Single-Molecule Magnets and Multifunctional Molecular Magnetic Materials Based on Polynuclear Metal Complexes

Our work on single molecule magnets and multifunctional magnetic materials is presented in four projects. In the first project we show for first time that heteroatomic-type pseudohalides, such as OCN-, can be employed as structure-directing ligands and ferromagnetic couplers in higher oxidation state metal cluster chemistry. The initial use of cyanato groups in Mn cluster chemistry has afforded structurally interesting MnII/III14 (1) and MnII/III/IV16 (2) clusters in which the end-on bridging cyanates show a preference in binding through their O-atom. The Mn14 compound shows entirely visible out-of-phase alternating currect signals below 5 K and large hysteresis loops below 2 K. Furthermore, the amalgamation of azido groups with the triethanolamine tripodal ligand in manganese carboxylate cluster chemistry has led to the isolation of a new ferromagnetic, high-nuclearity and mixed-valence MnII/III15Na2 (3) cluster with a large ground-state spin value of S = 14. In the second project we demonstrate a new synthetic route to purely inorganic-bridged, transition metal-azido clusters [CoII7 (4) and NiII7 (5)] and coordination polymers [{FeII/III2}n (6)] which exhibit strong ferromagnetic, SMM and long-range magnetic ordering behaviors. We also show that access to such a unique ferromagnetic class of inorganic, N-rich and O-free materials is feasible through the use of Me3SiN3 as the azido-ligand precursor without requiring the addition of any organic chelating/bridging ligand. In the last projects we have tried to bring together molecular magnetism and optics via the synthesis of multifunctional magnetic materials based on 3d- or 4f-metal ions. We decided to approach such challenge from two different directions: firstly, in our third project, by the deliberate replacement of non-emissive carboxylato ligands in known 3d-SMMs with their fluorescent analogues, without perturbing the metal-core structure and SMM properties (complexes 7, 8, and 9). The second route (last project) involves the use of naphthalene or pyridine-based polyalcohol bridging ligands for the synthesis of new polynuclear LnIII metal clusters (Ln = lanthanide) with novel topologies, SMM behaviors and luminescent properties arising from the increased efficiency of the “antenna” organic group. This approach has led us to the isolation of two new families of LnIII8 (complexes 10-13) and LnIII4 (complexes 14-20) clusters.

The Ligand and Membrane-binding Behaviour of the Phosphatidylinositol Transfer Proteins (PITPa & PITPb)

Human Class I phosphatidylinositol transfer proteins (PITPs) exists in two forms: PITPα and PITPβ. PITPs are believed to be lipid transfer proteins based on their capacity to transfer either phosphatidylinositol (PI) or phosphatidylcholine (PC) between membrane compartments in vitro. In Drosophila, the PITP domain is found to be part of a multi-domain protein named retinal degeneration B (RdgBα). The PITP domain of RdgBα shares 40 % sequence identity with PITPα and has been shown to possess PI and PC binding and transfer activity. The detailed molecular mechanism of ligand transfer by the human PITPs and the Drosophila PITP domain remains to be fully established. Here, we investigated the membrane interactions of these proteins using dual polarization interferometry (DPI). DPI is a technique that measures protein binding affinity to a flat immobilized lipid bilayer. In addition, we also measured how quickly these proteins transfer their ligands to lipid vesicles using a fluorescence resonance energy transfer (FRET)-based assay. DPI investigations suggest that PITPβ had a two-fold higher affinity for membranes compared to PITPα. This was reflected by a four-fold faster ligand transfer rate for PITPβ in comparison to PITPα as determined by the FRET assay. Interestingly, DPI analysis also demonstrated that PI-bound human PITPs have lower membrane affinity compared to PC-bound PITPs. In addition, the FRET studies demonstrated the significance of membrane curvature in the ligand transfer rate of PITPs. The ligand transfer rate was higher when the accepting vesicles were highly curved. Furthermore, when the accepting vesicles contained phosphatidic acid (PA) which have smaller head groups, the transfer rate increased. In contrast, when the accepting vesicles contained phosphoinositides which have larger head groups, the transfer rate was diminished. However, PI, the favorite ligand of PITPs, or the presence of anionic lipids did not appear to influence the ligand transfer rate of PITPs. Both DPI and FRET examinations revealed that the PITP domain of RdgBα was able to bind to membranes. However, the RdgBα PITP domain appears to be a poor binder and transporter of PC.

Synthèse diastéréosélective et énantiosélective de dérivés cyclopropaniques 1,2,3-substitués à l’aide de carbénoïdes gem-dizinciques

Les dérivés cyclopropaniques 1,2,3-substitutés sont des composés intéressants dans de nombreux domaines de la chimie. Au cours de cet ouvrage, nous nous sommes intéressés à la synthèse, tout d’abord diastéréosélective puis énantiosélective de ces composés. Nous nous sommes en particulier intéressés à l’utilisation de la zinciocyclopropanation pour l’obtention de ces dérivés cyclopropaniques 1,2,3-substitutés. Cette méthode consiste en l’utilisation d’un carbénoïde gem-dizincique pour effectuer une réaction de type Simmons-Smith. Cette stratégie a l’avantage d’être diastéréosélective favorisant la formation du zinciocyclopropane dont l’atome de zinc est dans une configuration cis avec le groupement directeur qu’est l’oxygène allylique basique. Lors de cette réaction, l’existence d’une réaction compétitive avec un réactif monozincique diminuait l’utilité de la zinciocyclopropanation. L’issue de la réaction s’est avérée dépendre fortement de la nature du carbénoïde utilisé, de la température réactionnelle et de la présence de ZnI2 dans le milieu. L’étude par GCMS de nombreuses conditions pour la formation des différents carbénoïdes a permis d’identifier les paramètres clés conduisant à la zinciocyclopropanation. Ces découvertes ont notamment permis d’étendre la réaction de zinciocyclopropanation aux alcools allyliques portant un seul groupement directeur (ie. non dérivé du 1,4-buténediol). Dans ces conditions, la réaction s’est avérée extrêmement diastéréosélective favorisant la formation du zinciocyclopropane dont l’atome de zinc est dans une configuration cis avec le groupement directeur. Afin de fonctionnaliser les zinciocyclopropanes ainsi obtenus, plusieurs réactions de fonctionnalisation in situ ont été développées. Chacune de ces méthodes a montré une conservation totale de la diastéréosélectivité obtenue lors de la réaction de zinciocyclopropanation. La versatilité de la zinciocyclopropanation a donc été démontrée. Avec une méthode diastéréosélective efficace pour la formation de zinciocyclopropanes à partir d’alcools allyliques ne portant qu’un seul groupement directeur, il est devenu possible d’envisager le développement énantiosélectif de la réaction. L’utilisation d’un dioxaborolane énantiopur a permis la zinciocyclopropanation avec de très bons excès énantiomères de divers alcools allyliques chiraux. La présence sur la même molécule d’un lien C–Zn nucléophile est d’un atome de bore électrophile a conduit à un échange bore-zinc in situ, formant un cyclopropylborinate énantioenrichi. La formation de ce composé bicyclique a permis d’obtenir une diastéréosélectivité parfaite. De nombreux alcools allyliques ont pu ainsi être convertis en cyclopropylborinates. Une réaction de Suzuki subséquente a permis la formation de dérivés cyclopropaniques 1,2,3-trisubstitués avec de très bons excès énantiomères et une excellente diastéréosélectivité. Les cyclopropylborinates obtenus à l’issue de la zinciocyclopropanation énantiosélective se sont avérés être des unités très versatiles puisque de nombreuses méthodes ont pu être développés pour leur fonctionnalisation.

Use of cellular impedance to characterize ligand functional selectivity at G protein-coupled receptors

Les récepteurs couplés aux protéines G (RCPGs) représentent la plus grande famille de cibles thérapeutiques pour le traitement d’une panoplie de pathologies humaines. Bien que plusieurs décennies de recherche aient permis de façonner nos connaissances sur ces protéines membranaires, notre compréhension des déterminants moléculaires de leur activité signalétique reste encore limitée. De ces domaines de recherche, une avancée récente a mis à jour un nouveau phénomène, appelé sélectivité fonctionnelle des ligands, qui a bouleversé les paradigmes décrivant leu fonctionnement de ces récepteurs. Ce concept émane d’observations montrant que l’activité pharmacologique de certains ligands n’est pas nécessairement conservée sur tout le répertoire signalétiques connu du récepteur et peu se restreindre à l'activation sélective d’un sous-groupe de voies de signalisation.Ce nouveau modèle pharmacologique de l'activation des RCPG ouvre de nouvelles possibilités pour la découverte de médicaments plus efficace et sûr, ciblant les RCPGs. En effet, il permet la conception de molécules modulant spécifiquement les voies signalétiques d’intérêt thérapeutique, sans engager les autres voies qui pourraient mener à des effets secondaires indésirables ou de la tolérance. Cette thèse décrit l'utilisation d'une nouvelle approche sans marquage, basée sur la mesure du changement l'impédance cellulaire. Par la mesure des changements cellulaires, comme la morphologie, l’adhésion et/ou la redistribution des macromolécules, cette approche permet de mesurer de façon simultanée l'activité de plusieurs voies de signalisation impliqués dans ces réponses. Utilisant le récepteur β2-adrénergique (β2AR) comme modèle, nous avons démontré que les variations dans l’impédance cellulaire étaient directement liées à l’activation de multiples voies de signalisation suite à la stimulation du récepteur par son ligand. L’agoniste type du β2AR, l’isoprotérénol, s’est avéré induire une réponse d’impédance dose-dépendante constituée, dans le temps, de plusieurs caractéristiques distinctes pouvant être bloquées de façon compétitive par l’antagoniste ICI118,551 Par l’utilisation d’inhibiteurs sélectifs, nous avons été en mesure de déterminer la contribution de plusieurs voies signalétiques canoniques, comme les voies dépendantes de Gs et Gi, la production d’AMPc et l’activation de ERK1/2, sur ces changements. De plus, la dissection de la réponse d’impédance a permis d’identifier une nouvelle voie de mobilisation du Ca2+ contribuant à la réponse globale des changements initiés par la stimulation du β2AR. Dans une autre étude, nous avons rapporté que la réponse calcique induite par le β2AR serait attribuable à une transactivation Gs-dépendant du récepteur purinergique P2Y11, lui-même couplé à la protéine Gq. La mesure d’impédance permettant de distinguer et de décrire une pléiade d’activités signalétiques, nous avons émis l’hypothèse que des ligands arborant des profils signalétiques différents généreraient des réponses d’impédance distinctes. Le criblage d’une librairie de ligands spécifiques au β2AR a révélé une grande variété de signatures d’impédance. Grâce au développement d’une approche computationnelle innovatrice, nous avons été en mesure de regrouper ces signatures en cinq classes de composés, un regroupement qui s’est avéré hautement corrélé avec le profil signalétique des différents ligands. Nous avons ensuite combiné le criblage de composés par impédance avec l’utilisation d’inhibiteurs sélectifs de voies signalétiques afin d’augmenter la résolution du regroupement. En évaluant l’impact d’une voie signalétique donnée sur la signature d’impédance, nous avons été en mesure de révéler une plus grande variété de textures parmi les ligands. De plus, cette méthode s’est avérée efficace pour prédire le profil signalétique d’une librairie de composés non caractérisés, ciblant le β2AR. Ces travaux ont mené à l’élaboration d’une méthode permettant d’exprimer visuellement la sélectivité fonctionnelle de ligands et ont révélé de nouvelles classes de composés pour ce récepteur. Ces nouvelles classes de composés ont ensuite été testées sur des cardiomyocytes humains, confirmant que les composés regroupés dans différentes classes produisent des effets distincts sur la contractilité de ces cellules. Globalement, ces travaux démontrent la pertinence de l’utilisation de l’impédance cellulaire pour une évaluation précise des différences fonctionnelles parmi les composés ciblant les RCPGs. En fournissant une représentation pluridimensionnelle de la signalisation émanant des RCPGs à l’aide d’un seul essai ne requérant pas de marquage, les signatures d’impédance représentent une stratégie simple et innovante pour l’évaluation de la fonctionnalité sélective des ligands. Cette méthode pourrait être d’une grande utilité dans le processus de découverte de nouveaux médicaments.

Design, synthèse et application en catalyse verte d’un ligand alkyl imidazolium β-cyclodextrine

Le 21e siècle est le berceau d’une conscientisation grandissante sur les impacts environnementaux des processus utilisés pour synthétiser des molécules cibles. Parmi les avancées qui ont marqué ces dernières décennies, il est également question de réduction de déchets, de conservation de l’énergie et de durabilité des innovations. Ces aspects constituent les lignes directrices de la chimie verte. De ce fait, il est impératif de développer des stratégies de synthèse dont les impacts environnementaux sont bénins. Dans ce mémoire nous présentons la synthèse, la caractérisation et l’étude des propriétés catalytiques en milieu aqueux d’un ligand composé d’une unité -cyclodextrine native, d’une unité imidazolium et d’une chaine alkyle à 12 carbones. Ce ligand hybride s’auto-assemble dans l’eau sous forme de micelles, permettant ainsi d’effectuer en sa présence des couplages de Suzuki-Miyaura dans l’eau, avec de bons rendements. La fonctionnalisation de la face primaire de la -cyclodextrine par un noyau alkyl-imidazolium, précurseur de ligand de type carbène N-hétérocyclique, a permis le développement d’un système catalytique vert et hautement recyclable. Dans un deuxième temps, nous présentons l’utilisation du même ligand hybride dans des couplages de Heck dans l’eau, démontrant ainsi la versatilité du ligand.

Propagation of Microwaves in the Troposphere with Potential Application to GPS based Navigation and Meteorology with emphasis on Indian region

Global Positioning System (GPS), with its high integrity, continuous availability and reliability, revolutionized the navigation system based on radio ranging. With four or more GPS satellites in view, a GPS receiver can find its location anywhere over the globe with accuracy of few meters. High accuracy - within centimeters, or even millimeters is achievable by correcting the GPS signal with external augmentation system. The use of satellite for critical application like navigation has become a reality through the development of these augmentation systems (like W AAS, SDCM, and EGNOS, etc.) with a primary objective of providing essential integrity information needed for navigation service in their respective regions. Apart from these, many countries have initiated developing space-based regional augmentation systems like GAGAN and IRNSS of India, MSAS and QZSS of Japan, COMPASS of China, etc. In future, these regional systems will operate simultaneously and emerge as a Global Navigation Satellite System or GNSS to support a broad range of activities in the global navigation sector.Among different types of error sources in the GPS precise positioning, the propagation delay due to the atmospheric refraction is a limiting factor on the achievable accuracy using this system. The WADGPS, aimed for accurate positioning over a large area though broadcasts different errors involved in GPS ranging including ionosphere and troposphere errors, due to the large temporal and spatial variations in different atmospheric parameters especially in lower atmosphere (troposphere), the use of these broadcasted tropospheric corrections are not sufficiently accurate. This necessitated the estimation of tropospheric error based on realistic values of tropospheric refractivity. Presently available methodologies for the estimation of tropospheric delay are mostly based on the atmospheric data and GPS measurements from the mid-latitude regions, where the atmospheric conditions are significantly different from that over the tropics. No such attempts were made over the tropics. In a practical approach when the measured atmospheric parameters are not available analytical models evolved using data from mid-latitudes for this purpose alone can be used. The major drawback of these existing models is that it neglects the seasonal variation of the atmospheric parameters at stations near the equator. At tropics the model underestimates the delay in quite a few occasions. In this context, the present study is afirst and major step towards the development of models for tropospheric delay over the Indian region which is a prime requisite for future space based navigation program (GAGAN and IRNSS). Apart from the models based on the measured surface parameters, a region specific model which does not require any measured atmospheric parameter as input, but depends on latitude and day of the year was developed for the tropical region with emphasis on Indian sector.Large variability of atmospheric water vapor content in short spatial and/or temporal scales makes its measurement rather involved and expensive. A local network of GPS receivers is an effective tool for water vapor remote sensing over the land. This recently developed technique proves to be an effective tool for measuring PW. The potential of using GPS to estimate water vapor in the atmosphere at all-weather condition and with high temporal resolution is attempted. This will be useful for retrieving columnar water vapor from ground based GPS data. A good network of GPS could be a major source of water vapor information for Numerical Weather Prediction models and could act as surrogate to the data gap in microwave remote sensing for water vapor over land.

Analysis of System Signals Based on Cross Recurrence Method for System Dynamics Characterization

Natural systems are inherently non linear. Recurrent behaviours are typical of natural systems. Recurrence is a fundamental property of non linear dynamical systems which can be exploited to characterize the system behaviour effectively. Cross recurrence based analysis of sensor signals from non linear dynamical system is presented in this thesis. The mutual dependency among relatively independent components of a system is referred as coupling. The analysis is done for a mechanically coupled system specifically designed for conducting experiment. Further, cross recurrence method is extended to the actual machining process in a lathe to characterize the chatter during turning. The result is verified by permutation entropy method. Conventional linear methods or models are incapable of capturing the critical and strange behaviours associated with the dynamical process. Hence any effective feature extraction methodologies should invariably gather information thorough nonlinear time series analysis. The sensor signals from the dynamical system normally contain noise and non stationarity. In an effort to get over these two issues to the maximum possible extent, this work adopts the cross recurrence quantification analysis (CRQA) methodology since it is found to be robust against noise and stationarity in the signals. The study reveals that the CRQA is capable of characterizing even weak coupling among system signals. It also divulges the dependence of certain CRQA variables like percent determinism, percent recurrence and entropy to chatter unambiguously. The surrogate data test shows that the results obtained by CRQA are the true properties of the temporal evolution of the dynamics and contain a degree of deterministic structure. The results are verified using permutation entropy (PE) to detect the onset of chatter from the time series. The present study ascertains that this CRP based methodology is capable of recognizing the transition from regular cutting to the chatter cutting irrespective of the machining parameters or work piece material. The results establish this methodology to be feasible for detection of chatter in metal cutting operation in a lathe.

Crystal Structures and Spectral Investigation of Aroylhydrazones and their Mixed Ligand Metal Chelates

Supra molecular architectures of coordination complexes of liydrazones through non covalent interactions have been explored. Molecular self—assernbly driven by weak interactions such as hydrogen— bonding, K '”T[, C-1-I‘ "TE, van der Waals interactions, and so forth are currently of tremendous research interest in the fields of molecule based materials. The directional properties of the hydrogembonding interaction associate discrete molecules into aggregate structures that are sufficiently stable to be considered as independent chemical species. Chemistry can borrow nature’s strategy to utilize hydrogen-bonding as Well as other noncovalent interactions as found in secondary and tertiary structures of proteins such as the double helix folding of DNA, hydrophobic selflorganization of phospholipids in cell membrane etc. In supramolecular chemistry hydrogen bonding plays an important role in forming a variety of architectures. Thus, the wise modulation and tuning of the complementary sites responsible for hydrogen—bond formation have led to its application in supramolecular electronics, host-guest chemistry, self-assembly of molecular capsules, nanotubes etc. The work presented in this thesis describes the synthesis and characterization of metal complexes derived from some substituted aroylhydrazones. The thesis is divided into seven chapters.

Master Plan for Renewable Energy based Electricity Generation in The Gambia

The principal objective of this paper is to develop a methodology for the formulation of a master plan for renewable energy based electricity generation in The Gambia, Africa. Such a master plan aims to develop and promote renewable sources of energy as an alternative to conventional forms of energy for generating electricity in the country. A tailor-made methodology for the preparation of a 20-year renewable energy master plan focussed on electricity generation is proposed in order to be followed and verified throughout the present dissertation, as it is applied for The Gambia. The main input data for the proposed master plan are (i) energy demand analysis and forecast over 20 years and (ii) resource assessment for different renewable energy alternatives including their related power supply options. The energy demand forecast is based on a mix between Top-Down and Bottom-Up methodologies. The results are important data for future requirements of (primary) energy sources. The electricity forecast is separated in projections at sent-out level and at end-user level. On the supply side, Solar, Wind and Biomass, as sources of energy, are investigated in terms of technical potential and economic benefits for The Gambia. Other criteria i.e. environmental and social are not considered in the evaluation. Diverse supply options are proposed and technically designed based on the assessed renewable energy potential. This process includes the evaluation of the different available conversion technologies and finalizes with the dimensioning of power supply solutions, taking into consideration technologies which are applicable and appropriate under the special conditions of The Gambia. The balance of these two input data (demand and supply) gives a quantitative indication of the substitution potential of renewable energy generation alternatives in primarily fossil-fuel-based electricity generation systems, as well as fuel savings due to the deployment of renewable resources. Afterwards, the identified renewable energy supply options are ranked according to the outcomes of an economic analysis. Based on this ranking, and other considerations, a 20-year investment plan, broken down into five-year investment periods, is prepared and consists of individual renewable energy projects for electricity generation. These projects included basically on-grid renewable energy applications. Finally, a priority project from the master plan portfolio is selected for further deeper analysis. Since solar PV is the most relevant proposed technology, a PV power plant integrated to the fossil-fuel powered main electrical system in The Gambia is considered as priority project. This project is analysed by economic competitiveness under the current conditions in addition to sensitivity analysis with regard to oil and new-technology market conditions in the future.

Ferrocene-Based Pyridylphosphine Ligands – Coordination Chemistry of Group 10, 11 and 12 Metals

English: The present thesis describes the synthesis of 1,1’-ferrocendiyl-based pyridylphosphine ligands, the exploration of their fundamental coordination chemistry and preliminary experiments with selected complexes aimed at potential applications. One main aspect is the synthesis of the bidentate ferrocene-based pyridylphosphine ligands 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene, 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene and 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. A specific feature of these ligands is the ball-bearing like flexibility of the ferrocenebased backbone. An additional flexibility element is the rotation around the C–C single bonds. Consequently, the donor atoms can realise a wide range of positions with respect to each other and are therefore able to adapt to the coordination requirements of different metal centres. The flexibility of the ligand also plays a role in another key aspect of this work, which concerns the coordination mode, i. e. bridging vs. chelating. In addition to the flexibility, also the position of the donor atoms to each other is important. This is largely affected by the position of the pyridyl nitrogen (pyrid-2-yl vs. pyrid-3-yl) and the methylen group in 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. Another interesting point is the combination of a soft phosphorus donor atom with a harder nitrogen donor atom, according to the HSAB principle. This combination generates a unique binding profile, since the pi-acceptor character of the P site is able to stabilise a metal centre in a low oxidation state, while the nitrogen sigma-donor ability can make the metal more susceptible to oxidative addition reactions. A P,N-donor combination can afford hemilabile binding profiles, which would be ideal for catalysis. Beyond 1,2-substituted ferrocene derivatives, which are quite successful in catalytic applications, 1,1’-derivatives are rather underrepresented. While a low-yield synthetic pathway to 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene was already described in the literature [I. R. Butler, Organometallics 1992, 11, 74.], it was possible to find a new, improved and simplified synthetic pathway. Both other ligands were unknown prior to this work. Satisfactory results in the synthesis of 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene could be achieved by working in analogy to the new synthetic procedure for 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene. The synthesis of 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene has been handled by the group of Prof. Petr Stepnicka from Charles University, Prague, Czech Republic. The synthesis of tridentate ligands with an analogous heterodentate arrangement, was investigated briefly as a sideline of this study. The major part of this thesis deals with the fundamental coordination chemistry towards transition metals of the groups 10, 11 and 12. Due to the well-established catalytic properties of analogous palladium complexes, the coordination chemistry towards palladium (group 10) is of particular interest. The metals zinc and cadmium (group 12) are also of substantial importance because they are redox-inert in their divalent state. This is relevant in view of electrochemical investigations concerning the utilisation of the ligands as molecular redox sensors. Also mercury and the monovalent metals silver and gold (group 11) are included because of their rich coordination chemistry. It is essential to answer questions concerning aspects of the ligands’ coordination mode bearing in mind the HSAB principle.

Adaptive Real-time Anomaly-based Intrusion Detection using Data Mining and Machine Learning Techniques

Die zunehmende Vernetzung der Informations- und Kommunikationssysteme führt zu einer weiteren Erhöhung der Komplexität und damit auch zu einer weiteren Zunahme von Sicherheitslücken. Klassische Schutzmechanismen wie Firewall-Systeme und Anti-Malware-Lösungen bieten schon lange keinen Schutz mehr vor Eindringversuchen in IT-Infrastrukturen. Als ein sehr wirkungsvolles Instrument zum Schutz gegenüber Cyber-Attacken haben sich hierbei die Intrusion Detection Systeme (IDS) etabliert. Solche Systeme sammeln und analysieren Informationen von Netzwerkkomponenten und Rechnern, um ungewöhnliches Verhalten und Sicherheitsverletzungen automatisiert festzustellen. Während signatur-basierte Ansätze nur bereits bekannte Angriffsmuster detektieren können, sind anomalie-basierte IDS auch in der Lage, neue bisher unbekannte Angriffe (Zero-Day-Attacks) frühzeitig zu erkennen. Das Kernproblem von Intrusion Detection Systeme besteht jedoch in der optimalen Verarbeitung der gewaltigen Netzdaten und der Entwicklung eines in Echtzeit arbeitenden adaptiven Erkennungsmodells. Um diese Herausforderungen lösen zu können, stellt diese Dissertation ein Framework bereit, das aus zwei Hauptteilen besteht. Der erste Teil, OptiFilter genannt, verwendet ein dynamisches "Queuing Concept", um die zahlreich anfallenden Netzdaten weiter zu verarbeiten, baut fortlaufend Netzverbindungen auf, und exportiert strukturierte Input-Daten für das IDS. Den zweiten Teil stellt ein adaptiver Klassifikator dar, der ein Klassifikator-Modell basierend auf "Enhanced Growing Hierarchical Self Organizing Map" (EGHSOM), ein Modell für Netzwerk Normalzustand (NNB) und ein "Update Model" umfasst. In dem OptiFilter werden Tcpdump und SNMP traps benutzt, um die Netzwerkpakete und Hostereignisse fortlaufend zu aggregieren. Diese aggregierten Netzwerkpackete und Hostereignisse werden weiter analysiert und in Verbindungsvektoren umgewandelt. Zur Verbesserung der Erkennungsrate des adaptiven Klassifikators wird das künstliche neuronale Netz GHSOM intensiv untersucht und wesentlich weiterentwickelt. In dieser Dissertation werden unterschiedliche Ansätze vorgeschlagen und diskutiert. So wird eine classification-confidence margin threshold definiert, um die unbekannten bösartigen Verbindungen aufzudecken, die Stabilität der Wachstumstopologie durch neuartige Ansätze für die Initialisierung der Gewichtvektoren und durch die Stärkung der Winner Neuronen erhöht, und ein selbst-adaptives Verfahren eingeführt, um das Modell ständig aktualisieren zu können. Darüber hinaus besteht die Hauptaufgabe des NNB-Modells in der weiteren Untersuchung der erkannten unbekannten Verbindungen von der EGHSOM und der Überprüfung, ob sie normal sind. Jedoch, ändern sich die Netzverkehrsdaten wegen des Concept drif Phänomens ständig, was in Echtzeit zur Erzeugung nicht stationärer Netzdaten führt. Dieses Phänomen wird von dem Update-Modell besser kontrolliert. Das EGHSOM-Modell kann die neuen Anomalien effektiv erkennen und das NNB-Model passt die Änderungen in Netzdaten optimal an. Bei den experimentellen Untersuchungen hat das Framework erfolgversprechende Ergebnisse gezeigt. Im ersten Experiment wurde das Framework in Offline-Betriebsmodus evaluiert. Der OptiFilter wurde mit offline-, synthetischen- und realistischen Daten ausgewertet. Der adaptive Klassifikator wurde mit dem 10-Fold Cross Validation Verfahren evaluiert, um dessen Genauigkeit abzuschätzen. Im zweiten Experiment wurde das Framework auf einer 1 bis 10 GB Netzwerkstrecke installiert und im Online-Betriebsmodus in Echtzeit ausgewertet. Der OptiFilter hat erfolgreich die gewaltige Menge von Netzdaten in die strukturierten Verbindungsvektoren umgewandelt und der adaptive Klassifikator hat sie präzise klassifiziert. Die Vergleichsstudie zwischen dem entwickelten Framework und anderen bekannten IDS-Ansätzen zeigt, dass der vorgeschlagene IDSFramework alle anderen Ansätze übertrifft. Dies lässt sich auf folgende Kernpunkte zurückführen: Bearbeitung der gesammelten Netzdaten, Erreichung der besten Performanz (wie die Gesamtgenauigkeit), Detektieren unbekannter Verbindungen und Entwicklung des in Echtzeit arbeitenden Erkennungsmodells von Eindringversuchen.

An alternative method for dating unknown tephras based on a segmented regression model

In CoDaWork’05, we presented an application of discriminant function analysis (DFA) to 4 different compositional datasets and modelled the first canonical variable using a segmented regression model solely based on an observation about the scatter plots. In this paper, multiple linear regressions are applied to different datasets to confirm the validity of our proposed model. In addition to dating the unknown tephras by calibration as discussed previously, another method of mapping the unknown tephras into samples of the reference set or missing samples in between consecutive reference samples is proposed. The application of these methodologies is demonstrated with both simulated and real datasets. This new proposed methodology provides an alternative, more acceptable approach for geologists as their focus is on mapping the unknown tephra with relevant eruptive events rather than estimating the age of unknown tephra. Kew words: Tephrochronology; Segmented regression

A geometric algorithm for an artificial life form based on anachronistic methods

Modern methods of spawning new technological motifs are not appropriate when it is desired to realize artificial life as an actual real world entity unto itself (Pattee 1995; Brooks 2006; Chalmers 1995). Many fundamental aspects of such a machine are absent in common methods, which generally lack methodologies of construction. In this paper we mix classical and modern studies in order to attempt to realize an artificial life form from first principles. A model of an algorithm is introduced, its methodology of construction is presented, and the fundamental source from which it sprang is discussed.

Alternative methodologies - stretching the in vitro box

Current gas-based in vitro evaluation systems are extremely powerful research techniques. However they have the potential to generate a great deal more than simple fermentation dynamics. Details from four experiments are presented in which adaptation, and novel application, of an in vitro system allowed widely differing objectives to be examined. In the first two studies, complement methodologies were utilised. In such assays, an activity or outcome is inferred through the occurrence of a secondary event rather than by direct observation. Using an N-deficient incubation medium, the increase in starch fermentation, when supplemented with individual amino acids (i.e., known level of N) relative to that of urea (i.e., known quantity and N availability), provided an estimate of their microbial utilisation. Due to the low level of response observed with some arnino acids (notably methionine and lysine), it was concluded, that they may not need to be offered in a rumen-inert form to escape rumen microbial degradation. In another experiment, the extent to which degradation of plant cell wall components was inhibited by lipid supplementation was evaluated using fermentation gas release profiles of washed hay. The different responses due to lipid source and level of inclusion suggested that the degree of rumen protection required to ameliorate this depression was supplement dependent. That in vitro inocula differ in their microbial composition is of little interest per se, as long as the outcome is the same (i.e., that similar substrates are degraded at comparable rates and end-product release is equivalent). However where a microbial population is deficient in a particular activity, increasing the level of inoculation will have no benefit. Estimates of hydrolytic activity were obtained by examining fermentation kinetics of specific substrates. A number of studies identified a fundamental difference between rumen fluid and faecal inocula, with the latter having a lower fibrolytic activity, which could not be completely attributed to microbial numbers. The majority of forage maize is offered as an ensiled feed, however most of the information on which decisions such as choice of variety, crop management and harvesting date are made is based on fresh crop measurements. As such, an attempt was made to estimate ensiled maize quality from an in vitro analysis of the fresh crop. Fermentation profiles and chemical analysis confirmed changes in crop composition over the growing season, and loss of labile carbohydrates during ensiling. In addition, examination of degradation residues allowed metabolizable energy (ME) contents to be estimated. Due to difficulties associated with starch analysis, the observation that this parameter could be predicted by difference (together with an assumed degradability), allowed an estimate of ensiled maize ME to be developed from fresh material. In addition, the contribution of the main carbohydrates towards ME showed the importance of delaying harvest until maximum starch content has been achieved. (c) 2005 Elsevier B.V. All rights reserved.

Transition metal-directed self-assembly of calix[4]arene based dithiocarbamate ligands

The transition metal-directed self-assembly of dithiocarbamate ligand functionalised upper and lower rim calix[4]arenes affords novel dimeric bimetallic bis(calix[4]arene) species as determined by a combination of analytical methods including X-ray crystallography. An exception is a zinc(II) dithiocarbamate upper rim calix[4]arene assembly which is monomeric in nature. Electrochemical investigations reveal the bimetallic copper(II) bis(calix[4]arene) systems can electrochemically sense dihydrogen phosphate and carboxylate anions via significant cathodic perturbations of the respective copper(II)/(III) dithiocarbamate oxidation wave.