Equilibrium studies of 2,2'-(5-bromo-6-methylpyrimidine-2,4-diyl)bis(azanediyl)dipropanoic acid with some transition-metal ions in aqueous solution

The stability constants of the 1:1 complexes formed between M2+ (M2+: Mn2+, Ni2+, Cu2+, or Cd2+) and BMADA2- (BMADA: 2,2'-(5-bromo-6-methylpyrimidine-2,4 diyl)bis(azanediyl)dipropanoic acid) were determined by potentiometric pH titration in aqueous solution (I = 0.1 mol L-1, NaNO3, 25 °C). The stability of the binary M - BMADA complexes is determined by the basicity of the carboxyl or amino groups. All the stability constants reported in this work exhibit the usual trend, and the order obtained was Mn2+< Ni2+ < Cu2+ > Cd2+. The observed stability order for BMADA approximately follows the Irving - Williams sequence. In the M - BMADA complexes, the M ion is able to form a macrochelate via the pyrimidine group of BMADA.

Synthesis, characterization and thermal studies on solid 3-methoxybenzoate of some bivalent transition metal ions

Solid-state M-3-MeO-Bz compounds, where M stands for bivalent Mn, Co, Ni, Cu and Zn and 3-MeO-Bz is 3-methoxybenzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy, and chemical analysis were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated compounds.

Synthesis, characterization and thermal behaviour of solid-state compounds of 2-methoxybenzoate with some bivalent transition metal ions

Solid-state M-2-MeO-Bz compounds, where M stands for bivalent Mn, Co, Ni, Cu and Zn and 2-MeO-Bz is 2-methoxybenzoate, have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), thermogravimetry, derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to have information about the composition, dehydration, thermal stability and thermal decomposition of the isolated compounds.

Electrochemical study and dependence of 'transition state' in Co(II) and Ni(II) complexes with some antibiotics and cephalothin

Electrode kinetics and study of 'transition state' with applied potential in case of [M - antibiotics - cephalothin] system were reported at pH = 7.30 ± 0.01 at suitable supporting electrolyte at 25.0ºC. The M = Co or Ni and antibiotics were doxycycline, chlortetracycline, oxytetracycline, tetracycline, minocycline, amoxicillin and chloramphenicol used as primary ligands and cephalothin as secondary ligand. Kinetic parameters viz. transfer coefficient (a), degree of irreversibility (l), diffusion coefficient (D) and rate constant (k) were determined. The values of a and k varied from 0.41 to 0.59 and 2.60 X 10-3 cm s-1 to 9.67 X 10-3 cm s-1 in case of [Co - antibiotics - cephalothin] system. In case of [Ni - antibiotics - cephalothin], a and k varied from 0.41 to 0.58 and 2.34 X 10-3 cm s-1 to 9.19 X 10-3 cm s-1 respectively confirmed that transition state behaves between oxidant and reductant response to applied potential and it adjusts it self in such a way that the same is located midway between dropping mercury electrode and solution interface. The values of rate constant confirmed the quasireversible nature of electrode processes. The stability constants (logb) of complexes were also determined.

Innovations of ageing and societal transition : Dynamics of change of the socio-technical regime of ageing

The purpose of this dissertation is to examine the dynamics of the socio-technical system in the field of ageing. The study stems from the notion that the ageing of the population as a powerful megatrend has wide societal effects, and is not just a matter for the social and health sector. The central topic in the study is change: not only the age structures and structures of society are changing, but also at the same time there is constant development, for instance, in technologies, infrastructures and cultural perceptions. The changing concept of innovation has widened the understanding of innovations related to ageing from medical and assistive technological innovations to service and social innovations, as well as systemic innovations at different levels, which means the intertwined and co-evolutionary change in technologies, structures, services and thinking models. By the same token, the perceptions of older people and old age are becoming more multi-faceted: old age is no longer equated to illnesses and decline, but visions of active ageing and a third age have emerged, which are framed by choices, opportunities, resources and consumption in later life. The research task in this study is to open up the processes and mechanisms of change in the field of ageing, which are studied as a complex, multi-level and interrelated socio-technical system. The question is about co-effective elements consisting of macro-level landscape changes, the existing socio-technical regime (the rule system, practices and structures) and bottom-up niche-innovations. Societal transitions do not account for the things inside the regime alone, or for the long-term changes in the landscape, nor for the radical innovations, but for the interplay between all these levels. The research problem is studied through five research articles, which offer micro-level case studies to macro-level phenomenon. Each of the articles focus on different aspects related to ageing and change, and utilise various datasets. The framework of this study leans on the studies of socio-technical systems and multi-level perspective on transitions mainly developed by Frank Geels. Essential factors in transition from one socio-technological regime to another are the co-evolutionary processes between landscape changes, regime level and experimental niches. Landscape level changes, like the ageing of the population, destabilise the regime in the forms of coming pressures. This destabilization offers windows for opportunity to niche-innovations outside or at fringe of the regime, which, through their breakthrough, accelerate the transition process. However, the change is not easy because of various kinds of lock-ins and inertia, which tend to maintain the stability of the regime. In this dissertation, a constructionist approach of society is applied leaning mainly to the ideas of Anthony Giddens’ theory of structuration, with the dual nature of structures. The change is taking place in the interplay between actors and structures: structures shape people’s practices, but at the same time these practices constitute and reproduce social systems. Technology and other material aspects, as part of socio-technical systems, and the use of them, also take part in the structuration process. The findings of the study point out that co-evolutionary and co-effective relationships between economic, cultural, technological and institutional fields, as well as relationships between landscape changes, changes in the local and regime-level practices and rule systems, are a very complex and multi-level dynamic socio-technical phenomenon. At the landscape level of ageing, which creates the pressures and triggers to the regime change, there are three remarkable megatrends: demographic change, changes in the global economy and the development of technologies. These exert pressures to the socio-technical regime, which as a rule system is experiencing changes in the form of new markets and consumer habits, new ways of perceiving ageing, new models of organising the health care and other services and as new ways of considering innovation and innovativeness. There are also inner dynamics in the relationships between these aspects within the regime. These are interrelated and coconstructed: the prevailing perceptions of ageing and innovation, for instance, reflect the ageing policies, innovation policies, societal structures, organising models, technology and scientific discussion, and vice versa. Technology is part of the inner dynamics of the sociotechnological regime. Physical properties of the artefacts set limitations and opportunities with regard to their functions and uses. The use of and discussion about technology, contributes producing and reproducing the perceptions of old age. For societal transition, micro-level changes are also needed, in form of niche-innovations, for instance new services, organisational models or new technologies, Regimes, as stabilitystriven systems, tend to generate incremental innovations, but radically new innovations are generated in experimental niches protected from ‘normal’ market selection. The windows of opportunity for radical novelties may be opened if the circumstances are favourable for instance by tensions in the socio-technical regime affected by landscape level changes. This dissertation indicates that a change is taking place, firstly, in the dynamic interactionbetween levels, as a result of purposive action and governance to some extent. Breaking the inertia and using the window of opportunity for change and innovation offered by dynamics between levels, presupposes the actors’ special capabilities and actions such as dynamic capabilities and distance management. Secondly, the change is taking place the socio-technological negotiations inside the regime: interaction between technological and social, which is embodied in the use of technology. The use of technology includes small-level contextual scripts that also participate in forming broader societal scripts (for instance defining old age at the society level), which in their turn affect the formation of policies for innovation and ageing. Thirdly, the change is taking place by the means of active formation of the multi-actor innovation networks, where the role of distance management is crucial to facilitate the communication between actors coming from different backgrounds as well as to help the niches born outside the regime to utilise the window of opportunity offered by regime destabilisation. This dissertation has both theoretical and practical contributions. This study participates in the discussion of action-oriented view on transition by opening up of the socio-technological, coevolutionary processes of the multi-faceted phenomenon of ageing, which has lacked systematic analyses. The focus of this study, however, is not on the large-scale coordination and governance, but rather on opening up the incremental elements and structuration processes, which contribute to the transition little by little, and which can be affected to. This increases the practical importance of this dissertation, by highlighting the importance of very tiny, everyday elements in the change processes in the long run.

Mapping financial stability

The ongoing global financial crisis has demonstrated the importance of a systemwide, or macroprudential, approach to safeguarding financial stability. An essential part of macroprudential oversight concerns the tasks of early identification and assessment of risks and vulnerabilities that eventually may lead to a systemic financial crisis. Thriving tools are crucial as they allow early policy actions to decrease or prevent further build-up of risks or to otherwise enhance the shock absorption capacity of the financial system. In the literature, three types of systemic risk can be identified: i ) build-up of widespread imbalances, ii ) exogenous aggregate shocks, and iii ) contagion. Accordingly, the systemic risks are matched by three categories of analytical methods for decision support: i ) early-warning, ii ) macro stress-testing, and iii ) contagion models. Stimulated by the prolonged global financial crisis, today's toolbox of analytical methods includes a wide range of innovative solutions to the two tasks of risk identification and risk assessment. Yet, the literature lacks a focus on the task of risk communication. This thesis discusses macroprudential oversight from the viewpoint of all three tasks: Within analytical tools for risk identification and risk assessment, the focus concerns a tight integration of means for risk communication. Data and dimension reduction methods, and their combinations, hold promise for representing multivariate data structures in easily understandable formats. The overall task of this thesis is to represent high-dimensional data concerning financial entities on lowdimensional displays. The low-dimensional representations have two subtasks: i ) to function as a display for individual data concerning entities and their time series, and ii ) to use the display as a basis to which additional information can be linked. The final nuance of the task is, however, set by the needs of the domain, data and methods. The following ve questions comprise subsequent steps addressed in the process of this thesis: 1. What are the needs for macroprudential oversight? 2. What form do macroprudential data take? 3. Which data and dimension reduction methods hold most promise for the task? 4. How should the methods be extended and enhanced for the task? 5. How should the methods and their extensions be applied to the task? Based upon the Self-Organizing Map (SOM), this thesis not only creates the Self-Organizing Financial Stability Map (SOFSM), but also lays out a general framework for mapping the state of financial stability. This thesis also introduces three extensions to the standard SOM for enhancing the visualization and extraction of information: i ) fuzzifications, ii ) transition probabilities, and iii ) network analysis. Thus, the SOFSM functions as a display for risk identification, on top of which risk assessments can be illustrated. In addition, this thesis puts forward the Self-Organizing Time Map (SOTM) to provide means for visual dynamic clustering, which in the context of macroprudential oversight concerns the identification of cross-sectional changes in risks and vulnerabilities over time. Rather than automated analysis, the aim of visual means for identifying and assessing risks is to support disciplined and structured judgmental analysis based upon policymakers' experience and domain intelligence, as well as external risk communication.

Investigating the role of apoptosis regulator EndoG on exogenous DNA uptake, stability, replication and recombination

Endonuclease G (EndoG) is a well conserved mitochondrial nuclease with dual lethal and vital roles in the cell. It non-specifically cleaves endogenous DNA following apoptosis induction, but is also active in non-apoptotic cells for mitochondrial DNA (mtDNA) replication and may also be important for replication, repair and recombination of genomic DNA. The aim of our study was to examine whether EndoG exerts similar activities on exogenous DNA substrates such as plasmid DNA (pDNA) and viral DNA vectors, considering their importance in gene therapy applications. The effects of EndoG knockdown on pDNA stability and levels of encoded reporter gene expression were evaluated in the cervical carcinoma HeLa cells. Transfection of pDNA vectors encoding short-hairpin RNAs (shRNAs) reduced levels of EndoG mRNA and nuclease activity in HeLa cells. In physiological circumstances, EndoG knockdown did not have an effect on the stability of pDNA or the levels of encoded transgene expression as measured over a four day time-course. However, when endogenous expression of EndoG was induced by an extrinsic stimulus (a cationic liposome transfection reagent), targeting of EndoG by shRNA improved the perceived stability and transgene expression of pDNA vectors. Therefore, EndoG is not a mediator of exogenous DNA clearance, but in non-physiological circumstances it may non-specifically cleave intracellular DNA regardless of its origin. To investigate possible effects of EndoG on viral DNA vectors, we constructed and evaluated AdsiEndoG, a first generation adenovirus (Ad5 ΔE1) vector encoding a shRNA directed against EndoG mRNA, along with appropriate Ad5 ΔE1 controls. Infection of HeLa cells with AdsiEndoG at a multiplicity of infection (MOI) of 10 p.f.u./cell resulted in an early cell proliferation defect, absent from cells infected at equivalent MOI with control Ad5 ΔE1 vectors. Replication of Ad5 ΔE1 DNA was detected for all vectors, but AdsiEndoG DNA accumulated to levels that were 50 fold higher than initially, four days after infection, compared to 14 fold for the next highest control Ad5 ΔE1 vector. Deregulation of the cell cycle by EndoG depletion, which is characterized by an accumulation of cells in the G2/M transition, is the most likely reason for the observed cell proliferation defect. The enhanced replication of AdsiEndoG is consistent with this conclusion, as Ad5 ΔE1 DNA replication is intimately related to cell cycling and prolongation or delay in G2/M greatly enhances this process. Furthermore, infection of HeLa with AdsiEndoG at MOI of 50 p.f.u./cell resulted in an almost complete disappearance of viable, adherent tumour cells from culture, whereas almost a third of the cells were still adherent after infection with control Ad5 ΔE1 vectors, relative to the non-infected control. Therefore, targeting of EndoG by RNAi is a viable strategy for improving the oncolytic properties of first generation adenovirus vectors. In addition, AdsiEndoG-mediated knockdown of EndoG reduced homologous recombination between pDNA substrates in HeLa cells. The effect was modest but, nevertheless demonstrated that the proposed role of EndoG in homologous recombination of cellular DNA also extends to exogenous DNA substrates.

Studies on Some Simple and Zeolite-Y Encapsulated 3d-Transition Metal Complexes of Schiff Bases Derived From 2-Aminobenzothiazole

In this regard Schiff base complexes have attracted wide attention. Furthermore, such complexes are found to play important role in analytical chemistry, organic synthesis, metallurgy, refining of metals, electroplating and photography. Many Schiff base complexes are reported in literature. Their properties depend on the nature of the metal ion as well as on the nature of the ligand. By altering the ligands it is possible to obtain desired electronic environment around the metal ion. Thus there is a continuing interest in the synthesis of simple and zeolite encapsulated Schiff base complexes of metal ions. Zeolites have a number of striking structural similarities to the protein portion of natural enzymes. Zeolite based catalysts are known for their remarkable ability of mimicking the chemistry of biological systems. In view of the importance of catalysts in all the areas of modern chemical industries, an effort has been made to synthesize some simple Schiff base complexes, heterogenize them by encapsulating within the supercages of zeoliteY cavities and to study their applications. The thesis deals with studies on the synthesis and characterization of some simple and zeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes and on the catalytic activity of these complexes on some oxidation reactions. Simple complexes were prepared from the Schiff base ligands SBT derived from 2-aminobenzothiazole and salicylaldehyde and the ligand VBT derived from 2-aminobenzothiazole and vanillin (4-hydroxy-3- methoxybenzaldehyde). ZeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes of Schiff base ligands SBT and VBT and also of 2-aminobenzothiazole were synthesized. All the prepared complexes were characterized using the physico-chemical techniques such as chemical analysis (employing AAS and CHN analyses), magnetic moment studies, conductance measurements and electronic and FTIR spectra. EPR spectra of the Cu(II) complexes were also carried out to know the probable structures and nature of Cu(II) complexes. Thermogravimetric analyses were carried out to obtain the information regarding the thermal stability of various complexes. The successful encapsulations of the complexes within the cavities of zeoliteY were ascertained by XRD, surface area and pore volume analysis. Assignments of geometries of simple and zeoliteY encapsulated complexes are given in all the cases. Both simple and zeoliteY encapsulated complexes were screened for catalytic activity towards oxidation reactions such as decomposition of hydrogen peroxide, oxidation of benzaldehyde, benzyl alcohol, 1-propanol, 2-propanol and cyclohexanol.

Studies on some supported transition metal complex and metal oxide catalysts for oxidation reactions

Zeolite encapsulated transition metal complexes have received wide attention as an effective heterogenized system that combines the tremendous activity of the metal complexes and the attractive features of the zeolite structure. Zeolite encapsulated complexes offer a bright future for attempts to replace homogeneous systems retaining its catalytic activity and minimizing the technical problems. especially for the partial oxidation of organic compounds. Studies on some zeolite encapsulated transition metal complexes are presented in this thesis. The ligands selected are technically important in a bio-mimetic or structural perspective. Attempts have been made in this study to investigate the composition, structure and stability of encapsulated complexes using available techniques. The catalytic activity of encapsulated complexes was evaluated for the oxidation of some organic compounds. The recycling ability of the catalyst as a result of the encapsulation was also studied.Our studies on Cu-Cr/Al2O3, a typical metal oxide catalyst. illustrate the use of design techniques to modify the properties of such conventional catalysts. The catalytic activity of this catalyst for the oxidation of carbon monoxide was measured. The effect of additives like Ce02 or Ti02 on the activity and stability of this system was also investigated. The additive is potent to improve the activity and stability ofthe catalyst so as to be more effective in commercial usage.

Transition metal complexes of quinoxaline based Schiff base ligands: Synthesis,characterization and catalytic activity study

Schiff base complexes of transition metal ions have played a significant role in coordination chemistry.The convenient route of synthesis and thermal stability of Schiff base complexes have contributed significantly for their possible applications in catalysis,biology,medicine and photonics.Significant variations in cataltytic activity with structure and type are observed for these complexes.The thesis deals with synthsis and characterization of transition metal complexes of quinoxaline based Schiff base ligands and their catalytic activity study.The Schiff bases synthesized in the present study are quinoxaline-2-carboxalidine-2-amino-5-methylphenol,3-hydroxyquinoxaline-2-carboxalidine-2-amino-5-methylphenol,quinoxaline-2-aminothiophenol.They provide great structural diversity during complexation.To the best of our knowledge, the transition metal complexes of quinoxaline based Schiff bases are poorly utilised in academic and industrial research.

Catalysis by Transition Metal Modified Ceria and Ceria-Zirconia Mixed Oxides Prepared via Sol-Gel Route

The aim of catalysis research is to apply the catalyst successfully in economically important reactions in an environmentally friendly way. The present work focuses on the modification of structural and surface properties of ceria and ceria-zirconia catalysts by the incorporation of transition metals. The applications of these catalysts in industrially important reactions like ethylbenzene oxidation, alkylation of aromatics are also investigated.Sol-gel method is effective for the preparation of transition metal modified ceria and ceria-zirconia mixed oxide since it produces catalyst with highly dispersed incorporated metal. Unlike that of impregnation method plugging of pores is not prominent for sol-gel derived catalyst materials. This prevents loss of surface area on metal modification as evident for BET surface area measurements.The powder X-ray diffraction analysis confirms the cubic structure of transition metal modified ceria and ceria-zirconia catalysts. The thermal stability is evident from TGA/DTA analysis. DR UV-vis spectra provide information on the coordination environment of the incorporated metal. EPR analysis ofCr, Mn and Cu modified ceria and a ceria-zirconia catalyst reveals the presence of different oxidation states of incorporated metal.Temperature programmed desorption of ammonia and thermogravimetric desorption of 2,6-dimethyl pyridine confirms the enhancement of acidity on metal incorporation. High a-methyl styrene selectivity in cumene cracking reaction implies the presence of comparatively more number of Lewis acid sites with some amount of Bronsted acid sites. The formation of cyclohexanone during cyclohexanol decomposition confirms the presence of basic sites on the catalyst surface.Mn and Cr modified catalysts show better activity towards ethylbenzene oxidation. A redox mechanism through oxometal pathway is suggested.All the catalysts were found to be active towards benzylation of toluene and a-xylene. The selectivity towards monoalkylated products remains almost 100%. The catalytic activity is correlated with the Lewis acidity of the prepared systems.The activity of the catalysts towards methylation of phenols depends on the strength acid sites as well as the redox properties of the catalysts. A strong dependence of methylation activity on the total acidity is illustrated.

On the stability of the bcc phase in Cu-Al-Mn shape memory alloys

Measurements of the entropy change at the martensitic transition of two composition-related sets of Cu-Al-Mn shape-memory alloys are reported. It is found that most of the entropy change has a vibrational origin, and depends only on the particular close-packed structure of the low-temperature phase. Using data from the literature for other Cu-based alloys, this result is shown to be general. In addition, it is shown that the martensitic structure changes from 18R to 2H when the ratio of conduction electrons per atom reaches the same value as the eutectoid point in the equilibrium phase diagram. This finding indicates that the structure of the metastable low-temperature phase is reminiscent of the equilibrium structure.

Innovation and Globalization Policy in Small Transition Countries ; Case study: Macedonia and Slovenia

Diese Arbeit befasst sich mit der Innovations- und Globalisierungspolitik in kleinen Transformationsländern am Beispiel Mazedoniens; diese wurde mit der Lage in Slowenien verglichen, einem Land von ungefähr gleicher Größe und mit gemeinsamer Vergangenheit als Teilrepublik der Jugoslawischen Föderation, aber mit einem wesentlich höheren ökonomischen Entwicklungsstand. Innovation wird dabei verstanden als „Herstellung, Anpassung und Ausnutzung von Neuerungen“, und sie wird durch das Umfeld, in dem sie stattfindet, beeinflusst. Anpassung und Ausnutzung sind gerade für kleine Transformationsländer von erheblicher Bedeutung, da ihre Fähigkeit zu Herstellung von Neuerungen sehr begrenzt sind. Die Rolle der Innovationspolitik besteht hierbei darin, institutionelle und organisationelle Regulierungen einzuführen, die ein günstiges Umfeld sowohl für Innovationen als auch für die Entwicklung eines nationalen Innovationssystems schaffen. Die Rolle der Politik besteht also nicht in der Innovation als solcher, sondern in der Herstellung der notwendigen Bedingungen für die Industrie und die Forschungseinrichtungen dahingehend zu schaffen, dass sie ihr Wissen, ihre Fertigkeiten und ihre praktischen Erfahrungen für innovative Tätigkeiten einsetzen können. Auf der einen Seite gibt es Institutionen und Organisationen, ohne die die Unternehmen rückständig und wenig leistungsstark wären (etwa das Patentamt oder Institutionen höherer Bildung), und auf der anderen Seite gibt es Institutionen und Organisationen, welche die Unternehmen dabei unterstützen, dass sie ihre Tätigkeit weiter unterstützen (z.B. durch Technologietransfer-Zentren und Netzwerke). Die Leistungen dieser Institutionen und Organisationen sind von großer Bedeutung für die nationalen Innovationssysteme und sollten ihrerseits durch Innovationspolitik unterstützt werden; dies bedeutet jedoch nicht, dass diese Leistungen vom Staat bereitgestellt werden, vielmehr sollte die Wirtschaftspolitik Möglichkeiten für die öffentlich/private oder sogar rein private Bereitstellung solcher Leistungen in Erwägung ziehen; dies würde nicht nur die Kosten für den Staat senken, sondern auch die Effizienz bei der Erstellung dieser Leistungen steigern. Die Arbeit kommt zu dem Schluss, dass das größte Problem der Innovationspolitik in Mazedonien darin besteht, dass es sie gar nicht gibt, und zwar nicht als Folge einer bewussten Entscheidung darüber. Tatsächlich müssen Ressourcen und Zeit für die Schaffung eines nationalen Innovationssystems eingesetzt werden mit Hilfe einer Politik, die sich auf die wesentlichen Umrisse konzentriert, wobei die Nachfrage nach Technologie im Unternehmensbereich gesteigert wird und das Wissen und das Informationsangebot restrukturiert wird. Dieses System muss offen sein, unter beständigem Verbesserungsdruck stehen und fähig sein, sich an Veränderungen anzupassen. Damit eine solche Politik erfolgreich ist, muss es einen Konsens darüber zwischen allen beteiligten Akteuren geben und darüber hinaus auch eine Kohärenz zwischen den verschiedenen politischen Institutionen. Das ist deswegen wichtig, weil der Innovationsprozess komplex ist und verschiedene Politikbereiche berührt. Ziel sollte die Schaffung eines Systems sein, das einerseits auf Autonomie und Kooperation aufbaut, andererseits aber auch Wettbewerb zwischen den beteiligten Institutionen und Organisationen fördert. Eine wichtige Bedingung für ein positives Investitionsklima im Bereich der Innovation ist die Erreichung von makroökonomischer Stabilität. Die gegenwärtige Situation ist gekennzeichnet durch Instabilität des Rechtswesens, durch Korruption und Probleme des Vertragsschutzes, die sowohl ausländische als auch inländische Akteure davon abhält, sich in wirtschaftlichen Aktivitäten in Mazedonien zu engagieren. Bei der Suche nach einem Ausweg aus diesen Problemen ist es wichtig für Mazedonien, von anderen Ländern wie Slowenien zu lernen, die ähnliche Probleme haben, aber auch schon Erfahrungen in der Problemlösung. Man muss dabei beachten, dass der Entwicklungsstand, das wirtschaftliche und das politische Umfeld in beiden Vergleichsländern sich erheblich unterscheiden, so dass die Lektionen, die Mazedonien von Slowenien lernen könnte, nicht direkt übertragen und kopiert werden können, sondern entsprechend angepasst werden müssen. Die vorliegende Arbeit liefert Einsichten in die Probleme der Innovationspolitik in Transformationsländern und liefert daher sowohl einen Anreiz als auch eine Quelle von Informationen für künftige Analysen der wirtschaftlichen Bedingungen und vor allem Innovationspolitik in Transformationsländern.

Many-body theory of laser-induced ultrafast demagnetization and angular momentum transfer in ferromagnetic transition metals

An electronic theory is developed, which describes the ultrafast demagnetization in itinerant ferromagnets following the absorption of a femtosecond laser pulse. The present work intends to elucidate the microscopic physics of this ultrafast phenomenon by identifying its fundamental mechanisms. In particular, it aims to reveal the nature of the involved spin excitations and angular-momentum transfer between spin and lattice, which are still subjects of intensive debate. In the first preliminary part of the thesis the initial stage of the laser-induced demagnetization process is considered. In this stage the electronic system is highly excited by spin-conserving elementary excitations involved in the laser-pulse absorption, while the spin or magnon degrees of freedom remain very weakly excited. The role of electron-hole excitations on the stability of the magnetic order of one- and two-dimensional 3d transition metals (TMs) is investigated by using ab initio density-functional theory. The results show that the local magnetic moments are remarkably stable even at very high levels of local energy density and, therefore, indicate that these moments preserve their identity throughout the entire demagnetization process. In the second main part of the thesis a many-body theory is proposed, which takes into account these local magnetic moments and the local character of the involved spin excitations such as spin fluctuations from the very beginning. In this approach the relevant valence 3d and 4p electrons are described in terms of a multiband model Hamiltonian which includes Coulomb interactions, interatomic hybridizations, spin-orbit interactions, as well as the coupling to the time-dependent laser field on the same footing. An exact numerical time evolution is performed for small ferromagnetic TM clusters. The dynamical simulations show that after ultra-short laser pulse absorption the magnetization of these clusters decreases on a time scale of hundred femtoseconds. In particular, the results reproduce the experimentally observed laser-induced demagnetization in ferromagnets and demonstrate that this effect can be explained in terms of the following purely electronic non-adiabatic mechanism: First, on a time scale of 10–100 fs after laser excitation the spin-orbit coupling yields local angular-momentum transfer between the spins and the electron orbits, while subsequently the orbital angular momentum is very rapidly quenched in the lattice on the time scale of one femtosecond due to interatomic electron hoppings. In combination, these two processes result in a demagnetization within hundred or a few hundred femtoseconds after laser-pulse absorption.

Optical amplification and stability of spiroquaterphenyl compounds and blends

In this contribution, we present a systematic investigation on a series of spiroquaterphenyl compounds optimised for solid state lasing in the near ultraviolet (UV). Amplified spontaneous emission (ASE) thresholds in the order of 1 μJ/cm2 are obtained in neat (undiluted) films and blends, with emission peaks at 390 1 nm for unsubstituted and meta-substituted quaterphenyls and 400 4 nm for para-ether substituted quaterphenyls. Mixing with a transparent matrix retains a low threshold, shifts the emission to lower wavelengths and allows a better access to modes having their intensity maximum deeper in the film. Chemical design and blending allow an independent tuning of optical and processing properties such as the glass transition.