The nature of interactions of fundamental particles is governed by symmetries. These interactions are well described by an elegant and simple SU(3)c x SU(2)L x U(1)Y symmetric gauge theory that we call the Standard Model (SM) of particle physics. Very recently the CMS and ATLAS experiments at the Large Hadron Collider (LHC) confirmed the discovery of a boson of mass of about 125 GeV. Already, the data collected from these experiments seem to indicate that this particle is in fact the last missing piece and essential ingredient of the Standard Model : the Higgs boson. The Higgs has the very distinct role of providing a mechanism through which masses for other particles can be generated without destroying gauge invariance and hence the renormalizability of the theory. While this discovery completes the picture we have of the SM, the SM itself does not account for several experimentally observed phenomena , notably, dark matter (DM) and the baryon asymmetry in the universe (BAU). From a theoretical perspective a possibility for gauge coupling unification, an explanation for the quark flavour structure and the stability of the Higgs mass to radiative corrections are features that are absent in the framework of SM. This provides a strong basis to the hypothesis that there must be some intermediate scale (between the Planck scale and electroweak scale) of new physics, i.e. physics beyond the SM (BSM). The renormalizability of SM guarantees that various parameters of SM can be determined from the electroweak scale all the way up to the Planck scale. It is interesting to note that the RG evolution of the Higgs quartic coupling is driven to smaller values and can also become negative as the energy scale increases. Naively, a negative quartic coupling indicates destabilization of the EWSB vacuum. The energy scale at which the quartic coupling becomes negative would signify a break down of the theory and would set a scale for new physics. In principle the potential can be made stable through Planck scale dynamics and other vacua (other than the EWSB vacuum) may crop up. In this scenario the EWSB vacuum may decay to the deeper vacua. It is safe to say that, within experimental uncertainties of the Higgs and top quark masses the EWSB vacuum appears to be metastable. We are now left clueless: neither do we have any hints as to the nature of BSM physics nor the scale at which SM breaks down and new physics is assured. One should also note that although the evidence for BSM is compelling, data analysed from 7 and 8 TeV runs of the LHC have not produced any signals of BSM physics so far. Thus any indications of TeV scale BSM physics have been eluding us. In such a scenario the Higgs boson has assumed the role of a portal to study the possibilities of new physics. This is also motivated by the key role that the Higgs plays in generation of mass in a gauge symmetric theory. It is therefore reasonable to assume that the Higgs boson does in fact couple to particles predicted in BSM physics. Such couplings would play a role in modifying the properties of this boson. It is now essential to determine the properties of the Higgs as precisely as possible to search for signs of BSM. This thesis explores the idea of using the Higgs as a portal to study BSM physics. The properties of the Higgs that have already been measured with data from the first two runs of the LHC are its mass, branching ratios, spin and CP. When placed in the framework of a particular new physics model, these properties impose restrictions on the couplings and masses of BSM particles. A strong candidate for a BSM scenario is a Supersymmetric extension of the SM. Supersymmetry is an extension of the Poincar´e group that describes space time symmetries. Fermionic and bosonic degrees of freedom are mixed through the generators of this extended symmetry. In the minimal supersymmetric extension of the SM (MSSM), each particle of SM has a corresponding superpartner with identical quantum numbers modulo its spin. Since we do not see, for example, a bosonic superpartner of the fermionic top quark of the same mass as that of the top quark, this must mean that the supersymmetry, even if it is realized in nature, is not exact and must be broken. Although the symmetry may be broken the MSSM has some very appealing features: stabilization of the Higgs mass to quantum corrections, gauge coupling unification and possible dark matter candidate if the lightest Supersymmetric particle happens to be both stable and neutral. It is interesting to note that in MSSM, the tree level Higgs mass is bounded from above by the Z boson mass ( ~90 GeV ). The measured value of the Higgs mass (~126 GeV ) is still achievable in the MSSM through quantum corrections, the largest contribution coming from the top quarks and stop squarks. One therefore sees that the mass of the Higgs can already provide information about top superpartners. The presence of additional charged and coloured scalars implies the possibility of existence of charge and colour breaking (CCB) minima which would affect the stability of the Electroweak Symmetry breaking (EWSB) minima generated by the Higgs potential. Stability of EWSB is then dependent on parameters in the scalar sector of MSSM. We explore the nexus between the Higgs mass and vacuum stability in this model and find restrictions on the MSSM parameter space. The lighter Higgs of the MSSM couples differently to SM particles than the SM Higgs boson. More specifically one expects the couplings of the MSSM Higgs to gauge bosons to be smaller than in SM and unlike the SM Higgs, up type quarks have couplings strengths that are different from that of down type quarks. In the decoupling regime these differences become negligible and the lighter MSSM Higgs behaves identically to the SM Higgs. The measured Higgs rates do not show any large deviations from the expectations of a SM Higgs. It is therefore reasonable to assume that MSSM, if realized, resides in the decoupling regime. While tree level processes are not altered significantly in this regime, the same cannot be said about loop induced processes such as (h→ γγ) or (gg → h). Such processes may be affected significantly by sparticles running in the loops. Higgs decays to two photons can be strongly affected by the stau sector of MSSM and we study this in connection with EWSB vacuum stability. In several models of dark matter, the dark matter candidate particle couples to the Higgs boson. It may well be that this candidate particle may be light enough so that the decay of the Higgs boson to these particles may be possible. For example, in the framework of the MSSM, the LSP (˜χ01) is the dark matter candidate and a decay of the form hχ˜→01χ˜01is possible depending on the mass and strength of coupling of such a particle. At the LHC this would show up as an branching ratio to particles that are invisible to the detectors. The dominant production mode of the Higgs at LHC proceeds through gluon fusion. In this channel a signal for an “invisibly” decaying Higgs would show up as missing energy plus jets at LHC. This has already been studied in quite some detail. We focus on other production modes, namely Vector Boson Fusion (VBF) and associated production (VH), in determining an invisible branching fraction at LHC. These two production channels are much less sensitive to any other BSM signals that may mimic an invisibly decaying Higgs and thus provide clean signals for the latter. A determination of the nature of interactions between the Higgs and gauge bosons is of paramount importance. An understanding of these interactions is closely tied to an understanding of the nature of EWSB. There are two aspects to probing these interactions. One is a determination of the Lorentz structure of the Higgs and gauge boson vertices and the second is to determine the strength of its couplings. The Higgs coupling to two gauge bosons (the hVV vertex) in SM is of the form ~ agµν . Under the assumption that BSM physics does not alter this Lorentz structure, information about possible new physics can be simply extracted through a determination of the strength of the coupling aV . However, the most general structure of this vertex is of the form (aV gµν + bV pµq ν + cV ɛ µνρσpρqσ) . Here p and q are the sum and difference of the two gauge boson momenta respectively and ɛµνρσ the completely antisymmetric Levi-Civita tensor. The term cV parametrizes CP-odd couplings while the rest are CP-even. The terms proportional to b V and cV may be generated by new physics. But which new physics model do we look at? There are a plethora of such models. Rather than shooting in the dark at random BSM directions one could adopt the following approach. In the absence of BSM signals at the LHC so far, one could assume that the scale of physics is relatively high and BSM particles are more massive than SM particles and can therefore be integrated out of the Lagrangian. It is also prudent to assume that new physics respects the SU(3)c x SU(2)L x U(1)Y gauge symmetry of SM. With these two assumptions in hand, one could supplement the SM Lagrangian with additional operators. These operators which generally have mass dimensions greater than four would destroy the renormalizability of the theory, though an interpretation as an effective theory up to a scale Λ is still valid. The idea is to now study the consequences that this effective theory would have on measurable properties of the Higgs. The effective theory could affect both the Lorentz structure as well as the strength of the couplings of the Higgs to the gauge bosons. This thesis deals with the determination of the Lorentz structure of the Higgs coupling to two gauge bosons , i.e the trilinear vertex. An analysis of this for the hZZ vertex has already been performed by ATLAS and CMS using h → ZZ *decays. A pure pseudoscalar Higgs (cZ ≠0, aZ = bZ = 0) coupling has been ruled out at about 2 ~ 3 σ level. Bounds have also been placed on a mixed scalar-pseudoscalar coupling (a Z =0,cZ =0,bZ = 0). This however, is not the end of the story. There are two important points to note here. Firstly it is important to be able to verify these findings in other production modes. To this end, we investigate the ability of VBF production to probe such anomalous couplings and find strong effects on the pseudo-rapidity distributions of the tagging jets in VBF. Secondly it is important to also look for such anomalous couplings in the hWW vertex. At this point, one might argue that the hZZ vertex and hWW vertex are connected by Custodial symmetry. However this symmetry is violated in SM by gauging of the hypercharge. It follows that violations of this symmetry should arise naturally in BSM physics. A study of the anomalous vertex is not easily achieved in h→ WW ∗ decays due to backgrounds and difficulties in reconstructing momenta. The VBF channel can be quite effective here although there is significant contamination from VBF production through the Z boson. We find that a cleaner production mode to use would be associated production. Until recently the low cross-section of Vh made it difficult to analyse this channel at LHC. An analysis of Vh has been made possible by the use of modern jet substructure techniques using (h→ bb) decays. We use these techniques and study how one can probe anomalous couplings in the Vh production mode at LHC. One of the most important couplings of the Higgs is that to the top, the heaviest SM particle. Not only is this coupling responsible for the main production channel of the SM Higgs at the LHC but the interaction with the top also has important consequences on spontaneous symmetry breaking within the SM – notably, vacuum stability arguments – as well as beyond the SM – supersymmetry, for instance, where the top drives electroweak symmetry breaking in some scenarios. The strength as well as the CP property of the Higgs top coupling is therefore an important aspect of to study. more specifically we investigate terms of the form ψ¯t(at + ibtγ5)ψth. here ψt and h corresponds to the top quark and Higgs fields respectively. at and bt parametrize scalar and pseudoscalar couplings respectively. Since the dominant production mode of the Higgs at the LHC (gluon fusion) proceeds through a top quark loop as do decays of the Higgs to two photons, some information about these couplings may be extracted just by looking at Higgs production and decay rates. However, an unambiguous determination of these couplings is possible only through Higgs production with a top and anti-top pair. Although the production rates are very small at the LHC, such a study is of prime importance. We investigate t¯th production at the LHC and list some useful observable that can probe the couplings described above. The outline of the thesis is as follows. We start with brief introduction to SM and Electroweak Symmetry breaking (EWSB) also briefly reviewing SM Higgs production and decay at the LHC. We then investigate the information that the Higgs mass in conjunction with stability of the EWSB vacuum provides about the stop sector of the MSSM. We further investigate the information that Higgs decay rates in conjunction with the stability of the EWSB vacuum could provide about the stau sector in the MSSM. We move on to examining the extent to which an invisible branching ratio of the Higgs could be measured or excluded directly at the LHC. Coming to the second part of the thesis we examine in a model independent way the nature of the Higgs-gauge boson couplings. We first give a brief description of the Higgs gauge boson vertex and the effective theory approach following it up with a description of how this could be probed using Higgs decays. We then follow it up with a study on how the Lorentz structure could affect Higgs production in Vector Boson fusion and Higgs production in association with W or Z boson. Finally, we show how the CP properties of the Higgs coupling to the top quark can be investigated using tth production along with Higgs rates.

Aussagen zur Reaktivität von Metalloxidclustern in der Gasphase wurden aus Messungen von totalen integralen Wechselwirkungsquerschnitten an Gastargets abgeleitet und diese mit Untersuchungen des Reaktionsverlaufes unter thermalisierten Bedingungen in einem Fließreaktor korreliert. Diese Untersuchungen konnten mit einer speziell entwickelten Molekularstrahlapparatur ausgeführt werden, die detailliert beschrieben wird. Mittels dieser beider Methoden wurden die Reaktionen von Bismutoxid-Clusterkationen mit Alkenen untersucht. Als Hauptreaktionskanal wird hier eine Assoziation des Alkens festgestellt. Einzelne Clusterkationen lagern zusätzlich zum Alken molekularen Sauerstoff an. Aus der massenspektrometrisch beobachteten Reaktionsfolge wird ein Mechanismus für die Aktivierung des molekularen Sauerstoffs und die Übertragung auf den Kohlenwasserstoff abgeleitet. Diese Resultate werden durch jüngste quantenchemische Rechnungen bestätigt. (M. Bienati, Dissertation, Humboldt-Universität zu Berlin, 2001) / Insights into the reactivity of metal oxide clusters in the gas phase have been gained from total integral cross sections measured with gas targets and investigations of the reaction sequences at thermalized conditions in a fast flow reactor. These experiments have been carried out with a newly designed molecular beam apparatus, which is described in detail. Applying these two techniques, the reactions of bismuth oxide cluster cations with alkenes have been probed. The main reaction channel is the association of alkenes, but particular clusters bind molecular oxygen additionally. A mechanism for this activation of molecular oxygen and its transfer towards the hydrocarbon has been derived from the mass spectrometrically measured reaction sequence, which is supported by recent theoretical calculations (M. Bienati, Doctoral Thesis, Humboldt-Universität zu Berlin, 2001)

Die kürzliche globale COVID-19-Pandemie hat deutlich gezeigt, dass hohe medizinische Kosten eine große Herausforderung für unser Gesundheitssystem darstellen. Daher besteht eine wachsende Nachfrage nach personalisierten tragbaren Geräten zur kontinuierlichen Überwachung des Gesundheitszustands von Menschen durch nicht-invasive Erfassung physiologischer Signale. Diese Dissertation fasst die Forschung zur Laserkarbonisierung als Werkzeug für die Synthese flexibler Gassensoren zusammen und präsentiert die Arbeit in vier Teilen. Der erste Teil stellt ein integriertes zweistufiges Verfahren zur Herstellung von laserstrukturiertem (Stickstoff-dotiertem) Kohlenstoff (LP-NC) ausgehend von molekularen Vorstufen vor. Der zweite Teil demonstriert die Herstellung eines flexiblen Sensors für die Kohlendioxid Erfassung basierend auf der Laserumwandlung einer Adenin-basierten Primärtinte. Die unidirektionale Energieeinwirkung kombiniert mit der tiefenabhängigen Abschwächung des Laserstrahls ergibt eine neuartige geschichtete Sensorheterostruktur mit porösen Transducer- und aktiven Sensorschichten. Dieser auf molekularen Vorläufern basierende Laserkarbonisierungsprozess ermöglicht eine selektive Modifikation der Eigenschaften von gedruckten Kohlenstoffmaterialien. Im dritten Teil wird gezeigt, dass die Imprägnierung von LP-NC mit Molybdäncarbid Nanopartikeln die Ladungsträgerdichte verändert, was wiederum die Empfindlichkeit von LP-NC gegenüber gasförmigen Analyten erhöht. Der letzte Teil erläutert, dass die Leitfähigkeit und die Oberflächeneigenschaften von LP-NC verändert werden können, indem der Originaltinte unterschiedliche Konzentrationen von Zinknitrat zugesetzt werden, um die selektiven Elemente des Sensormaterials zu verändern. Basierend auf diesen Faktoren zeigte die hergestellte LP-NC-basierte Sensorplattform in dieser Studie eine hohe Empfindlichkeit und Selektivität für verschiedene flüchtige organische Verbindungen. / The recent global COVID-19 pandemic clearly displayed that the high costs of medical care on top of an aging population bring great challenges to our health systems. As a result, the demand for personalized wearable devices to continuously monitor the health status of individuals by non-invasive detection of physiological signals, thereby providing sufficient information for health monitoring and even preliminary medical diagnosis, is growing. This dissertation summarizes my research on laser-carbonization as a tool for the synthesis of functional materials for flexible gas sensors. The whole work is divided into four parts. The first part presents an integrated two-step approach starting from molecular precursor to prepare laser-patterned (nitrogen-doped) carbon (LP-NC). The second part shows the fabrication of a flexible LP-NC sensor architecture for room-temperature sensing of carbon dioxide via laser conversion of an adenine-based primary ink. By the unidirectional energy impact in conjunction with depth-dependent attenuation of the laser beam, a novel layered sensor heterostructure with a porous transducer and an active sensor layer is formed. This molecular precursor-based laser carbonization method enables the modification of printed carbon materials. In the third part, it is shown that impregnation of LP-NC with molybdenum carbide nanoparticle alters the charge carrier density, which, in turn, increases the sensitivity of LP-NC towards gaseous analytes. The last part explains that the electrical conductivity and surface properties of LP-NC can be modified by adding different concentrations of zinc nitrate into the primary ink to add selectivity elements to the sensor materials. Based on these factors, the LP-NC-based sensor platforms prepared in this study exhibited high sensitivity and selectivity for different volatile organic compounds.

Kleine Moleküle wie Treibhausgase, aber auch Distickstoff und Disauerstoff stehen im Fokus der chemischen Forschung. Solche Moleküle sind durch ihr Vorkommen in der Atmosphäre ubiquitär vorhanden, preiswert und könnten als Synthesebausteine für die Darstellung von komplexeren Molekülen verwendet werden. In dieser Arbeit wurde die Reaktion koordinativ ungesättigter Diketiminato-Nickelkomplexe ([LNi] Komplexe) mit kleinen Molekülen untersucht. Zunächst wurden die Mechanismen der N2-Aktivierung durch reduzierte [LtBuNiI]- und [LMe6NiI] Komplexe miteinander verglichen. Dabei konnte das distickstoffaktivierende Schlüsselintermediat identifiziert und strukturell charakterisiert werden. Weiter wurden die N2-Komplexe [(LtBuNiI)( 1 1 N2)] bzw. K2[(LtBuNiI)( 1 1 N2)], die Vorläufer für [LNiI]- und [LNi0]– Komplexfragmente darstellen, hinsichtlich ihrer Potentials zur Aktivierung der reaktionsträgen Treibhausgase SF6 und NF3 untersucht. Über Reaktionen von Übergangsmetallkomplexen mit NF3 war bis dahin noch nicht berichtet worden; zur Umsetzung von SF6 existierten wenige Publikationen, in denen aber sehr viele mechanistische Fragen offengeblieben sind. Die Mechanismen der SF6- und NF3-Aktivierung wurden durch Kombination einer Vielzahl von ex- und in situ Analysen beleuchtet. Im Falle der SF6 Aktivierung gelang es zudem, ein Nickel(I)-Intermediat zu isolieren. Ein Produkt beider Systeme war der Fluorido-Nickel(II)-Komplex [LtBuNiIIF], dessen Reaktionsverhalten ebenfalls studiert wurde. Doch nicht nur Komplexe mit Nickelatomen in niedrigen Oxidationsstufen erwiesen sich für die Aktivierung kleiner Moleküle geeignet, sondern auch kationische [LtBuNiII(D)]+-Komplexe. Diese Nickel(II)-Komplexe reagierten mit fluorierten Molekülen, N2O sowie O2, was bemerkenswert ist, da Nickel(II)-Komplexe üblicherweise inert gegenüber O2 sind. Im Zuge der O2-Studien wurde ein metastabiler Oranoperoxidkomplex isoliert und strukturell charakterisiert, was beispiellos in der Literatur ist. / Current research focuses on the activation of small molecules like greenhouse gases, thermodynamically stable molecules like N2 and kinetically stabilized molecules like O2, which are all abundant in the atmosphere. Thus, it appears to be alluring to use them as cheap and readily available building blocks for the synthesis of value-added compounds. This dissertation deals with the reaction of low-coordinate diketiminate nickel complexes [LNi] and such small molecules. Initially, the mechanisms of the dinitrogen activation by reduced [LtBuNiI] and [LMe6NiI] complexes were studied. As a result, the key intermediate [(LtBuNiI)x(3 Br)xKx] (x > 1) was identified and structurally characterized. Subsequently, the nickel complexes [(LtBuNiI)( 1 1 N2)] and K2[(LtBuNiI)( 1 1 N2)], which represent sources for [LtBuNiI] and [LtBuNi0]– moieties, were applied to the activation of the inert, but very efficient greenhouse gases SF6 and NF3. Prior to these investigations, no transition metal complex had been reported to react with NF3. Publications dealing with the conversion of SF6 had been scarce, too, while at same time, the mechanisms involving its activation had been speculative. The mechanisms of the NF3 and SF6 activation reactions were deduced combining numerous ex-situ and in situ analytical methods. In case of the SF6 activation, even an intermediate could be isolated. In both systems, the nickel fluoride complex [LtBuNiIIF] was formed and its reaction behaviour was also studied. Furthermore, not only [LtBuNiI]- and [LtBuNi0]– moieties proved to be reactive towards small molecules, but also cationic [LtBuNiII(D)]+ complexes, which were specifically developed for this purpose. The reactions of [LtBuNiII(D)]+ complexes with fluorinated molecules (e. g. PhF, NF3), O2 and N2O were studied. In course of the O2 activation, a metastable organoperoxide complex was isolated and structurally characterized, which is unparalleled in the literature.

Der Cr2O3 ist einer der wichtigsten Katalysatoren im Chlor/Fluor (Cl/F) Austauschreaktionen für die Produktion von chlorofluorocarbon (CFC) Alternativen. Es wird als ein ausgezeichneter heterogener Katalysator für Fluorierung Reaktionen gegründet. Die Dismutierung von CCl2F2 wurde verwendet, um die Wirkung von Halogenierung von Chrom(III) Oxyd auf Cl/F-Austauschreaktionen zu untersuchen und um den Unterschied zwischen den inaktiven und aktiven Katalysatoren herauszufinden. Die heterogenen Reaktionen wurden in einem tubular-flow Ni Reaktor und auch unter simulierten Reaktionsbedingungen in einem Reaktor durchgeführt, wo nach der Reaktion die Photoelektronspektroskopie (XPS) und die Auger-Elektronspektroskopie (XAES) Analysen konnte direkt ohne Luftkontakt, unter so genannt "in - situ" Bedingungen gefolgt werden. Es wurde gezeigt, dass die Probleme der Behandlung von Cr (III) 2p Photoelektronenspektren so gelöst werden können, dass ihnen relevante Daten für die chemische Charakterisierung von Oberflächen entnommen werden können. Hochaufgelöste Photoelektronspektroskopie von Cr2O3 Pulverproben zeigte deutlich die Existenz von spektralen Strukturen, die mit Multiplet-Aufspaltungen im jeweiligen Cr 2p Spektrum verbunden sind. Das Spektrum kann durch eine Peakfit-Analyse vertieft interpretiert werden in dem die Anfangswerte für die Peakparameter der Multiplet-Strukturen den jeweiligen Cr L2,3 XANES Spektren entnommen werden. Vom theoretischen Gesichtspunkt sollte dasselbe Verfahren auch eine Analyse der Cr 2p Photoelektronenspektren von alpha-CrF3, CrCl3 und anderen Chrom (III) Verbindungen ermöglichen. Die Unterschiede, die im Experiment für die Cr2O3, alpha-CrF3 und CrCl Photoelektronenspektren beobachtet werden, deuten auf die Tatsache, dass, obwohl in all diesen Fällen dieselben Multiplet-Aufspaltungen für Cr3+ erwartet werden, individuelle Einflüsse der Symmetrie und Ligandenfelder die Endgestalt des jeweiligen Cr 2p Photoelektronenspektrums definieren. Eine Analyse von Cr 3s Spektren kann zusätzlich wertvolle Finger-print Informationen zu chemischen Zuständen von Chrom in Cr (III) Verbindungen erbringen. Sowohl ex-situ als auch ´´in-situ´´ ESCA zeigen, dass sobald CCl2F2 zu Cr2O3 an 390 °C geführt wird, Fluorierung sowie Chlorierung an der Katalysator-Oberfläche findet statt. Wenn die XPS Oberflächenzusammensetzung etwa 4 Atom - % Fluorierung und 6 Atom - %-Chlorierung erreicht, wird die maximale katalytische Aktivität erhalten. Die längeren Reaktionszeiten ändern bedeutsam die erhaltene Oberflächenzusammensetzung von aktiviertem Chrom(III) Oxyd nicht. Der Fluorierung und Chlorierung von Chrom(III) Oxyd wurden weiter durch verschiedenen HF und HCl Behandlungen ebenso untersucht. Die aktivierten Chrom(III) Oxyd Proben und Referenzproben mit der weithin bekannten chemischen Struktur wurden auch durch Kantennahe Röntegenabsorptionsuntersuchungen (XANES), Flugzeit-statischesekundärionenmassenspektroskopie (TOF-SSIMS), Rasterelektronenmikroskopie (SEM), Fluor-Festkörper-NMR, Pyridin-FTIR, Nasschemie (F und Cl) Analyse, Pulver Röntgensbeugung (XRD) und Oberflächen (BET) Analyse untersucht. Die Ergebnisse der Referenzproben Cr2O3, Cr (OH) 3, CrF2 (OH), CrF3.3H2O, Alpha-CrF3, Beta-CrF3 und CrCl3 und aktivierte Cr2O3 Proben wurden verglichen. Die angewandten Charakterisierungsmethoden schlagen vor, dass die Bildung der Chrom-Oxydchlorid-Fluorid-Arten, bzw. Chrom-Oxyd Halogenide, an der Oberfläche ist genügend die katalytische Aktivität zu versorgen. Die Anwesenheit jedes CrF3 und/oder CrCl3 Phasen auf den aktivierten Chrom(III) Oxyd Proben wurde nicht entdeckt. / The Cr2O3 is one of the most important catalysts in the chlorine/fluorine (Cl/F) exchange reactions for the production of chlorofluorocarbon (CFC) alternatives. It is established as an excellent heterogeneous catalyst for fluorination reactions. The dismutation of CCl2F2 was used to probe the effect of halogenation of chromia on Cl/F exchange reactions in order to find out the difference between the inactive and active catalysts. The heterogeneous reactions were performed in a continuous flow Ni reactor and also under simulated reaction conditions in a reactor where after the reaction the X-ray photoelectron spectroscopy (XPS) and the X-ray excited Auger electron spectroscopy (XAES) analyses could be followed directly without air contact, under so called ´´in-situ´´ conditions. In order to be able to apply the Cr(III) 2p XPS analysis in the proper manner the spectroscopic features of the chromium(III) compounds of O, F and Cl were re-investigated. Latest generation of XPS spectrometers, which are able to analyze non-conductive powders with ultimate energy resolution, were used to reveal multiplet splitting features and satellite emission in the Cr 2p spectra. The energy positions of the multiplets were determined by total electron yield (TEY)- X-ray absorption near edge structure (XANES) spectroscopy. Using both high resolution XPS and XANES spectra a peak-fit analysis, which is also applicable for normally resolved Cr 2p XPS spectrum, was proposed. In order to overcome the known background problem by drawing the background in the broad Cr 2p window including the high binding energy satellite, a modified Shirley background, which is a combination of a linear and Shirley function, was used. Moreover, the spectroscopic features of the Cr(III) 3s XPS spectrum, which is relatively simpler than the Cr 2p one, were also surveyed. An alternative chemical analysis was proposed by using chemical state plots for Cr 3s. Both ex- and in-situ ESCA show that as soon as Cr2O3 is conducted to CCl2F2 at 390 °C fluorination as well as chlorination takes place at the catalyst surface. When the XPS surface composition reaches approximately 4 atom-% fluorination and 6 atom-% chlorination, maximum catalytic activity is obtained. Applying longer reaction times do not change significantly the obtained surface composition of the activated chromia. The fluorination and chlorination of chromia was further investigated by various HF and HCl treatments as well. The activated chromia samples and reference samples with well known chemical structure were also characterized by XANES, time of flight - static secondary ion mass spectroscopy (TOF-SSIMS), scanning electron microscopy (SEM), fluorine solid state NMR, pyridine-FTIR, wet chemical (F and Cl) analysis, X-ray powder diffraction (XRD) and surface area (BET) analysis. The results for the references Cr2O3, Cr(OH)3, CrF2(OH), CrF3.3H2O, alpha-CrF3, beta-CrF3 and CrCl3 and activated Cr2O3 samples were compared. The applied characterization methods suggest that the formation of chromium oxide chloride fluoride species, e.g. chromium oxide halides, at the surface is sufficient to provide catalytic activity. The presence of any CrF3 and/or CrCl3 phases on the activated chromia samples was not detected.

Marine aerosols have attracted increasing attention over the past 15 years because of their potential significance for global climate modelling. The size distribution of these aerosols extends from super-micrometer sea salt mode particles down through 150 nm accumulation mode particles, 40 nm Aitken mode particles and nucleation mode particles which extend from 25 nm right down to clusters of a few molecules. The process by which the submicrometer modes form and grow and their composition have remained topics of debate throughout this time in large part because of the difficulties associated with determining their composition and relating it to proposed models of the formation process. The work compared the modality of marine aerosol influencing the South-east-Queensland region with that of other environmental aerosols in the region. The aerosol was found to be consistent with marine aerosols observed elsewhere with concentrations below 1000 cm-3 and frequently exhibiting the distinct bimodal structure associated with cloud processing, consisting of an Aitken mode at approximately 40 nm, an accumulation mode in the range 100-200 nm and a coarse mode attributed to sea salt between 600 and 1200 nm. This work included the development of two new techniques for aerosol research. The first technique measures aerosol density using a combination of aerosol size distribution and gravimetric mass concentration measurements. This technique was used to measure the density of a number of submicrometer aerosols including laboratory generated NaCl aerosol and ambient aerosol. The densities for the laboratory generated aerosols were found to be similar to those for the bulk materials used to produce them. The technique, extended to super-micrometer particle size range may find application in ambient aerosol research where it could be used to discriminate between periods when the aerosol is dominated by NaCl and periods when the density is more representative of crustal material or sulfates. The technique may also prove useful in laboratory or industrial settings for investigating particle density or in case where the composition is known, morphology and porosity. The second technique developed, integrates the existing physicochemical techniques of volatilisation and hygroscopic growth analysis to investigate particle composition in terms of both the volatilisation temperatures of the chemical constituents and their contribution to particle hygroscopic behaviour. The resulting volatilisation and humidification tandem differential mobility analyser or VH-TDMA, has proven to be a valuable research tool which is being used in ongoing research. Findings of investigations relating the composition of the submicrometer marine aerosol modes to candidate models for their formation are presented. Sea salt was not found in the numerically dominant particle type in coastal nucleation mode or marine Aitken and accumulation modes examined on the Southeast Queensland coast during periods where back trajectories indicated marine origin. The work suggests that all three submicrometer modes contain the same four volatile chemical species and an insoluble non-volatile residue. The volatility and hygroscopic behaviours of the particles are consistent with a composition consisting of a core composed of sulfuric acid, ammonium sulfate and an iodine oxide coated with a volatile organic compound. The volume fraction of the sulfuric acid like species in the particles shows a strong dependence on particle size.

Helper T cells direct the immunological response to foreign pathogens and cancer. To become activated, helper T cells must recognize unique peptides presented on major histocompatibility complex II (pMHCII) by antigen presenting cells (APCs) with their T cell receptor (TCR). While much is known about helper T cell activation signaling cascades and the subsequent roles of helper T cell subsets, the initiation of helper T cell activation by the TCR and other co-receptors is less well understood. Specifically, the affinity of the TCR for its pMHCII can change helper T cell subset fate, proliferation, and alter the risk for activation induced cell death. High affinity TCRs are attractive targets for immunotherapies, but little is known about how helper T cells respond to high affinity TCRs. Here we describe high affinity TCR activation thresholds for both full length TCRs and chimeric antigen receptor TCRs both with and without the presence of the coreceptor CD4 and propose a mechanism whereby CD4 inhibits T cell activation via Lck sequestration and a CD4-independent method. Dysregulated helper T cells play critical roles in the development and perpetuation of systemic lupus erythematosus (SLE), a systemic autoimmune disease that causes widespread inflammation and organ damage throughout the body. Chronic inflammation in SLE affects the immune response to viruses and the risk of developing cancer. However, in SLE patients, it is unclear if viruses initiate the development of cancer directly or if the effects are non-interacting and concomitant. Here we describe the interactions between SLE, viruses, and cancer risk revealing that viruses and SLE do interact to increase the both the overall cancer risk and the risk for hematological malignancies. Due to vaccine efficacy, vaccine preventable diseases (VPDs) are no longer commonly experienced or understood by the public. Vaccines are a victim of their own success and according to the World Health Organization (WHO), vaccine hesitancy (VH) is one of the top threats to global health. VH is the refusal to accept vaccinations and the reasons for VH vary across time, place, and vaccine. Refuting VH is difficult as directly confronting false assumptions can cause individuals to become more entrenched in their position resulting in confirmation bias. Adults with VH attitudes are often motivated by concerns over personal liberty, harm, independence, and body purity. Here we describe the results of a VPD interview- and education-based intervention geared towards promoting positive vaccine attitudes for young adults and demonstrate that education focused on VPDs is more effective than vaccine safety.

Die zwei Chelatbildner für Schwermetallionen, Carboxymethylthio- (CMT) und Piperazinyl- (PPz), wurden erfolgreich über die direkte kathodische Elektroreduktion ihres Aryl diazoniumsalzes auf Wasserstoff–terminiertes Silizium (Si-H)- und auf Gold (Au)-Substratoberflächen aus den Derivaten: 4-(Carboxymethylthio)benzenediazoniumsalz [4-CMTBD]+BF4- und 4-(Piperazinyl)benzenediazoniumsalz [4-PPzBD]+BF4- abgeschieden. Die elektrochemische Anbindung wurde unter Verwendung von zyklischer Voltammetrie (CV) und chronoamperometrie (CA) Techniken durchgeführt. Die IRSE-Spektren bestätigten die Anwesenheit der organischen CMT- und PPz-Komplexbildnergruppen durch ihre charakteristischen Absorptionsbanden auf den elektrotransplantierten Si(111) - und Au-Substraten, was eine erfolgreiche Oberflächenfunktionalisierung anzeigt. Die Analyse, der bei der chronoamperometrischen Elektroreduktion gemessenen Ströme, der beiden Diazoniumkationen [4-CMTBD]+ und [4-PPzBD]+ sowohl auf Si (111)-H- als auch auf Au-Oberfläche, zeigt eine Korrelation mit der kinetischen Reaktionsgleichung zweiter Ordnung während der frühen Stufen der jeweiligen elektrochemischen Deposition. Die Behandlung der funktionalisierten Oberflächen, Si(4-CMTB) mit Cu- und Pb- Ionen, und Si(4-PPzB) mit Cu-Ionen unter niedrigen hydrothermalen Druckbedingungen führte zur Bildung von organometallischen Chelatkomplexen auf den Oberflächen. Die Aufnahme von Cu-Ionen sowohl auf der Si(4-CMTB)- als auch auf der Si(4-PPzB)-Oberfläche wurde ebenfalls mittels XPS untersucht. Die Schwermetallionen-chelatisierenden Nanokompositoberflächen, die in dieser Arbeit erfolgreich hergestellt und charakterisiert wurden, stellen neuartige funktionelle Materialien dar, die potentiell technische Interesse haben könnten. / The two heavy-metal-ion (HMI) chelating groups, carboxymethylthio- (CMT), and piperazinyl- (PPz), were successfully electrografted on Si(111)-H and Au substrate surfaces via the direct cathodic electroreduction of their aryl diazonium salt derivatives: the 4-(carboxymethylthio)benzenediazonium salt [4-CMTBD]+BF4-, and the 4-(piperazinyl)benzenediazonium salt [4-PPzBD]+BF4-. The IRSE spectra confirmed the successful surface functionalization by the CMT and PPz chelating groups by their characteristic absorption bands on the electrografted Si(111) and Au substrates. The analysis of the chronoamperometric electroreduction of the two diazonium cations [4-CMTBD]+ and [4-PPzBD]+, on both Si(111)-H and Au surfaces, revealed that the rate of decay in currents correlates with the second-order kinetic rate law during the early stages of the electrografting reactions. The treatment of the functionalized surfaces, Si-(4-CMTB) with the Cu and Pb ions, and Si-(4-PPzB) with Cu ions under low pressure hydrothermal conditions led to the formation of organometallic chelate complexes on the surfaces. The uptake of Cu ions on both the Si-(4-CMTB) and Si-(4-PPzB) surfaces was also elucidated by XPS measurements. The HMI chelating nanocomposite surfaces successfully fabricated and characterized in this work constitute novel functional materials that may be of potential engineering interests.

In dieser Dissertation wird der Einfluss unterschiedlicher Sauerstoff-Koordinationsgeometrien um ein zentrales Kobaltatom evaluiert. Genauer werden Oxide, die tetraedrisch und oktaedrisch koordiniertes Kobalt enthalten, synthetisiert und charakterisiert. Zudem wird ihre Aktivität in Hinblick auf die Sauerstoffentwicklungsreaktion (OER) unter alkalischen Bedingungen untersucht. Die elektrochemischen Analysen zeigen dabei, dass Materialien, die Kobalt in tetraedrischer Sauerstoffkoordination enthalten, die besseren Katalysatorvorläufer für die OER sind. Weiterhin kann demonstriert werden, dass das Herauslösen von inaktiven Metallen aus einer Struktur die Aktivität erhöht. Darauf basierend wird das neue Material Zn0.35Co0.65O vorgeschlagen. Es kristallisiert in der Wurtzitstruktur und enthält nur tetraedrisch koordinierte Atome. In alkalischen Lösungen wandelt sich die Wurtzitstruktur über die Zwischenstufe Co(OH)2 zum gamma-Co(O)OH um, und nahezu alles Zink wird aus der Struktur herausgelöst. Dadurch wird ein Material mit einer großen elektrochemisch aktiven Oberfläche gewonnen, das unterkoordinierte CoO(6-x) Oktaeder als aktive Zentren für die OER enthält. Hierdurch wird eine herausragende katalytische Leistung erreicht. Um weitere Einblicke in die OER zu generieren, wird Diffuse Reflexions UV/Vis (DRUV) Spektroskopie verwendet. Es werden neuartige Durchflusszellendesigns vorgeschlagen, die es erlauben, DRUV Spektren während der Katalyse aufzunehmen, d.h. operando. Durch diesen spektroelektrochemischen Ansatz werden Veränderungen der Katalysatoren während der OER beobachtet. So kann die Phasenumwandlung von Zn0.35Co0.65O erfolgreich verfolgt werden. Ebenso kann gezeigt werden, dass CoAl2O4 und Co2SnO4 nur an ihrer Oberfläche katalytische Aktivität aufweisen. Durch den Vergleich mit ex situ Analysen werden eindeutige Struktur-Eigenschaftsbeziehungen vorgeschlagen und tiefere Einsichten in die katalytisch aktiven Strukturmotive erhalten. / In this PhD thesis, the influence of different coordination geometries of oxygen atoms around a central cobalt atom is evaluated. Specifically, oxides containing tetrahedral and octahedral coordinated cobalt are synthesized, characterized and their activity towards the OER under alkaline conditions is evaluated. The electrochemical analyses reveal, that materials containing cobalt in tetrahedral oxygen coordination are better precatalysts for the OER. Furthermore, it is demonstrated that leaching of inactive metals from a structure increases the activity as well. Based on the previous mentioned, the new material Zn0.35Co0.65O is proposed. It crystallizes in the wurtzite structure and contains solely tetrahedrally coordinated atoms. In alkaline solutions, it transforms from wurtzite structure via a hydroxide to gamma-Co(O)OH, and nearly all Zn is leached from the structure. By this, a material with a large electrochemically active surface area is generated, that contains under-coordinated CoO(6-x) octahedra as active centers for the OER. Thus, outstanding catalytic performance is achieved. To generate further insights into the OER, diffuse reflectance ultraviolet visible (DRUV) spectroscopy is facilitated. Novel flow-cell designs are proposed, that allow to record DRUV spectra of catalysts under working conditions, i.e. operando. By this spectroelectrochemical approach, changes the catalysts undergo during the OER are observed. The phase transitions of Zn0.35Co0.65O are successfully followed, and it can be further shown, that CoAl2O4 and Co2SnO4 are only active at their surface. By comparison to ex situ analyses, clear structure-activity correlations are proposed, and deeper insights in the catalytically active structural motifs are obtained.

In dieser Arbeit werden die nanoskaligen Partikel von Magnesiumfluorid (MgF2) und Calciumfluorid (CaF2), die als Nano-Metallfluoride (NMFs) bekannt sind, auf ihr Potenzial zur Verbesserung der Beständigkeit von Holz-basierten Materialien untersucht. Ihre besondere Eigenschaft der geringen Wasserlöslichkeit ist Grundlage dafür, einen langanhaltenden Schutz des behandelten Holzes aufrechtzuerhalten, indem die Auslaugung von Fluorid reduziert wird. Die Partikelgröße der synthetisierten NMFs und ihre Verteilung in behandelten Holzproben wurde charakterisiert. Rasterelektronenemikroskopaufnahmen und der zugehörigen energiedispersiven Röntgenspektroskopie zeigen, dass Aggregate dieser Partikel eine homogene verteilung in der untersuchten Holzmatrix von behandelten Proben. Die Fluoridaggregate bilden eine Schutzschicht um die Zellwände und blockieren deren Hoftüpfel, dadurch ist der mögliche Fließweg für die Wasseraufnahme ins Holz eingeschränkt. Dies zeigt sich in erhöhter Hydrophobie des mit Nano-Metallfluorid (NMF)-behandelten Holzproben. Die biozide Wirkung der NMFs wurde gegen Braunfäulepilzen (Coniophora puteana und Rhodonia placenta), am Weißfäulepilz (Trametes versicolor) und den Termiten (Coptotermes formosanus) geprüft. Im Vergleich zu unbehandelten Proben weist das mit Fluorid behandelte Holz eine höhere Beständigkeit gegen Fäulnis und Termitenfraß auf. Obwohl alle NMF-Behandlungen den durch Fäulnis verursachten Masseverlust des Holzes reduzieren, zeigt nur eine kombinierte Behandlung mit MgF2 and CaF2 eine höhere Wirksamkeit gegen Fäulnis und Termitenfraß auf. Die Ergebnisse dieser Arbeit zeigen, dass NMFs robust genug sind für Anwendungen im Freien mit Bodenkontakt. Darüber hinaus stellen sie aufgrund ihrer sehr schlechten Wasserlöslichkeit ein geringeres Risiko für die menschliche Gesundheit und Umwelt dar. Die neuartigen Ergebnisse dieser Arbeit zeigen das Potenzial von NMFs, die Lebensdauer von Baumaterialien aus nicht haltbarem Holz zu erhöhen. / In this study, nanoscopic particles of magnesium fluoride (MgF2) and calcium fluoride (CaF2) also known as nano metal fluorides (NMFs), were evaluated for their potential to improve wood durability. Their distinct property of low-water solubility is proposed to maintain long-lasting protection of treated wood by reducing the leaching of fluoride. Analytical methods were used to characterize the synthesized NMFs and their distribution in treated wood specimens. In nano metal fluoride (NMF) treated specimens, aggregates of these particles are uniformly distributed in the wood matrix as confirmed with scanning electron microscopy images and their corresponding energy-dispersive X-ray spectroscopy maps. The fluoride aggregates form a protective layer around the tracheid walls and block the bordered pits, thus reducing the possible flow path for water absorption into wood. This is reflected in the increased hydrophobicity of NMF treated wood. The biocidal efficacy of NMFs was tested against brown-rot fungi (Coniophora puteana and Rhodonia placenta), white-rot fungus (Trametes versicolor), and termites (Coptotermes formosanus). Compared to untreated specimens, the NMF treated specimens have a higher resistance to decay caused by brown-rot fungi, white-rot fungus, and termites. Although all NMF treatments in wood reduce the mass loss caused by fungal decay and termite attack, only the combined treatment of MgF2 and CaF2 has efficacy against brown-rot fungi and white-rot fungus. Similarly, wood treated with the combined NMF formulation is the least susceptible to attack by C. formosanus. In this thesis, it was proven that NMFs are robust enough for above ground contact outdoor applications of wood in permanent wetness conditions. Also, they pose a low risk to human health and the environment because they are sparingly soluble. Overall, the novel results of this study show the potential of NMFs to increase the service life of building materials made from non-durable wood.