Novel [3+2] annulation reaction of nitrones with Burgess reagent and a few related reactions

Burgess reagent first prepared by E. M. Burgess in 1968, is a mild and selective dehydrating agent for secondary and tertiary alcohols and due to the amphipolar nature it is gainfully employed in a number of creative synthetic ventures. A close examination of the structure of Burgess reagent reveals that it can act as a 1,2-dipole. To the best of our knowledge, no attempts have been made to tap full synthetic potential of the amphipolar nature of this reagent and no reports on 1,3-dipolar addition to a σ-bond in acyclic systems are available in literature. In this context, we propose to unravel novel applications of Burgess reagent based on its amphipolar nature. Rich and multifaceted chemistry of nitrones form the basis of many successful chemical transformations used in attractive synthetic strategies. For the last 50 years special attention has been given to nitrones due to their successful application as building blocks in the synthesis of various natural and biologically active compounds. Our interest in nitrones stems out of its unique character: i.e. it is a 1,3-dipole exhibiting distinct nucleophilic activity. We reasoned that 1,3-dipole possessing significant nucleophilicity should react with amphipolar Burgess reagent with elimination of triethylamine to give the corresponding five-membered ring product by formal dipolar addition to a σ bond. To test this hypothesis we studied the reaction of nitrones with Burgess reagent. This thesis reveals our attempts to explore the [3+2] annulation reaction of nitrones with Burgess reagent which was found to be followed by a rearrangementinvolving C-to-N aryl migration, ultimately resulting in diarylamines and carbamates. We have also examined the reaction of cyanuric chloride with nitrones in DMF with a view to exploit the nucleophilicty of nitrones and to unravel the migratory aptitude, if any, observed in this reaction

A novel heteroditopic terpyridine-pincer ligand as building block for mono- and heterometallic Pd(II) and Ru(II) complexes

A palladium-catalyzed Stille coupling reaction was employed as a versatile method for the synthesis of a novel terpyridine-pincer (3, TPBr) bridging ligand, 4'-{4-BrC6H2(CH2NMe2)(2)-3,5}-2,2':6',2 ''-terpyridine. Mononuclear species [PdX(TP)] (X = Br, Cl), [Ru(TPBr)(tpy)](PF6)(2), and [Ru(TPBr)(2)](PF6)(2), synthesized by selective metalation of the NCNBr-pincer moiety or complexation of the terpyridine of the bifunctional ligand TPBr, were used as building blocks for the preparation of heterodi- and trimetallic complexes [Ru(TPPdCl)(tpy)](PF6)(2) (7) and [Ru(TPPdCl)(2)]-(PF6)(2) (8). The molecular structures in the solid state of [PdBr(TP)] (4a) and [Ru(TPBr)(2)](PF6)(2) (6) have been determined by single-crystal X-ray analysis. Electrochemical behavior and photophysical properties of the mono-and heterometallic complexes are described. All the above di- and trimetallic Ru complexes exhibit absorption bands attributable to (MLCT)-M-1 (Ru -> tpy) transitions. For the heteroleptic complexes, the transitions involving the unsubstituted tpy ligand are at a lower energy than the tpy moiety of the TPBr ligand. The absorption bands observed in the electronic spectra for TPBr and [PdCl(TP)] have been assigned with the aid of TD-DFT calculations. All complexes display weak emission both at room temperature and in a butyronitrile glass at 77 K. The considerable red shift of the emission maxima relative to the signal of the reference compound [Ru(tpy)(2)](2+) indicates stabilization of the luminescent (MLCT)-M-3 state. For the mono- and heterometallic complexes, electrochemical and spectroscopic studies (electronic absorption and emission spectra and luminescence lifetimes recorded at room temperature and 77 K in nitrile solvents), together with the information gained from IR spectroelectrochemical studies of the dimetallic complex [Ru(TPPdSCN)(tpy)](PF6)(2), are indicative of charge redistribution through the bridging ligand TPBr. The results are in line with a weak coupling between the {Ru(tpy)(2)} chromophoric unit and the (non)metalated NCN-pincer moiety.

Na5(Ga4S)(GaS4)3·6H2O: a three-dimensional thiogallate containing a novel octahedral building block

The new thiogallate Na5(Ga4S)(GaS4)3·6H2O has been prepared solvothermally, using 3,5-dimethyl pyridine as a solvent, and characterised by powder and single crystal X-ray diffraction. This material, which exhibits a three-dimensional crystal structure, crystallises in the cubic space group View the MathML sourceF4¯3c (a = 17.557(4) Å). The crystal structure contains octahedral building blocks [Ga4S (GaS4)6]20−, linked into a three-dimensional network with a perovskite-type topology, and sodium hydrate clusters, [Na5(H2O)6]5+, filling the cavities in the [Ga4S(GaS4)6/2]5− framework. UV–Vis diffuse reflectance measurements indicate that this material is a wide band gap semiconductor, with a band gap of ca. 4.4 eV.

Silsesquioxane as a New Building Block Material for Modified Electrodes Fabrication and Application as Neurotransmitters Sensors

Nanostructured films comprising a 3-n-propylpyridiniunn silsesquioxane polymer (designated as SiPy(+)Cl(-)) and copper (II) tetrasulfophthalocyanine (CuTsPc) were produced using the Layer-by-Layer technique (LbL). To our knowledge this is the first report on the use of silsesquioxane derivative polymers as building blocks for nanostructured thin films fabrication. Deposition of the multilayers were monitored by UV-Vis spectroscopy revealing the linear increment in the absorbance of the Q-band from CuTsPc at 617 nm with the number of SiPy(+)Cl(-)/CuTsPc or CuTsPc/SiPy(+)Cl(-) bilayers. FTIR analyses showed that specific interactions between SiPy+Cl- and CuTsPc occurred between SO(3)(-) groups of tetrasulfophthalocyanine and the pyridinium groups of the polycation. Morphological studies were carried out using the AFM technique, which showed that the roughness and thickness of the films increase with the number of bilayers. The films displayed electroactivity and were employed to detection of dopamine (DA) and ascorbic acid (AA) using cyclic voltammetry, at concentrations ranging from 1.96 x 10(-4) to 1.31 x 10(-3) molL(-1). The number and the sequence of bilayers deposition influenced the electrochemical response in presence of DA and AA. Using differential pulse technique, films comprising SiPy(+)/CuTsPc were able to distinguish between DA and ascorbic acid (AA), with a potential difference of approximately with 500 mV, in the concentration range of 9.0 x 10(-5) to 2.0 x 10(-4) molL(-1), in pH 3.0.

The Purely Reflected Self

Belief in the concept of the self causes suffering. Unfortunately, although conceptual constructions like this may help to define our goal—the casting off of the belief in the self—this is a much more difficult thing to actualize and attain in daily practice. Our building blocks can form a neat tower, and we can climb to the top and gaze at the horizon, but they will topple, leaving us once again over our heads in the hedgerow. Buddha describes his teachings as a raft to ford the river of suffering in order to reach the far off bank of enlightenment: as one does not take the raft after crossing the river, so we must not lean on his teachings to make our way through life. So I intend here to abandon the raft for other accounts of existence written by other thinkers, and in this my purpose is twofold: First, in reading other interpretations we can gain new tools with which to study the architecture of the concept of the self, and second, in studying the history of the concept of self as it progresses through history we can better understand the non-inherentness of this problematic construct. I intend to examine the philosophies of self in the Chinese and European traditions, and their subsequent deconstructive traditions in order to achieve this goal.

Reshaping Rural Extension: Learning for Sustainability (LforS): An Integrative and Learning-Based Advisory Approach for Rural Extension with Small-Scale Farmers

This publication offers concrete suggestions for implementing an integrative and learning-oriented approach to agricultural extension with the goal of fostering sustainable development. It targets governmental and non-governmental organisations, development agencies, and extension staff working in the field of rural development. The book looks into the conditions and trends that influence extension today, and outlines new challenges and necessary adaptations. It offers a basic reflection on the goals, the criteria for success and the form of a state-of-the-art approach to extension. The core of the book consists of a presentation of Learning for Sustainability (LforS), an example of an integrative, learning-oriented approach that is based on three crucial elements: stakeholder dialogue, knowledge management, and organizational development. Awareness raising and capacity building, social mobilization, and monitoring & evaluation are additional building blocks. The structure and organisation of the LforS approach as well as a selection of appropriate methods and tools are presented. The authors also address key aspects of developing and managing a learning-oriented extension approach. The book illustrates how LforS can be implemented by presenting two case studies, one from Madagascar and one from Mongolia. It addresses conceptual questions and at the same time it is practice-oriented. In contrast to other extension approaches, LforS does not limit its focus to production-related aspects and the development of value chains: it also addresses livelihood issues in a broad sense. With its focus on learning processes LforS seeks to create a better understanding of the links between different spheres and different levels of decision-making; it also seeks to foster integration of the different actors’ perspectives.

Electron density building block approach for metal organic frameworks

A general introduction to the state of the art in modeling metal organic materials using transferable atomic multipoles is provided. The method is based on the building block partitioning of the electron density, which is illustrated with some examples of potential applications and with detailed discussions of the advantages and pitfalls. The interactions taking place between building blocks are summarized and are used to discuss the properties that can be calculated.

A Developmental Approach to Sport Expertise

This chapter examines the personal and contextual factors of youth sport that affect sport expertise and developmental outcomes. The developmental model of sport participation (DMSP) is used as a comprehensive framework that outlines different pathways of involvement in sport. Activities and contexts that promote continued sport participation and expert performance are discussed as the building blocks of all effective youth sport programs. This chapter provides evidence that performance in sport, participation, and psychological development should be considered as a whole instead of as separate entities by youth sport programmers. Adults in youth sports (i.e. coaches, parents, sport psychologists, administrators) must consider the differing implications of concepts such as deliberate play, deliberate practice, sampling, specialization, and program structure at different stages of an athlete's talent development. Seven postulates are presented regarding important transitions in youth sport and the role that sampling and deliberate play, as opposed to specialization and deliberate practice, can have during the childhood in promoting continued participation and elite performance in sport

(Table T1) Amino acid ratios and concentrations in interstitial waters of seven ODP Leg 201 sites

Proteins and their amino acid building blocks form a major group of biomolecules in all organisms. In the sedimentary environment, proteins and amino acids have two sources: (1) soft tissues and detritus and (2) biotic skeletal structures, dominantly from calcium carbonate-secreting organisms. The focus of this report is on D/L ratios and concentrations of selected amino acids in interstitial waters collected during ODP Leg 201. The Peru margin sites are generally low in carbonates, whereas the open-ocean sites are more carbonate rich. Seifert et al. (1990, doi:10.2973/odp.proc.sr.112.152.1990) reported amino acid concentrations in interstitial waters from Site 681 (ODP Leg 112) comparable to Leg 201 Site 1229.

Improving novice analyst performance in modeling the sequence diagram in systems analysis: A cognitive complexity approach

The Unified Modeling Language (UML) has quickly become the industry standard for object-oriented software development. It is being widely used in organizations and institutions around the world. However, UML is often found to be too complex for novice systems analysts. Although prior research has identified difficulties novice analysts encounter in learning UML, no viable solution has been proposed to address these difficulties. Sequence-diagram modeling, in particular, has largely been overlooked. The sequence diagram models the behavioral aspects of an object-oriented software system in terms of interactions among its building blocks, i.e. objects and classes. It is one of the most commonly-used UML diagrams in practice. However, there has been little research on sequence-diagram modeling. The current literature scarcely provides effective guidelines for developing a sequence diagram. Such guidelines will be greatly beneficial to novice analysts who, unlike experienced systems analysts, do not possess relevant prior experience to easily learn how to develop a sequence diagram. There is the need for an effective sequence-diagram modeling technique for novices. This dissertation reports a research study that identified novice difficulties in modeling a sequence diagram and proposed a technique called CHOP (CHunking, Ordering, Patterning), which was designed to reduce the cognitive load by addressing the cognitive complexity of sequence-diagram modeling. The CHOP technique was evaluated in a controlled experiment against a technique recommended in a well-known textbook, which was found to be representative of approaches provided in many textbooks as well as practitioner literatures. The results indicated that novice analysts were able to perform better using the CHOP technique. This outcome seems have been enabled by pattern-based heuristics provided by the technique. Meanwhile, novice analysts rated the CHOP technique more useful although not significantly easier to use than the control technique. The study established that the CHOP technique is an effective sequence-diagram modeling technique for novice analysts.

Improving Novice Analyst Performance in Modeling the Sequence Diagram in Systems Analysis: A Cognitive Complexity Approach

The Unified Modeling Language (UML) has quickly become the industry standard for object-oriented software development. It is being widely used in organizations and institutions around the world. However, UML is often found to be too complex for novice systems analysts. Although prior research has identified difficulties novice analysts encounter in learning UML, no viable solution has been proposed to address these difficulties. Sequence-diagram modeling, in particular, has largely been overlooked. The sequence diagram models the behavioral aspects of an object-oriented software system in terms of interactions among its building blocks, i.e. objects and classes. It is one of the most commonly-used UML diagrams in practice. However, there has been little research on sequence-diagram modeling. The current literature scarcely provides effective guidelines for developing a sequence diagram. Such guidelines will be greatly beneficial to novice analysts who, unlike experienced systems analysts, do not possess relevant prior experience to easily learn how to develop a sequence diagram. There is the need for an effective sequence-diagram modeling technique for novices. This dissertation reports a research study that identified novice difficulties in modeling a sequence diagram and proposed a technique called CHOP (CHunking, Ordering, Patterning), which was designed to reduce the cognitive load by addressing the cognitive complexity of sequence-diagram modeling. The CHOP technique was evaluated in a controlled experiment against a technique recommended in a well-known textbook, which was found to be representative of approaches provided in many textbooks as well as practitioner literatures. The results indicated that novice analysts were able to perform better using the CHOP technique. This outcome seems have been enabled by pattern-based heuristics provided by the technique. Meanwhile, novice analysts rated the CHOP technique more useful although not significantly easier to use than the control technique. The study established that the CHOP technique is an effective sequence-diagram modeling technique for novice analysts.

Sediment rates and structures in Bay of Kiel, Baltic Sea

Density and diversity of bottom fauna population as dependent on sediment types and water depth is largely well known in Kiel Bay. This is in contrast to structures and processes of bioturbation, although generally it has a big influence on the benthic boundary layer and its processes, e.g., the metabolism of the bottom fauna, the mechanical properties, the age dating, and the large field of chemical processes. In the densely inhabited sands and muddy sands of the shallower waters with sediment thicknesses of some decimeters only, bioturbation is usually ubiquitous, and most of the structures left are monotonously of "biodeformational" character. At greater water depths, however, where a sedimentary column of several meters of Holocene is developed, the X-ray radiographs of numerous sediment cores show heterogeneous biogenic structures with regional and stratigraphical differentiation. They are described in terms of ichnofabrics and are interpreted on ethological knowledge of the related macrobenthos species. lmportant organisms creating specific traces include the bivalve Arctica (Cyprina) islandica and the polychaete worm Pectinaria koreni. These species are abundant in Kiel Bay and produce by their crawling-plowing mode of locomotion, a characteristic biogenic stratification, the "plow-sole structure". Other typical biogenic structures are tube traces, which are left by a number of different polychaetes occurring either singly, or as U-pairs mainly in mud sediments. Although sea urchins are rare to absent in Kiel Bay, layers of their characteristic traces Scolicia occur as witness of paleohydrographic events in channel sediments of the central bay. Plow-sole traces, polychaete-tube ichnofabric, Scolicia layers and alternations of laminated and bioturbated layers are considered as building blocks of a future "ichnostratigraphy" of Kiel Bay.

A Developmental Approach to Sport Expertise

This chapter examines the personal and contextual factors of youth sport that affect sport expertise and developmental outcomes. The developmental model of sport participation (DMSP) is used as a comprehensive framework that outlines different pathways of involvement in sport. Activities and contexts that promote continued sport participation and expert performance are discussed as the building blocks of all effective youth sport programs. This chapter provides evidence that performance in sport, participation, and psychological development should be considered as a whole instead of as separate entities by youth sport programmers. Adults in youth sports (i.e. coaches, parents, sport psychologists, administrators) must consider the differing implications of concepts such as deliberate play, deliberate practice, sampling, specialization, and program structure at different stages of an athlete's talent development. Seven postulates are presented regarding important transitions in youth sport and the role that sampling and deliberate play, as opposed to specialization and deliberate practice, can have during the childhood in promoting continued participation and elite performance in sport

Speeches and paradoxes of cultural mediation: A practice between the elite and the cultural poverty

This text analyzes the speeches of a group of cultural mediators working in Madrid in public and private institutions of arts. The group was organized as part of the activities of the European Project Divercity: Diving into Diversity in Museums and the City of the Complutense University in March 2015. The aim of the interview was to unravel what they mean by diversity in the profession, and analyze the contradictions and objectives professions that arise in this new field of work.

The art of building trust via e-communication channels: Post-acquisition integration as a special context

This study discusses the importance of establishing trust in post-acquisition integration context and how the use of e-channels facilitates or inhibits this process. The objective of this study is to analyze how the use of electronic communication channels influences the post-acquisition integration process in terms of trust establishment and overall integration efficiency, developing a framework as a result. Three sub-objectives are introduced: to find out the building blocks of trust in M&A’s, to analyse how the use of e-channels influence the process of trust establishment in post-acquisition integration context, and to define the consequences trust and use of e-channels have for the process. The theoretical background of the study includes literature and theories relating to trust establishment in post-acquisition integration context and how the use of e-channels influences the process of trust development on a general level. The empirical research is conducted as a single case study, based on key informant interviews. The interview data was collected between October 2015 and January 2016. Altogether nine interviews were realised; six with representatives from the acquiring firm and three with target firm members. Thematic analysis was selected as the main method for analysing and processing the qualitative data. This study finds that trust has an essential role in post-acquisition integration context, facilitating the integration process in various different ways. Hence, identifying the different building blocks of trust is important in order for members of the organisations to be better able establish and maintain trust. In today’s international business, the role of electronic communication channels has also increased in importance significantly and it was confirmed that these pose both challenges and possibilities for the development of interpersonal trust. One of the most important underlying factors influencing the trust levels via e-communication channels is the level of user’s comfort in using the different e-channels. Without sufficient and meaningful training, the communication conducted via these channels in inhibited in a number of ways. Hence, understanding the defining characteristics of e-communication together with the risks and opportunities related to the use of these can have far-reaching consequences for the post-acquisition integration process as a whole. The framework based on the findings and existing theory introduces the most central factors influencing the trust establishment together with the positive and negative consequences these have for the integration process. Moreover, organizational level consistency and the existence of shared guidelines on appropriate selection of communication channels according to the nature of the task at hand are seen as important