Practical applications of a systematic approach to the chemical abatement of pollutants in water and air

The present dissertation is devoted to the systematic approach to the development of organic toxic and refractory pollutants abatement by chemical decomposition methods in aqueous and gaseous phases. The systematic approach outlines the basic scenario of chemical decomposition process applications with a step-by-step approximation to the most effective result with a predictable outcome for the full-scale application, confirmed by successful experience. The strategy includes the following steps: chemistry studies, reaction kinetic studies in interaction with the mass transfer processes under conditions of different control parameters, contact equipment design and studies, mathematical description of the process for its modelling and simulation, processes integration into treatment technology and its optimisation, and the treatment plant design. The main idea of the systematic approach for oxidation process introduction consists of a search for the most effective combination between the chemical reaction and the treatment device, in which the reaction is supposed to take place. Under this strategy,a knowledge of the reaction pathways, its products, stoichiometry and kinetics is fundamental and, unfortunately, often unavailable from the preliminary knowledge. Therefore, research made in chemistry on novel treatment methods, comprisesnowadays a substantial part of the efforts. Chemical decomposition methods in the aqueous phase include oxidation by ozonation, ozone-associated methods (O3/H2O2, O3/UV, O3/TiO2), Fenton reagent (H2O2/Fe2+/3+) and photocatalytic oxidation (PCO). In the gaseous phase, PCO and catalytic hydrolysis over zero valent ironsare developed. The experimental studies within the described methodology involve aqueous phase oxidation of natural organic matter (NOM) of potable water, phenolic and aromatic amino compounds, ethylene glycol and its derivatives as de-icing agents, and oxygenated motor fuel additives ¿ methyl tert-butyl ether (MTBE) ¿ in leachates and polluted groundwater. Gas-phase chemical decomposition includes PCO of volatile organic compounds and dechlorination of chlorinated methane derivatives. The results of the research summarised here are presented in fifteenattachments (publications and papers submitted for publication and under preparation).

The anticancer drug metabolites endoxifen and 4-hydroxy-tamoxifen induce toxic effects on Daphnia pulex in a two-generation study.

Although pharmaceutical metabolites are found in the aquatic environment, their toxicity on living organisms is poorly studied in general. Endoxifen and 4-hydroxy-tamoxifen (4OHTam) are two metabolites of the widely used anticancer drug tamoxifen for the prevention and treatment of breast cancers. Both metabolites have a high pharmacological potency in vertebrates, attributing prodrug characteristics to tamoxifen. Tamoxifen and its metabolites are body-excreted by patients, and the parent compound is found in sewage treatment plan effluents and natural waters. The toxicity of these potent metabolites on non-target aquatic species is unknown, which forces environmental risk assessors to predict their toxicity on aquatic species using knowledge on the parent compounds. Therefore, the aim of this study was to assess the sensitivity of two generations of the freshwater microcrustacean Daphnia pulex towards 4OHTam and endoxifen. Two chronic tests of 4OHTam and endoxifen were run in parallel and several endpoints were assessed. The results show that the metabolites 4OHTam and endoxifen induced reproductive and survival effects. For both metabolites, the sensitivity of D. pulex increased in the second generation. The intrinsic rate of natural increase (r) decreased with increasing 4OHTam and endoxifen concentrations. The No-Observed Effect Concentrations (NOECs) calculated for the reproduction of the second generation exposed to 4OHTam and endoxifen were <1.8 and 4.3μg/L, respectively, whereas the NOECs that were calculated for the intrinsic rate of natural increase were <1.8 and 0.4μg/L, respectively. Our study raises questions about prodrug and active metabolites in environmental toxicology assessments of pharmaceuticals. Our findings also emphasize the importance of performing long-term experiments and considering multi-endpoints instead of the standard reproduction outcome.

Hépatite C: épidémiologie, histoire naturelle et diagnostic [Hepatitis C: epidemiology natural course and diagnosis].

L'infection par le virus de l'hépatite C (HCV) représente une des causes les plus fréquentes d'hépatite chronique, de cirrhose et de carcinome hépatocellulaire au niveau mondial. D'énormes progrès ont été réalisés durant ces 25 dernières années depuis la découverte du HCV, notamment dans la compréhension de la virologie moléculaire, de la pathogenèse et de l'histoire naturelle ainsi que dans la prévention, le diagnostic et le traitement de l'hépatite C. Ces avancées seront résumées dans cet article et discutées à la lumière de nouveaux défis. Hepatitis C virus (HCV) infection represents a major cause of chronic hepatitis, liver cirrhosis and hepatocellular carcinoma worldwide. Great progress in the understanding of the molecular virology, pathogenesis and natural course as well as the prevention, diagnosis and treatment of hepatitis C have been made in over the last 25 years since the discovery of HCV. Here, we review recent advances and discuss them in the light of new challenges.

Total synthesis of lamellarin D and analogs library

Larnellarins are a group of marine natural products isolated from the prosobranch mollusc Lamellaria sp., the ascidian Didemnum sp., and the sponge Dendrilla Cactos. Several of them exhibit interesting biological activities. Natural as well as synthetic lamellarins should be excellent candidates for the development of new drugs due to their unique skeletal structure and their important biological activities especially as antitumor agents. Lamelarin O has been recently characterized as a topoisomerase 1-targeted anti tumor agent. A variety of synthetic approaches have been developed for this family of alkaloids. Herein we describe a new route to the synthesis of Lamellarin D, from a methyl 2-pyrrolecarboxylate. Transformation of the starting material into the scaffold, a substituted 5,6-dihydropyrrolo (2,l ­a)isoquinoline (5,6-DHPl), was afforded by N-alkylation followed by intramolecular Heck cyclization. From this scaffold the synthetic strategy is based on two sequential regioselective bromination!Suzuki cross-coupling reactions which permitted the introduction of differently substituted aryl groups on positions 1 and 2 followed by oxidation, deprotection, and lactonization.

The interaction between sulfathiazole and cobalt(II): potentiometric studies

Potentiometric studies of sulfathiazole (HST) in the presence and absence of cobalt(II) were performed. Equilibrium constants for the formation of the detected species, [Co(ST)]+ and [Co(ST)(OH)], are reported. UV-Vis spectrophotometric measurements suggest that the coordination Co(II)-sulfathiazole might be through a N atom, which, in agreement with MO calculations, could be a thiazolic one. In spite of sulfonamides being better ligands at pH >7, [Co(ST)]+ was found at pH » 3.

Sustainable drugs and global health care

Each day, Earth's finite resources are being depleted for energy, for material goods, for transportation, for housing, and for drugs. As we evolve scientifically and technologically, and as the population of the world rapidly approaches 7 billion and beyond, among the many issues with which we are faced is the continued availability of drugs for future global health care. Medicinal agents are primarily derived from two sources, synthetic and natural, or in some cases, as semi-synthetic compounds, a mixture of the two. For the developed world, efforts have been initiated to make drug production "greener", with milder reagents, shorter reaction times, and more efficient processing, thereby using less energy, and reactions which are more atom efficient, and generate fewer by-products. However, most of the world's population uses plants, in either crude or extract form, for their primary health care. There is relatively little discussion as yet, about the long term effects of the current, non-sustainable harvesting methods for medicinal plants from the wild, which are depleting these critical resources without concurrent initiatives to commercialize their cultivation. To meet future public health care needs, a paradigm shift is required in order to adopt new approaches using contemporary technology which will result in drugs being regarded as a sustainable commodity, irrespective of their source. In this presentation, several approaches to enhancing and sustaining the availability of drugs, both synthetic and natural, will be discussed, including the use of vegetables as chemical reagents, and the deployment of integrated strategies involving information systems, biotechnology, nanotechnology, and detection techniques for the development of medicinal plants with enhanced levels of bioactive agents.

Synthesis and antifungal activity of halogenated aromatic bis-γ-lactones analogous to avenaciolide

Here we describe the total syntheses and characterization by elemental analyses, infrared and NMR spectroscopy of three new compounds analogous to avenaciolide, a bis-γ-lactone isolated from Aspergillus avenaceus that possesses antifungal activity, where the octyl group of the natural product was replaced by aromatic groups containing chlorine and fluorine atoms. The effects of the avenaciolide, the novel compounds and their synthetic precursors on mycelia development and conidia germination of Colletotrichum gloeosporioides and Fusarium solani were evaluated in vitro. The title compounds were almost as active as avenaciolide. The absolute structures of the chlorinated analogs were determined by X-ray diffraction analysis.

Neolignans from Licaria chrysophylla and Licaria aurea with DNA topoisomerase II-α inhibitory activity

Seven natural neolignans isolated from Licaria chrysophylla and Licaria aurea along with five semisynthetic derivatives were tested for their inhibitory action on DNA-topoisomerase by relaxation assays on pBR322 plasmid DNA. All compounds tested showed strong inhibition at a concentration of 100 µM, while none showed activity between 5 and 70 µM. These results indicate that no obvious correlation can be derived between the structure of these compounds and their inhibitory effect on the DNA relaxation activity of topoisomerase II. This is the first report on DNA topoisomerase II inhibitors from Licaria chrysophylla and Licaria aurea leading to the identification of lignoids as topoisomerase II-α inhibitors.

HS-SPME-GC-MS ANALYSIS OF VOLATILE AND SEMI-VOLATILE COMPOUNDS FROM DRIED LEAVES OF Mikania glomerata Sprengel

This paper reports on the identification of volatile and semi-volatile compounds and a comparison of the chromatographic profiles obtained by Headspace Solid-Phase Microextraction/Gas Chromatography with Mass Spectrometry detection (HS-SPME-GC-MS) of dried leaves of Mikania glomerata Sprengel (Asteraceae), also known as 'guaco.' Three different types of commercial SPME fibers were tested: polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB) and polyacrylate (PA). Fifty-nine compounds were fully identified by HS-SPME-HRGC-MS, including coumarin, a marker for the quality control of guaco-based phytomedicines; most of the other identified compounds were mono- and sesquiterpenes. PA fibers performed better in the analysis of coumarin, while PDMS-DVB proved to be the best choice for a general and non-selective analysis of volatile and semi-volatile guaco-based compounds. The SPME method is faster and requires a smaller sample than conventional hydrodistillation of essential oils, providing a general overview of the volatile and semi-volatile compounds of M. glomerata.

The physico-chemical properties of 2-methoxyphenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)

The complexes of 2-methoxyhenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)with the general formula: M(C9H9O4)3·4H2O, where M(II) = Mn, Co, Ni and Cu have been synthesized and characterized by elemental analysis, IR spectroscopy, magnetic and thermogravimetric studies and also X-ray diffraction measurements. The complexes have colours typical for M(II) ions (Mn(II) - a pale pink, Co(II) - pink, Ni(II) - green, and Cu(II) - blue). The carboxylate group binds as monodentate and bidentate ligands. On heating to 1273K in air the complexes decompose in the same way. At first, they dehydrate in one step to anhydrous salts, that next decompose to the oxides of respective metals with the intermediate formation of the oxycarbonates. Their solubility in water at 293K is of the order of 10-5 mol·dm-3. The magnetic moments of analysed complexes were determined in the range of 76-303K. The results reveal them to be high-spin complexes of weak ligand fields.

Biogeochemistry in acid sulphate soil landscapes and small urban centres in Western Finland

The overall purpose of this thesis was to increase the knowledge on the biogeochemistry of rural acid sulphate (AS) soil environments and urban forest ecosystems near small towns in Western Finland. In addition, the potential causal relationship between the distribution of AS soils and geographical occurence of multiple sclerosis (MS) disease was assessed based on a review of existing literature and data. Acid sulphate soils, which occupy an area of approximately 17–24 million hectare worldwide, are regarded as the nastiest soils in the world. Independent of the geographical locality of these soils, they pose a great threat to their surrounding environment if disturbed. The abundant metal-rich acid drainage from Finnish AS soils, which is a result of sulphide oxidation due to artificial farmland drainage, has significant but spatially and temporally variable ecotoxicological impacts on biodiversity and community structure of fish, benthic invertebrates and macrophytes. This has resulted in mass fish kills and even eradication of sensitive fish species in affected waters. Moreover, previous investigations demonstrated significantly enriched concentrations of Co, Ni, Mn and Al, metals which are abundantly mobilised in AS soils, in agricultural crops (timothy grass and oats) and approximately 50 times higher concentrations of Al in cow milk originating from AS soils in Western Finland. Nevertheless, the results presented here demonstrate, in general, relatively moderate metal concentrations in oats and cabbage grown on AS soils in Western Finland, although some of the studied fields showed anomalous values of metals (e.g. Co and Ni) in both the soil and target plants (especially oats), similar to that of the previous investigations. The results indicated that the concentrations of Co, Ni, Mn and Zn in oats and Co and Zn in cabbage were governed by soil geochemistry as these metals were correlated with corresponding concentrations extracted from the soil by NH4Ac-EDTA and NH4Ac, respectively. The concentrations of Cu and Fe in oats and cabbage were uncorrelated to that of the easily soluble concentrations in the soils, suggesting that biological processes (e.g. plant-root processes) overshadow geochemical variation. The concentrations of K and Mg in cabbage, which showed a low spread and were strongly correlated to the NH4Ac extractable contents in the soil, were governed by both the bioavailable fractions in the topsoil and plant-uptake mechanisms. The plant´s ability to regulate its uptake of Ca and P (e.g. through root exudates) seemed to be more important than the influence of soil geochemistry. The distribution of P, K, Ca, Mg, Mn and S within humus, moss and needles in and around small towns was to a high degree controlled by biological cycling, which was indicated by the low correlation coefficients for P, K, Ca, Mg and S between humus and moss, and the low spread of these nutrients in moss and needles. The concentration variations of elements in till are mainly due to natural processes (e.g. intrusions, weathering, mineralogical variations in the bedrock). There was a strong spatial pattern for B in humus, moss and needles, which was suggested to be associated with anthropogenic emissions from nearby town centres. Geogenic dust affected the spatial distribution of Fe and Cr in moss, while natural processes governed the Fe anomaly found in the needles. The spatial accumulation patterns of Zn, Cd, Cu, Ni and Pb in humus and moss were strong and diverse, and related to current industry, the former steel industry, coal combustion, and natural geochemical processes. An intriguing Cu anomaly was found in moss. Since it was located close to a main railway line and because the railway line´s electric cables are made of Cu, it was suggested that the reason for the Cu anomaly is corrosion of these cables. In Western Finland, where AS soils are particularly abundant and enrich the metal concentrations of stream waters, cow milk and to some extent crops, an environmental risk assessment would be motivated to elucidate if the metal dispersion affect human health. Within this context, a topic of concern is the distribution of multiple sclerosis as high MS prevalence rates are found in the main area of AS soils. Regionally, the AS soil type in the Seinäjoki area has been demonstrated to be very severe in terms of metal leaching, this area also shows one of the highest MS rates reported worldwide. On a local scale, these severe AS soil types coincide well with the corresponding MS clustering along the Kyrönjoki River in Seinäjoki. There are reasons to suspect that these spatial correlations are causal, as multiple sclerosis has been suggested to result from a combination of genetic and environmental factors.

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.

The Interplay between Market Orientation and Entrepreneurial Orientation - Empirical Evidence from SMEs

The purpose of this thesis is to investigate how the dimensions of market orientation and entrepreneurial orientation are carried out in small and medium-sized enterprises (SME). In addition, the research aims to answer how these strategic orientations are apparent in SMEs, how the orientations co-vary, and how the dimensions of orientations are carried out in successful SMEs. The qualitative case study was participated by 16 SMEs. The research sample was gathered trough face-to-face interviews, consisting of Likert scale statements and open-ended questions. The main restriction of implementing market and entrepreneurial orientations in SMEs were scarce resources. Thus, the enterprises were required to make trade-offs between the different dimensios of orientations. Risk-aversive enterprises had emphasis on reactive customer orientation whereas, willing to take risks was generally related to proactiveness. Proactive enterprises utilized interfunctional coordination, and innovativeness was supported by value network coordination. The majority of the successful enterprises were growth-oriented, aiming to be technologial leaders in their industries. The successful firms placed similar emphasis on customer and product orientation.

Apple, Nokia and RIM – Rivalry and Co-operation between Three Mobile Phone Corporations

The purpose of this paper is to gather enough evidence to speculate the future of Nokia, Rim and Apple. The thesis goes over the history, current events and business model of each company. This paper includes differences between the companies and co-operation and rivalry, such as patent infringement cases. The study is limited to smartphones and their future. The result of this study is that Apple will continue its steady increase in market share, while Nokia will first decrease and after the launch of the Windows Phone it will rise again. RIM‟s result has not been as good as in past years and it has lost market share. The decrease of share price may lead to acquisition by a company interested in RIM technology.

The purpose of consumer co-operation: implications for the management and governance of co-operatives

Extant research on consumer co-operation has acknowledged that the corporate purpose of consumer co-operatives deviates significantly from the purpose of investor-owned firms (IOFs – the dominant form in market economies and in theory development in the field of business economics) and also suggested that the management of consumer co-operatives differs from the management of IOFs. Despite this, there is a scarcity of research focusing on the management of consumer co-operatives in general and the ways this different purpose manifests in their management in particular. In other words, research on consumer cooperatives has only started to discover the importance of identifying the premises of these organizations and generating management and organization theories that take them into account. The overall objective of this study is to map out some of the implications that the purpose of consumer co-operation has for the management and governance of consumer co-operatives. To put it more precisely, by combining interview data gathered from Finnish consumer cooperatives (S Group, OP Bank Group and POP Bank) and extant literature, this study aims to generate or elaborate on definitions and outlines of the features that co-operative purpose poses for the strategic management, governance and managerial competence needed for consumer co-operatives. The study consists of two parts. The first part introduces the research topic, methods and publications, as well as discusses the overall outcomes. The second part consists of four publications that address the research questions from different viewpoints. The analyses of this study indicate that due to the purpose of consumer co-operation, the roles of locality and regionality become emphasized in their management. While locality and regionality are potential sources of competitive advantage for consumer co-operatives, geographic boundness sets significant boundary conditions for the strategic management of these organizations. Further, the purpose of consumer co-operation may pose several challenges to governance and set specific competence demands for the managers of these organizations. Associating the observations from various streams of research on management and governance with the purpose of consumer co-operation and examining these issues further, the thesis contributes to elaboration of theory in the field. While the thesis is by no means comprehensive (but instead reflects a co-operative research project in its early stages), it does shed light on some key ideas of management and governance and offers leads to theory and, thereby, will prove useful to elaborators, disseminators and appliers of knowledge on co-operation.