A novel single pot synthesis of binuclear copper(II) complexes of macrocyclic and macroacyclic compartmental ligands: Structures and magnetic properties

Two binuclear copper(II) complexes one (complex 1) with a macrocyclic ligand (H(2)L1) and other (complex 2) with a macroacyclic (end-off type) compartmental ligand (HL2) have been synthesized from single pot template synthesis involving copper(II) nitrate, 1,2diaminoethane, 4-methyl-2,6-diformylphenol, and sodium azide. Structure analysis of complex I reveals that there are actually two half molecules present in the asymmetric unit and so two complexes (molecule-I and molecule-II) are present in unit cell, although they show slight differences. The two Cu(II) centers are in distorted square pyramidal coordination environment with two endogenous phenoxo bridges provided by the phenolate of H(2)L1 I having Cu-Cu separations of 2.9133(10) angstrom and 2.9103(10) in the two molecules. In complex 2 the coordination environments around two Cu(II) centers are asymmetric, Cu1 is in distorted square pyramidal environment whereas, the coordination environment around Cu2 is distorted octahedral. The two Cu(II) centers in complex 2 are connected by two different kinds of bridges, one is endogenous phenoxo bridge provided by the phenolate of the ligand HL2 and the other is exogenous azido bridge (mu-(1),(l) type) with Cu-Cu distance of 3.032(10) angstrom. Variable temperature magnetic studies show that two Cu(II) centers in both the complexes are strongly antiferromagnetically coupled with J = -625 +/- 5 cm(-1) and J = -188.6 +/- 1cm(-1) for complex 1 and 2, respectively. (C) 2006 Elsevier B.V. All rights reserved.

Structural Insights into the acyl-intermediates of plasmodium falciparum fatty acid synthesis pathway; the mechanism of expansion of acyl carrier protein core

Acyl carrier protein (ACP) plays a central role in fatty acid biosynthesis. However, the molecular machinery that mediates its function is not yet fully understood. Therefore, structural studies were carried out on the acyl-ACP intermediates of Plasmodium falciparum using NMR as a spectroscopic probe. Chemical shift perturbation studies put forth a new picture of the interaction of ACP molecule with the acyl chain, namely, the hydrophobic core can protect up to 12 carbon units, and additional carbons protrude out from the top of the hydrophobic cavity. The latter hypothesis stems from chemical shift changes observed in C-alpha and C-beta of Ser-37 in tetradecanoyl-ACP. C-13, N-15-Double-filtered nuclear Overhauser effect (NOE) spectroscopy experiments further substantiate the concept; in octanoyl (C-8)- and dodecanoyl (C-12)-ACP, a long range NOE is observed within the phosphopantetheine arm, suggesting an arch-like conformation. This NOE is nearly invisible in tetradecanoyl (C-14)-ACP, indicating a change in conformation of the prosthetic group. Furthermore, the present study provides insights into the molecular mechanism of ACP expansion, as revealed from a unique side chain-to-backbone hydrogen bond between two fairly conserved residues, Ile-55 HN and Glu-48 O. The backbone amide of Ile-55 HN reports a pK(a) value for the carboxylate, similar to 1.9 pH units higher than model compound value, suggesting strong electrostatic repulsion between helix II and helix III. Charge-charge repulsion between the helices in combination with thrust from inside due to acyl chain would energetically favor the separation of the two helices. Helix III has fewer structural restraints and, hence, undergoes major conformational change without altering the overall-fold of P. falciparum ACP.

Branch-branch connections in trees analogous to hyphal fusions in fungal colonies

the leopard tree Caesalpinia ferrea (Leguminosae) a native of eastern Brazil-some of the leader branches connect to and fuse with neighbouring branches of the same tree. The bridge initials project out as pegs or protuberances and apparently extend in a coordinated manner, connecting branches up to 4 ft apart. The fusion of two branches of the same tree implies intra-plant communication involving signaling factor(s). The bridges resemble fusions between hyphae in a fungal colony. Whereas hyphal fusions are common and the process is apparently completed in <1 h, branch fusions in C. ferrea tree are limited and a slow process, apparently requiring several months to years to complete. Branch fusions in C. ferrea are in accord with Claus Mattheck's analysis that tree branches actually seek contact rather than avoid contacts.

Vibration characteristics and damage detection in a suspension bridge

Suspension bridges are flexible and vibration sensitive structures that exhibit complex and multi-modal vibration. Due to this, the usual vibration based methods could face a challenge when used for damage detection in these structures. This paper develops and applies a mode shape component specific damage index (DI) to detect and locate damage in a suspension bridge with pre-tensioned cables. This is important as suspension bridges are large structures and damage in them during their long service lives could easily go un-noticed. The capability of the proposed vibration based DI is demonstrated through its application to detect and locate single and multiple damages with varied locations and severity in the cables of the suspension bridge. The outcome of this research will enhance the safety and performance of these bridges which play an important role in the transport network.

Cystine peptides Antiparallel β-sheet conformation of the cyclic biscystine peptide [Boc-Cys-Ala-Cys-NHCH3]2

The crystal structure analysis of the cyclic biscystine peptide [Boc-Cys1-Ala2-Cys3-NHCH3]2 with two disulfide bridges confirms the antiparallel ?-sheet conformation for the molecule as proposed for the conformation in solution. The molecule has exact twofold rotation symmetry. The 22-membered ring contains two transannular NH ? OC hydrogen bonds and two additional NH ? OC bonds are formed at both ends of the molecule between the terminal (CH3)3COCO and NHCH3 groups. The antiparallel peptide strands are distorted from a regularly pleated sheet, caused mainly by the L-Ala residue in which ?=� 155° and ?= 162°. In the disulfide bridge C? (1)-C? (1)-S(1)-(3')-C?(3')-C?(3'), S�S = 2.030 Å, angles C? SS = 107° and 105°, and the torsional angles are �49, �104, +99, �81, �61°, respectively. The biscystine peptide crystallizes in space group C2 with a = 14.555(2) Ã…, b = 10.854(2) Ã…, c = 16.512(2)Ã…, and ?= 101.34(1) with one-half formula unit of C30H52N8O10S4· 2(CH3)2SO per asymmetric unit. Least-squares refinement of 1375 reflections observed with |F| > 3?(F) yielded an R factor of 7.2%.

Toiminta, valta ja kokemus organisaation muutoksessa : Tutkimus kolmesta suuryrityksestä

Action, Power and Experience in Organizational Change - A Study of Three Major Corporations This study explores change management and resistance to change as social activities and power displays through worker experiences in three major Finnish corporations. Two important sensitizing concepts were applied. Firstly, Richard Sennett's perspective on work in the new form of capitalism, and its shortcomings - the lack of commitment and freedom accompanied by the disruption to lifelong career planning and the feeling of job insecurity - offered a fruitful starting point for a critical study. Secondly, Michel Foucault's classical concept of power, treated as anecdotal, interactive and nonmeasurable, provided tools for analyzing change-enabling and resisting acts. The study bridges the gap between management and social sciences. The former have usually concentrated on leadership issues, best practices and goal attainment, while the latter have covered worker experiences, power relations and political conflicts. The study was motivated by three research questions. Firstly, why people resist or support changes in their work, work environment or organization, and the kind of analyses these behavioural choices are based on. Secondly, the kind of practical forms which support for, and resistance to change take, and how people choose the different ways of acting. Thirdly, how the people involved experience and describe their own subject position and actions in changing environments. The examination focuses on practical interpretations and action descriptions given by the members of three major Finnish business organizations. The empirical data was collected during a two-year period in the Finnish Post Corporation, the Finnish branch of Vattenfal Group, one of the leading European energy companies, and the Mehiläinen Group, the leading private medical service provider in Finland. It includes 154 non-structured thematic interviews and 309 biographies concentrating on personal experiences of change. All positions and organizational levels were represented. The analysis was conducted using the grounded theory method introduced by Straus and Corbin in three sequential phases, including open, axial and selective coding processes. As a result, there is a hierarchical structure of categories, which is summarized in the process model of change behaviour patterns. Key ingredients are past experiences and future expectations which lead to different change relations and behavioural roles. Ultimately, they contribute to strategic and tactical choices realized as both public and hidden forms of action. The same forms of action can be used in both supporting and resisting change, and there are no specific dividing lines either between employer and employee roles or between different hierarchical positions. In general, however, it is possible to conclude that strategic choices lead more often to public forms of action, whereas tactical choices result in hidden forms. The primary goal of the study was to provide knowledge which has practical applications in everyday business life, HR and change management. The results, therefore, are highly applicable to other organizations as well as to less change-dominated situations, whenever power relations and conflicting interests are present. A sociological thesis on classical business management issues can be of considerable value in revealing the crucial social processes behind behavioural patterns. Keywords: change management, organizational development, organizational resistance, resistance to change, change management, labor relations, organization, leadership

Local Politicizations : A Comparison of Finns and French Practicing Democracy

This study examines how do the processes of politicization differ in the Finnish and the French local contexts, and what kinds of consequences do these processes have on the local civic practices, the definitions and redefinitions of democracy and citizenship, the dynamics of power and resistance, and the ways of solving controversies in the public sphere. By means of comparative anthropology of the state , focusing on how democracy actually is practiced in different contexts, politicizations the processes of opening political arenas and recognizing controversy are analyzed. The focus of the study is on local activists engaged in different struggles on various levels of the local public spheres, and local politicians and civil servants participating in these struggles from their respective positions, in two middle-size European cities, Helsinki and Lyon. The empirical analyses of the book compare different political actors and levels of practicing democracy simultaneously. The study is empirically based on four different bodies of material: Ethnographic notes taken during a fieldwork among the activities of several local activist groups; 47 interviews of local activists and politicians; images representing different levels of public portrayals from activist websites (Helsinki N=274, Lyon N=232) and from city information magazines (Helsinki-info N=208, Lyon Citoyen N= 357); and finally, newspaper articles concerning local conflict issues, and reporting on the encounters between local citizens and representatives of the cities (January-June in 2005; Helsingin Sanomat N=96 and Le Progrès N= 102). The study makes three distinctive contributions to the study of current democratic societies: (1) a conceptual one by bringing politicization at the center of a comparison of political cultures, and by considering in parallel the ethnographic group styles theory by Nina Eliasoph and Paul Lichterman, the theory on counter-democracy by Pierre Rosanvallon and the pragmatist justification theory by Luc Boltanski and Laurent Thévenot; (2) an empirical one through the triangulation of ethnographic, thematic interview, visual, and newspaper data through which the different aspects of democratic practices are examined; and (3) a methodological one by developing new ways of analyzing comparative cases an application of Frame Analysis to visual material and the creation of Public Justification Analysis for analyzing morally loaded claims in newspaper reports thus building bridges between cultural, political, and pragmatic sociology. The results of the study indicate that the cultural tools the Finnish civic actors had at their disposal were prone to hinder more than support politicization, whereas the tools the French actors mainly relied on were frequently apt for making politicization possible. This crystallization is defined and detailed in many ways in the analyses of the book. Its consequences to the understanding and future research on the current developments of democracy are multiple, as politicization, while not assuring good results as such, is central to a functioning and vibrant democracy in which injustices can be fixed and new directions and solutions sought collectively.

Cultural Trauma and Life Stories

The purpose of this work is to use the concepts of human time and cultural trauma in a biographical study of the turning points in the recent history of Estonia. This research is primarily based on 148 in-depth biographical interviews conducted in Estonia and Sweden in 1995-2005, supplemented by excerpts from 5 collections and 10 individually published autobiographies. The main body of the thesis consists of six published and of two forthcoming separate refereed articles, summarised in the theoretical introduction, and Appendix of the full texts of three particular life stories. The topic of the first article is the generational composition and the collective action frames of anti-Soviet social mobilisation in Estonia in 1940-1990. The second article details the differentiation of the rites of passage and the calendar traditions as a strategy to adapt to the rapidly changed political realities, comparatively in Soviet Estonia and among the boat-refugees in Sweden. The third article investigates the life stories of the double-minded strategic generation of the Estonian-inclined Communists, who attempted to work within the Soviet system while professing to uphold the ideals of pre-war Estonia. The fourth article is concentrated on the problems of double mental standards as a coping strategy in a contradictory social reality. The fifth article implements the theory of cultural trauma for the social practice of singing nationalism in Estonia. The sixth article bridges the ideas of Russian theoreticians concerning cultural dialogue and the Western paradigm of cultural trauma, with examples from Estonian Russian life stories. The seventh article takes a biographical look at the logic of the unraveling of cultural trauma through four Soviet decades. The eighth article explores the re-shaping of citizen activities as a strategy of coping with the loss of the independent nation state, comparatively in Soviet Estonia and among Swedish Estonians. Cultural trauma is interpreted as the re-ordering of the society s value-normative constellation due to sharp, violent, usually political events. The first one under consideration was caused by the occupations of the Republic of Estonia by the Soviet army in 1940-45. After half a century of suppression the memories of these events resurfaced as different stories describing the long-term, often inter-generational strategies of coping with the value collapse. The second cultural trauma is revealed together with the collapse of the Soviet power and ideology in Estonia in 1991. According to empirical data, the following three trauma discourses have been reconstructed: - the forced adaptation to Soviet order of the homeland Estonians; - the difficulty of preserving Estonian identity in exile (Sweden); - the identity crisis of the Russian population of Estonia. Comparative analyses of these discourses have shown that opposing experiences and worldviews cause conflicting interpretations of the past. Different social and ethnic groups consider coping with cultural trauma as a matter of self-defence and create appropriate usable pasts to identify with. Keywords: human time, cultural trauma, frame analysis, discourse, life stories

Covalent tethering of the dimer interface annuls aggregation in thymidylate synthase

Thymidylate synthase (TS), a dimeric enzyme, forms large soluble aggregates at concentrations of urea (3.3-5 M), well below that required for complete denaturation, as established by fluorescence and size-exclusion chromatography. In contrast to the wild-type enzyme, an engineered mutant of TS (T155C/E188C/C244T), TSMox, in which two subunits are crosslinked by disulfide bridges between residues 155-188' and 188-155', does not show this behavior. Aggregation behavior is restored upon disulfide bond reduction in the mutant protein, indicating the involvement of interface segments in forming soluble associated species. Intermolecular disulfide crosslinking has been used as a probe to investigate the formation of larger non-native aggregates. The studies argue for the formation of large multimeric species via a sticky patch of polypeptide from the dimer interface region that becomes exposed on partial unfolding. Covalent reinforcement of relatively fragile protein-protein interfaces may be a useful strategy in minimizing aggregation of non-native structures in multimeric proteins.

Structural Insights into the Acyl Intermediates of the Plasmodium falciparum Fatty Acid Synthesis Pathway THE MECHANISM OF EXPANSION OF THE ACYL CARRIER PROTEIN CORE

Acyl carrier protein (ACP) plays a central role in fatty acid biosynthesis. However, the molecular machinery that mediates its function is not yet fully understood. Therefore, structural studies were carried out on the acyl-ACP intermediates of Plasmodium falciparum using NMR as a spectroscopic probe. Chemical shift perturbation studies put forth a new picture of the interaction of ACP molecule with the acyl chain, namely, the hydrophobic core can protect up to 12 carbon units, and additional carbons protrude out from the top of the hydrophobic cavity. The latter hypothesis stems from chemical shift changes observed in C-alpha and C-beta of Ser-37 in tetradecanoyl-ACP. C-13, N-15-Double-filtered nuclear Overhauser effect (NOE) spectroscopy experiments further substantiate the concept; in octanoyl (C-8)- and dodecanoyl (C-12)-ACP, a long range NOE is observed within the phosphopantetheine arm, suggesting an arch-like conformation. This NOE is nearly invisible in tetradecanoyl (C-14)-ACP, indicating a change in conformation of the prosthetic group. Furthermore, the present study provides insights into the molecular mechanism of ACP expansion, as revealed from a unique side chain-to-backbone hydrogen bond between two fairly conserved residues, Ile-55 HN and Glu-48 O. The backbone amide of Ile-55 HN reports a pK(a) value for the carboxylate, similar to 1.9 pH units higher than model compound value, suggesting strong electrostatic repulsion between helix II and helix III. Charge-charge repulsion between the helices in combination with thrust from inside due to acyl chain would energetically favor the separation of the two helices. Helix III has fewer structural restraints and, hence, undergoes major conformational change without altering the overall-fold of P. falciparum ACP.

Studies on the structure of the chromosomes - I. Allium cepa-Stain fixatives and their utility

The structure of the mitotic chromosomes of Allium cepa has been elucidated by controlling the temperature and time of exposure of fresh roots to stain fixatives. The details seen in material stained in N HCl-orcein for 8 min. at 60° C. and squashed after varying intervals of storage at room temperature were essentially similar to pictures obtained with 1% aceto-orcein and 1% aceto-orcein-N HCl (10:1) under identical conditions of handling. The chromosomes appear quadri-partite at metaphase and bi-partite at anaphase. A rare instance of the precocious assumption of a quadri-partite condition by two anaphase chromosomes is illustrated. Caduceus coiling of chromonemata was seen in chromosome bridges also. Chromosomes have material easily dissociable from the chromonemata and their removal does not affect the structural integrity of the chromosome.

Conditional Moments in Asset Pricing

A better understanding of stock price changes is important in guiding many economic activities. Since prices often do not change without good reasons, searching for related explanatory variables has involved many enthusiasts. This book seeks answers from prices per se by relating price changes to their conditional moments. This is based on the belief that prices are the products of a complex psychological and economic process and their conditional moments derive ultimately from these psychological and economic shocks. Utilizing information about conditional moments hence makes it an attractive alternative to using other selective financial variables in explaining price changes. The first paper examines the relation between the conditional mean and the conditional variance using information about moments in three types of conditional distributions; it finds that the significance of the estimated mean and variance ratio can be affected by the assumed distributions and the time variations in skewness. The second paper decomposes the conditional industry volatility into a concurrent market component and an industry specific component; it finds that market volatility is on average responsible for a rather small share of total industry volatility — 6 to 9 percent in UK and 2 to 3 percent in Germany. The third paper looks at the heteroskedasticity in stock returns through an ARCH process supplemented with a set of conditioning information variables; it finds that the heteroskedasticity in stock returns allows for several forms of heteroskedasticity that include deterministic changes in variances due to seasonal factors, random adjustments in variances due to market and macro factors, and ARCH processes with past information. The fourth paper examines the role of higher moments — especially skewness and kurtosis — in determining the expected returns; it finds that total skewness and total kurtosis are more relevant non-beta risk measures and that they are costly to be diversified due either to the possible eliminations of their desirable parts or to the unsustainability of diversification strategies based on them.

Modeling Nonlinearities and Asymmetries in Asset Pricing

Financial time series tend to behave in a manner that is not directly drawn from a normal distribution. Asymmetries and nonlinearities are usually seen and these characteristics need to be taken into account. To make forecasts and predictions of future return and risk is rather complicated. The existing models for predicting risk are of help to a certain degree, but the complexity in financial time series data makes it difficult. The introduction of nonlinearities and asymmetries for the purpose of better models and forecasts regarding both mean and variance is supported by the essays in this dissertation. Linear and nonlinear models are consequently introduced in this dissertation. The advantages of nonlinear models are that they can take into account asymmetries. Asymmetric patterns usually mean that large negative returns appear more often than positive returns of the same magnitude. This goes hand in hand with the fact that negative returns are associated with higher risk than in the case where positive returns of the same magnitude are observed. The reason why these models are of high importance lies in the ability to make the best possible estimations and predictions of future returns and for predicting risk.

Understanding Customer Loyalty and Disloyalty The Effect of Loyalty-Supporting and -Repressing Factors (first edition sold out, 'print on demand' 60 €)

Customer loyalty has been a central topic of both marketing theory and practice for several decades. Customer disloyalty, or relationship ending, has received much less attention. Despite the close relation between customer loyalty and disloyalty, they have rarely been addressed in the same study. The thesis bridges this gap by focusing on both loyal and disloyal customers and the factors characterising them. Based on a qualitative study of loyal and disloyal bank customers in the Finnish retail banking market, both factors that are common to the groups and factors that differentiate between them are identified. A conceptual framework of factors that affect customer loyalty or disloyalty is developed and used to analyse the empirical data. According to the framework, customers’ loyalty status (behavioural and attitudinal loyalty) is influenced by positive, loyalty-supporting, and negative, loyalty-repressing factors. Loyalty-supporting factors either promote customer dedication, making the customer want to remain loyal, or act as constraints, hindering the customer from switching. Among the loyalty-repressing factors it is especially important to identify those that act as triggers of disloyal behaviour, making customers switch service providers. The framework further suggests that by identifying the sources of loyalty-supporting and -repressing factors (the environment, the provider, the customer, the provider-customer interaction, or the core service) one can determine which factors are within the control of the service provider. Attitudinal loyalty is approached through a customer’s “feeling of loyalty”, as described by customers both orally and graphically. By combining the graphs with behavioural loyalty, seven customer groups are identified: Stable Loyals, Rescued Loyals, Loyals at Risk, Positive Disloyals, Healing Disloyals, Fading Disloyals, and Abrupt Disloyals. The framework and models of the thesis can be used to analyse factors that affect customer loyalty and disloyalty in different service contexts. Since the empirical study was carried out in a retail bank setting, the thesis has managerial relevance especially for banks. Christina Nordman is associated with CERS, Center for Relationship Marketing and Service Management at the Swedish School of Economics and Business Administration. The doctoral thesis is part of the Göran Collert Research Project in Customer Relationships and Retail Banking and has been funded by The Göran Collert Foundation.

An Empirical Investigation of Value-at-Risk in Long and Short Trading Positions

This paper uses the Value-at-Risk approach to define the risk in both long and short trading positions. The investigation is done on some major market indices(Japanese, UK, German and US). The performance of models that takes into account skewness and fat-tails are compared to symmetric models in relation to both the specific model for estimating the variance, and the distribution of the variance estimate used as input in the VaR estimation. The results indicate that more flexible models not necessarily perform better in predicting the VaR forecast; the reason for this is most probably the complexity of these models. A general result is that different methods for estimating the variance are needed for different confidence levels of the VaR, and for the different indices. Also, different models are to be used for the left respectively the right tail of the distribution.