. This could be exactly observed for the QPVP35 sample. The experimental results were compared to a newly developed theory of uniform spherical collapse induced by concomitant counterion binding developed by M. Muthukumar and A. Kundagrami. The theory agrees qualitatively with the location of the phase boundary as well as the trend of an increasing expansion with an increase of the degree of quaternization. However experimental determined g for the samples QPVP4.3, QPVP20 and QPVP35 decreases linearly with the degree of quaternization whereas this theory predicts an almost constant value.

Applications of infrared thermography in the food industry

In the last 20-30 years, the implementation of new technologies from the research centres to the food industry process was very fast. The infrared thermography is a tool used in many fields, including agriculture and food science technology, because of it's important qualities like non-destructive method, it is fast, it is accurate, it is repeatable and economical. Almost all the industrial food processors have to use the thermal process to obtain an optimal product respecting the quality and safety standards. The control of temperature of food products during the production, transportation, storage and sales is an essential process in the food industry network. This tool can minimize the human error during the control of heat operation, and reduce the costs with personal. In this thesis the application of infrared thermography (IRT) was studies for different products that need a thermal process during the food processing. The background of thermography was presented, and also some of its applications in food industry, with the benefits and limits of applicability. The measurement of the temperature of the egg shell during the heat treatment in natural convection and with hot-air treatment was compared with the calculated temperatures obtained by a simplified finite element model made in the past. The complete process shown a good results between calculated and observed temperatures and we can say that this technique can be useful to control the heat treatments for decontamination of egg using the infrared thermography. Other important application of IRT was to determine the evolution of emissivity of potato raw during the freezing process and the control non-destructive control of this process. We can conclude that the IRT can represent a real option for the control of thermal process from the food industry, but more researches on various products are necessary.

Attualità del divieto assoluto di procreazione medicalmente assistita eterologa in Italia e prospettive di superamento

La presente ricerca si fonda su un’attenta ed approfondita analisi della normativa vigente in Italia in materia di procreazione medicalmente assistita (P.M.A.), con particolare riferimento al divieto assoluto di P.M.A. eterologa, di cui all’art. 4, comma 3, L. 19 febbraio 2004, n. 40, consentita invece – sia pure con la previsione di limitazioni differenti – nella quasi totalità dei paesi europei. Dopo aver esaminato la “questione etica” del ricorso alle tecniche di fecondazione assistita e le normative vigenti in Europa in materia di P.M.A. eterologa, il presente lavoro analizza i profili civilistici della L. n. 40/2004 ed i conseguenti dubbi interpretativi che la normativa italiana pone in materia di fecondazione eterologa, con specifico riguardo al consenso prestato dai coniugi o conviventi, al divieto di disconoscimento di paternità e di anonimato della madre ed, infine, al diritto del nato da fecondazione eterologa di conoscere le proprie origini biologiche. Ne consegue che, in una materia che coinvolge la sfera più intima e personale della vita privata e familiare, quale quella della P.M.A., il legislatore avrebbe dovuto intervenire con misura, individuando soluzioni ragionevoli ed equilibrate nel rispetto della pluralità di etiche contrapposte ed interessi in conflitto. Attraverso una capillare analisi della recente giurisprudenza nazionale ed europea, la presente ricerca mira, dunque, a valutare possibili prospettive di superamento del divieto assoluto di P.M.A. eterologa previsto dalla L. n. 40/2004. I risultati a cui la presente indagine ha consentito di pervenire dimostrano quanto sia opportuna l’adozione in Italia di un “modello liberale”, in cui sia lecita anche la fecondazione eterologa (con la previsione di limiti e condizioni volti a tutelare primariamente il superiore interesse del nascituro), onde consentire l’adeguamento al nuovo concetto di “genitorialità” ormai prevalente e l’arresto del cd. “turismo procreativo”.

Use of shared memory in the context of embedded multi-core processors: exploration of the technology and its limits

Modern embedded systems embrace many-core shared-memory designs. Due to constrained power and area budgets, most of them feature software-managed scratchpad memories instead of data caches to increase the data locality. It is therefore programmers’ responsibility to explicitly manage the memory transfers, and this make programming these platform cumbersome. Moreover, complex modern applications must be adequately parallelized before they can the parallel potential of the platform into actual performance. To support this, programming languages were proposed, which work at a high level of abstraction, and rely on a runtime whose cost hinders performance, especially in embedded systems, where resources and power budget are constrained. This dissertation explores the applicability of the shared-memory paradigm on modern many-core systems, focusing on the ease-of-programming. It focuses on OpenMP, the de-facto standard for shared memory programming. In a first part, the cost of algorithms for synchronization and data partitioning are analyzed, and they are adapted to modern embedded many-cores. Then, the original design of an OpenMP runtime library is presented, which supports complex forms of parallelism such as multi-level and irregular parallelism. In the second part of the thesis, the focus is on heterogeneous systems, where hardware accelerators are coupled to (many-)cores to implement key functional kernels with orders-of-magnitude of speedup and energy efficiency compared to the “pure software” version. However, three main issues rise, namely i) platform design complexity, ii) architectural scalability and iii) programmability. To tackle them, a template for a generic hardware processing unit (HWPU) is proposed, which share the memory banks with cores, and the template for a scalable architecture is shown, which integrates them through the shared-memory system. Then, a full software stack and toolchain are developed to support platform design and to let programmers exploiting the accelerators of the platform. The OpenMP frontend is extended to interact with it.

L(ocus) d(atos) d(ecreto) d(ecurionum): La concessione di spazi pubblici nelle comunita' cittadine dell'italia romana

La tesi riguarda la concessione di spazi di proprietà pubblica a privati, intesi come singole persone o enti, quali ad esempio i collegi, da parte delle autorità cittadine. Le fonti a disposizione per indagare tale pratica burocratica sono quasi totalmente di natura epigrafica, per lo più attestanti l’espressione locus datus decreto decurionum, variamente abbreviata, o formule similari. Questo aspetto della vita civica è stata cursoriamente oggetto di studio in diversi contributi, ma si tratta di articoli che circoscrivono il tema, analizzandolo in relazione a ristrette aree geografiche, oppure considerandone determinati aspetti (ad esempio l’ambito sacro o quello funerario). Si è perciò ritenuto utile proseguire questa linea di ricerca affrontando uno studio di più ampio raggio, che comprenda la documentazione epigrafica dell’intero territorio italico (costituito dalle undici regioni augustee ad esclusione di Roma), per tutte le tipologie testuali (iscrizioni sacre, funerarie, onorarie, su opera pubblica, exempla decreti), allo scopo di formulare osservazioni più precise e puntuali sulla procedura burocratica in esame, pur con tutti i limiti noti a chi affronti questo genere di indagine. Tra le conclusioni raggiunte, è emerso come durante il I-II sec. d.C. vi fosse la tendenza a concedere, sporadicamente, dei loca sepulturae extraurbani a membri delle famiglie delle élites cittadine, anche donne e fanciulli, mentre il foro e le altre aree pubbliche interne alla città erano soprattutto utilizzate direttamente dai decurioni per l’elevazione di dediche e statue. Nel corso del II sec. d.C., con massima diffusione nell’età antonina e poi in quella severiana, prese invece piede l’uso privato a scopo onorario degli spazi pubblici siti all’interno delle città, ovvero in aree prima pressoché precluse all’intervento di singoli cittadini: familiari e liberti, collegi e altri organismi commissionavano statue dedicate prevalentemente agli amministratori locali, magistrati cittadini spesso divenuti anche cavalieri.

Chemical composition measurements of cloud condensation nuclei and ice nuclei by aerosol mass spectrometry

In this study the Aerodyne Aerosol Mass Spectrometer (AMS) was used during three laboratory measurement campaigns, FROST1, FROST2 and ACI-03. The FROST campaigns took place at the Leipzig Aerosol Cloud Interaction Simulator (LACIS) at the IfT in Leipzig and the ACI-03 campaign was conducted at the AIDA facility at the Karlsruhe Institute of Technology (KIT). In all three campaigns, the effect of coatings on mineral dust ice nuclei (IN) was investigated. During the FROST campaigns, Arizona Test Dust (ATD) particles of 200, 300 and 400 nm diameter were coated with thin coatings (< 7 nm) of sulphuric acid. At these very thin coatings, the AMS was operated close to its detection limits. Up to now it was not possible to accurately determine AMS detection limits during regular measurements. Therefore, the mathematical tools to analyse the detection limits of the AMS have been improved in this work. It is now possible to calculate detection limits of the AMS under operating conditions, without losing precious time by sampling through a particle filter. The instrument was characterised in more detail to enable correct quantification of the sulphate loadings on the ATD particle surfaces. Correction factors for the instrument inlet transmission, the collection efficiency, and the relative ionisation efficiency have been determined. With these corrections it was possible to quantify the sulphate mass per particle on the ATD after the condensation of sulphuric acid on its surface. The AMS results have been combined with the ice nucleus counter results. This revealed that the IN-efficiency of ATD is reduced when it is coated with sulphuric acid. The reason for this reduction is a chemical reaction of sulphuric acid with the particle's surface. These reactions are increasingly taking place when the aerosol is humidified or heated after the coating with sulphuric acid. A detailed analysis of the solubility and the evaporation temperature of the surface reaction products revealed that most likely aluminium sulphate is produced in these reactions.

Mitochondrial respiratory supercomplex association limits production of reactive oxygen species from Complex I

Evidence accumulated in the last ten years has demonstrated that a large proportion of the mitochondrial respiratory chain complexes in a variety of organisms is arranged in supramolecular assemblies called supercomplexes or respirasomes. Besides conferring a kinetic advantage (substrate channeling) and being required for the assembly and stability of Complex I, indirect considerations support the view that supercomplexes may also prevent excessive formation of reactive oxygen species (ROS) from the respiratory chain. Following this line of thought we have decided to directly investigate ROS production by Complex I under conditions in which the complex is arranged as a component of the supercomplex I1III2 or it is dissociated as an individual enzyme. The study has been addressed both in bovine heart mitochondrial membranes and in reconstituted proteoliposomes composed of complexes I and III in which the supramolecular organization of the respiratory assemblies is impaired by: (i) treatment either of bovine heart mitochondria or liposome-reconstituted supercomplex I-III with dodecyl maltoside; (ii) reconstitution of Complexes I and III at high phospholipids to protein ratio. The results of this investigation provide experimental evidence that the production of ROS is strongly increased in either model; supporting the view that disruption or prevention of the association between Complex I and Complex III by different means enhances the generation of superoxide from Complex I . This is the first demonstration that dissociation of the supercomplex I1III2 in the mitochondrial membrane is a cause of oxidative stress from Complex I. Previous work in our laboratory demonstrated that lipid peroxidation can dissociate the supramolecular assemblies; thus, here we confirm that preliminary conclusion that primary causes of oxidative stress may perpetuate reactive oxygen species (ROS) generation by a vicious circle involving supercomplex dissociation as a major determinant.