Synthetic approaches towards the Lycopodium alkaloids

The Lycopodium alkaloids are a structurally diverse group of natural products isolated from Lycopodium with important biological effects for the potential treatment of cancer and severe neurodegenerative diseases. To date, full biological studies have been hampered by lack of material from natural sources. Total synthesis represents a possible solution to meet this demand as well as the most effective way to design new compounds to determine structural activity relationships and obtain more potent compounds. The aim of this chapter is to summarise the work carried out in this field so far by presenting an overview of the synthetic strategies used to access each of the four key Lycopodium alkaloid types. Particular emphasis has been placed on methods that rapidly construct each nucleus utilizing tandem reactions.

Synthetic approaches towards the Lycopodium alkaloids

The Lycopodium alkaloids are a structurally diverse group of natural products isolated from Lycopodium with important biological effects for the potential treatment of cancer and severe neurodegenerative diseases. To date, full biological studies have been hampered by lack of material from natural sources. Total synthesis represents a possible solution to meet this demand as well as the most effective way to design new compounds to determine structural activity relationships and obtain more potent compounds. The aim of this chapter is to summarise the work carried out in this field so far by presenting an overview of the synthetic strategies used to access each of the four key Lycopodium alkaloid types. Particular emphasis has been placed on methods that rapidly construct each nucleus utilizing tandem reactions.

Late Roman amphorae in the eastern Tarraconensis. Some chronological and quantitative approaches

Since the classic study of Simon J. Keay published in 1984, knowledge of late Roman amphorae has progressed markedly, thanks to scholars such as Michel Bonifay and Paul Reynolds, amongst others. The area studied by Keay was Catalonia, the ancient Eastern Tarraconensis. The overview here offered for this same region reveals the central role played by African imports in late Antique times, with a minor presence of the Eastern-Mediterranean and South-Hispanic (both Baetican and Lusitanian) productions. Progress in research in the last 25 years has been centred on a series of new and well-dated contexts: the data they have yielded has clarified more precisely the chronology and the proportions of the different imports. On occasion a quantitative approach may even be applied. At the same time the relationship between town and country with respect to the late Roman amphorae is proving of interest and providing results of significance.

Visões de meio ambiente e suas implicações pedagógicas no ensino de química na escola média

This study was realized with high school Chemistry teachers from the region of and around Florianópolis (SC). It examines the pedagogical implications of these teachers' views on environmental issues, and discusses the possibilities and difficulties of bringing these issues into the Chemistry classroom. The semi-structured interviews were analyzed using Textual Discourse Analysis principles. The dominance of content-based teaching and traditional pedagogical approaches appears to hinder curricular changes. Most subjects pay little heed to environmental issues and their relation to Chemistry, and endorse a view of science as neutral, and the environment as anthropocentric - views far from Green Chemistry principles.

The Importance of Semantics: Visual World Studies on Drawing Inferences and Resolving Anaphors

The present thesis investigated the importance of semantics in generating inferences during discourse processing. Three aspects of semantics, gender stereotypes, implicit causality information and proto-role properties, were used to investigate whether semantics is activated elaboratively during discourse comprehension and what its relative importance is in backward inferencing compared to discourse/structural cues. Visual world eye-tracking studies revealed that semantics plays an important role in both backward and forward inferencing: Gender stereotypes and implicit causality information is activated elaboratively during online discourse comprehension. Moreover, gender stereotypes, implicit causality and proto-role properties of verbs are all used in backward inferencing. Importantly, the studies demonstrated that semantic cues are weighed against discourse/structural cues. When the structural cues consist of a combination of cues that have been independently shown to be important in backward inferencing, semantic effects may be masked, whereas when the structural cues consist of a combination of fewer prominent cues, semantics can have an earlier effect than structural factors in pronoun resolution. In addition, the type of inference matters, too: During anaphoric inferencing semantics has a prominent role, while discourse/structural salience attains more prominence during non-anaphoric inferencing. Finally, semantics exhibits a strong role in inviting new inferences to revise earlier made inferences even in the case the additional inference is not needed to establish coherence in discourse. The findings are generally in line with the Mental Model approaches. Two extended model versions are presented that incorporate the current findings into the earlier literature. These models allow both forward and backward inferencing to occur at any given moment during the course of processing; they also allow semantic and discourse/structural cues to contribute to both of these processes. However, while the Mental Model 1 does not assume interactions between semantic and discourse/structural factors in forward inferencing, the Mental Model 2 does assume such a link.

Lo que no es nuevo puede ser actual: hacia distintos puntos de mira de la didáctica del arte What is not new can be current - towards different approaches of the didactics of art

With this article we want to present a state of affairs of the didactics of art in our context, and at the same time we want todiscuss on its pluri- and interdisciplinary construction. We check the different disciplines that configure it and we analysethe paradigm of artistic education as a discipline (DBAE) and its passage to post-modernity. This example focuses thediscussion about the opportunity of adapting holistic educative models and the transition of the current educativeinnovation towards skill models

Carbon sequestration rates in Swedish forest soils : a comparison of three approaches

Selective papers of the workshop on "Development of models and forest soil surveys for monitoring of soil carbon", Koli, Finland, April 5-9 2006.

Developing a Comprehensive Model for Marketing Planning — Combining the Major Approaches

Mix marketing and relationships marketing are two major approaches that often form a basis for organizational marketing planning. The superiority of these approaches has been debated for long without any rational conclusion. Lately there have been studies indicating that both of the major approaches are many times used side by side in marketing planning. There have been also studies suggesting that even combining the mix marketing and relationship marketing approaches might be possible. The aim of this thesis is to provide knowledge about the usage of mix marketing and relationship marketing approaches in organizations and possibilities in combining the approaches. Also a settlement of strengths, weaknesses and risks of combining is intended to provide. The objectives were met through the literature and a case study research. In the case study, interviews were conducted in order to gain a deeper knowledge about marketing planning in various organizations. Based on this study, the combining of the major marketing approaches will be possible and even recommended when keeping in mind few aspects which might cause some troubles in the combining process.

Lipase-catalyzed Approaches towards Secondary Alcohols: Intermediates for Enantiopure Drugs

The use of enantiopure intermediates for drug synthesis is a trend in pharmaceutical industry. Different physiological effects are associated with the enantiomers of chiral molecules. Thus, the safety profile of a drug based on an enantiopure active pharmaceutical ingredient is more reliable. Biocatalysis is an important tool to access enantiopure molecules. In biocatalysis, the advantage of selectivity (chemo-, regio- and stereoselectivity) is combined with the benefits of a green synthesis strategy. Chemoenzymatic syntheses of drug molecules, obtained by combining biocatalysis with modern chemical synthesis steps usually consists of fewer reaction steps, reduced waste production and improved overall synthetic efficiency both in yields and enantio- and/or diastereoselectivities compared with classical chemical synthesis. The experimental work together with the literature review clearly indicates that lipase catalysis is highly applicable in the synthesis of enantiopure intermediates of drug molecules as the basis to infer the correct stereochemistry. By lipase catalysis, enantiopure secondary alcohols used as intermediates in the synthesis of Dorzolamide, an antiglaucoma drug, were obtained. Enantiopure _-hydroxy nitriles as potential intermediates for the synthesis of antidepressant drugs with 1-aryl-3- methylaminopropan-1-ol structure were also obtained with lipases. Kinetic resolution of racemates was the main biocatalytic approach applied. Candida Antarctica lipase B, Burkholderia cepacia lipase and Thermomyces lanuginosus lipase were applied for the acylation of alcohols and the alcoholysis of their esters in organic solvents, such as in diisopropyl ether and tert-butyl methyl ether. Candida Antarctica lipase B was used under solvent free conditions for the acylation of ethyl 3-hydroxybutanoate.

The concept of solution: Industry’s insights compared to theoretical views

Many manufacturing companies have started to offer complete solutions to their customers’ unique needs due to toughening competition and customer demand. Discourse on this kind of solution business is still developing, hence, there is not an established definition for the concept of solution. The aim of the study is to profoundly identify the concept of solution and to understand how the industry’s current views differ from the theoretical concepts. The describing dimensions are identified from selected 13 theoretical notions, and from responses, that the employees of five different companies have given. The 32 interview transcripts are analyzed with thematic analysis and qualitative content analysis. According to the findings, the concept of solution is characterized by integration, customization, risk-sharing, value co-creation, long-term orientation, and desired outcomes. The industry’s insights differ in terms of them all. The results illustrate, that a solution is a bundle, and the whole solution is customized on some level for a client. A solution supplier needs to be customer-focused, in which value co-creation is only a part. The solution solves the customer’s problem, and improves both the customer’s, and the supplier’s business. Neither long-term focus nor risks-sharing were directly employed to characterize the concept of solution. Differences are mainly due to the different approaches to the definitions and inexperience of the companies.

Rebuilding Defenses: Explorations in Norman Fairclough’s Theory of Critical Discourse Analysis

Tutkielmassa eritellään Norman Faircloughin kriittisen diskurssianalyysin teoriaa ja siihen kohdistettua kritiikkiä. Pyrkimyksenä on sovittaa näitä erilaisia näkemyksiä keskenään ja tarjota ratkaisuja yhteen kiriittisen diskurssianalyysin keskeiseen ongelmaan eli emansipaation (sosiaalisten epäkohtien tunnistamisen ja ratkaisemisen) puutteellisuuteen. Teoriaosuudesta esiin nousevia mahdollisuuksia sovelletaan tekstianalyysiin. Tutkimuksen kohteena on teksti Rebuilding America’s Defenses: Strategy, Forces and Resources For a New Century ja jossain määrin sen tuottanut järjestö Project for the New American Century. Näitä tarkastellaan ennen kaikkea sosiaalisina ilmiöinä ja suhteessa toisiinsa. Faircloughin mallin suurimmiksi ongelmiksi muodostuvat perinteinen käsitys kielestä, jonka mukaan kielen järjestelmän abstraktit ja sisäiset suhteet ovat tärkeimpiä, sekä ideologinen vastakkainasettelu kritiikin lähtökohtana. Ensimmäinen johtaa kielellisten tutkimustulosten epätyydyttävään kykyyn selittää sosiaalisia havaintoja ja jälkimmäinen poliittiseen tai maailmankatsomukselliseen väittelyyn, joka ei mahdollista uusia näkemyksiä. Tutkielman lopputulema on, että keskittymällä asiasisältöön kielen rakenteen sijasta ja ymmärtämällä tekstin tuottaja yksittäisenä, rajattuna sosiaalisena toimijana voidaan analyysiin saada avoimuutta ja täsmällisyyttä. Kriittiinen diskurssianalyysi kaipaa tällaista näkemystä kielellisten analyysien tueksi ja uudenlaisen relevanssin löytääkseen.

Teaching mathematics and programming : new approaches with empirical evaluation

Programming and mathematics are core areas of computer science (CS) and consequently also important parts of CS education. Introductory instruction in these two topics is, however, not without problems. Studies show that CS students find programming difficult to learn and that teaching mathematical topics to CS novices is challenging. One reason for the latter is the disconnection between mathematics and programming found in many CS curricula, which results in students not seeing the relevance of the subject for their studies. In addition, reports indicate that students' mathematical capability and maturity levels are dropping. The challenges faced when teaching mathematics and programming at CS departments can also be traced back to gaps in students' prior education. In Finland the high school curriculum does not include CS as a subject; instead, focus is on learning to use the computer and its applications as tools. Similarly, many of the mathematics courses emphasize application of formulas, while logic, formalisms and proofs, which are important in CS, are avoided. Consequently, high school graduates are not well prepared for studies in CS. Motivated by these challenges, the goal of the present work is to describe new approaches to teaching mathematics and programming aimed at addressing these issues: Structured derivations is a logic-based approach to teaching mathematics, where formalisms and justifications are made explicit. The aim is to help students become better at communicating their reasoning using mathematical language and logical notation at the same time as they become more confident with formalisms. The Python programming language was originally designed with education in mind, and has a simple syntax compared to many other popular languages. The aim of using it in instruction is to address algorithms and their implementation in a way that allows focus to be put on learning algorithmic thinking and programming instead of on learning a complex syntax. Invariant based programming is a diagrammatic approach to developing programs that are correct by construction. The approach is based on elementary propositional and predicate logic, and makes explicit the underlying mathematical foundations of programming. The aim is also to show how mathematics in general, and logic in particular, can be used to create better programs.

Verbal learning in mild cognitive impairment and alzheimer's disease : behavioural and neural approaches

The main focus of the present thesis was at verbal episodic memory processes that are particularly vulnerable to preclinical and clinical Alzheimer’s disease (AD). Here these processes were studied by a word learning paradigm, cutting across the domains of memory and language learning studies. Moreover, the differentiation between normal aging, mild cognitive impairment (MCI) and AD was studied by the cognitive screening test CERAD. In study I, the aim was to examine how patients with amnestic MCI differ from healthy controls in the different CERAD subtests. Also, the sensitivity and specificity of the CERAD screening test to MCI and AD was examined, as previous studies on the sensitivity and specificity of the CERAD have not included MCI patients. The results indicated that MCI is characterized by an encoding deficit, as shown by the overall worse performance on the CERAD Wordlist learning test compared with controls. As a screening test, CERAD was not very sensitive to MCI. In study II, verbal learning and forgetting in amnestic MCI, AD and healthy elderly controls was investigated with an experimental word learning paradigm, where names of 40 unfamiliar objects (mainly archaic tools) were trained with or without semantic support. The object names were trained during a 4-day long period and a follow-up was conducted one week, 4 weeks and 8 weeks after the training period. Manipulation of semantic support was included in the paradigm because it was hypothesized that semantic support might have some beneficial effects in the present learning task especially for the MCI group, as semantic memory is quite well preserved in MCI in contrast to episodic memory. We found that word learning was significantly impaired in MCI and AD patients, whereas forgetting patterns were similar across groups. Semantic support showed a beneficial effect on object name retrieval in the MCI group 8 weeks after training, indicating that the MCI patients’ preserved semantic memory abilities compensated for their impaired episodic memory. The MCI group performed equally well as the controls in the tasks tapping incidental learning and recognition memory, whereas the AD group showed impairment. Both the MCI and the AD group benefited less from phonological cueing than the controls. Our findings indicate that acquisition is compromised in both MCI and AD, whereas long13 term retention is not affected to the same extent. Incidental learning and recognition memory seem to be well preserved in MCI. In studies III and IV, the neural correlates of naming newly learned objects were examined in healthy elderly subjects and in amnestic MCI patients by means of positron emission tomography (PET) right after the training period. The naming of newly learned objects by healthy elderly subjects recruited a left-lateralized network, including frontotemporal regions and the cerebellum, which was more extensive than the one related to the naming of familiar objects (study III). Semantic support showed no effects on the PET results for the healthy subjects. The observed activation increases may reflect lexicalsemantic and lexical-phonological retrieval, as well as more general associative memory mechanisms. In study IV, compared to the controls, the MCI patients showed increased anterior cingulate activation when naming newly learned objects that had been learned without semantic support. This suggests a recruitment of additional executive and attentional resources in the MCI group.