Structural studies of analgesics and their interactions. XII. Structure and interactions of anti-inflammatory fenamates. A concerted crystallographic and theoretical conformational study

A theoretical conformational analysis of fenamates, which are N-arylated derivatives of anthranilic acid or 2-aminonicotinic acid with different substituents on the aryl (phenyl) group, is reported. The analysis of these analgesics, which are believed to act through the inhibition of prostaglandin biosynthesis, was carried out using semi-empirical potential functions. The results and available crystallographic observations have been critically examined in terms of their relevance to drug action. Crystallographic studies of these drugs and their complexes have revealed that the fenamate molecules share a striking invariant feature, namely, the sixmembered ring bearing the carboxyl group is coplanar with the carboxyl group and the bridging imino group,the coplanarity being stabilized by resonance interactions and an internal hydrogen bond between the imino and carboxyl groups. The results of the theoretical analysis provide a conformational rationale for the observed invariant coplanarity. The second sixmembered ring, which provides hydrophobicity in a substantial part of the molecule, has limited conformational flexibility in meclofenamic, mefenamic and flufenamic acids. Comparison of the conformational energy maps of these acids shows that they could all assume the same conformation when bound to the relevant enzyme. The present study provides a structural explanation for the difference in the activity of niflumic acid, which can assume a conformation in which the whole molecule is nearly planar. The main role of the carboxyl group appears to be to provide a site for intermolecular interactions in addition to helping in stabilizing the invariant coplanar feature and providing hydrophilicity at one end of the molecule. The fenamates thus provide a good example of conformation- dependent molecular asymmetry.

Paganism, Traditionalism, Nationalism : Narratives of Russian Rodnoverie

The topic of this dissertation is Rodnoverie, a religion that revives pre-Christian Slavic spirituality. Rodnoverie has been noted to be one of the fastest growing new religions in Russia and the aim of the study is to analyse why and how the movement has attained its popularity. First, the analysis asks how Rodnovers themselves explain the revival of ancient Paganism at this particular historical moment. Secondly, these interpretations are reflected in the framework of sociological discussions about contemporary religiosity. The analysis discusses how the Rodnoverie movement corresponds to some tendencies that are considered to characterise late modern religiosity. The primary material of the research is Rodnoverie texts: books, newspapers and electronic articles. The published literature is supplemented by fieldwork material which includes interviews with some Rodnoverie leaders and the author s participant observation of rituals and gatherings. Methodologically, the study draws on a sociological narrative approach that is focused on examining how individuals and groups use narratives to construct their identities and to challenge mainstream discussions and interpretations. The analysis discerns three narratives. The first one of these portrays Rodnoverie as a revival of the native Russian or Slavic religion. The narrative provides a new version of the old Slavophile idea, according to which imitation of the West has misguided Russia and, therefore, Russians should turn to their own tradition. In the second narrative, Rodnoverie is presented as a nature religion that features tolerance and pluralistic values. According to these perceptions, the emergence of Rodnoverie marks the dead-end of the earlier hegemonic universalistic world-views, the mono-ideologies . While the nationalist narrative focuses on Russia s national heritage, the third narrative interprets the tradition in more universal terms as an alternative to modern values and way of life. The main argument of this narrative is that contemporary people have become alienated from nature, their roots and their community. The themes that are discussed in the theoretical literature on late modern religiosity often configure in Rodnovers interpretations either directly or when looked at through an analytical framework. Of the various themes that are addressed in a sociological study of religion the ones that have most relevance for Rodnoverie are the discussions on individualisation, globalisation and secularisation. Rodnoverie reflects such tendencies as the subjectivisation of religion and the modern crisis of authority. The movement also both exemplifies and actively promotes religious pluralisation in Russia.

Theoretical studies on alpha-helix--DNA interactions

The interaction energies between (Ala)10 and alpha-helix fragment and different nucleotide sequences in right-handed B-form have been optimized using semi-empirical potential energy functions. The energies are calculated for two different orientations of the alpha-helix, viz., when the alpha-helix axis taken in the N----C direction is (i) parallel and (ii) antiparallel to the 5'-3' ascending strand of DNA, proximal to it. When both the DNA molecule as well as the alpha-helix are treated as rigid molecules it is found that a polyalanine alpha-helix has slightly more favourable contacts when it is in the proximity of a four nucleotide sequence of 5'-(N-A-T-N)-3' type, where N is either a purine or a pyrimidine. However, when the two interacting molecules are allowed to undergo local structural variations then the interaction energy appears to be independent of the base sequence confirming the non-specific nature of these interactions.

Theoretical Treatment of Interaction Parameters in Multicomponent Metallic Solutions

A new theoretical equation for interaction parameter in multicomponent metallic solutions is developed using the pseudopotential formalism coupled with the free energy of the hard sphere system. The approximate expression for the pseudopotential term is given in terms of the heat of solution at infinite dilution, to allow easy evaluation of the interaction parameter in various multicomponent systems. This theory has been applied to 23 non-ferrous alloys based on Pb, Sn, Bi and indium. Comparison with the results of previous theoretical calculations using only the hard sphere model suggests that the inclusion of the pseudopotential term yields a quantitatively more correct prediction of interaction parameters in multicomponent metallic solutions. Numerical calculations were also made for 320 Fe-base solutions relevant to steelmaking and the agreement between calculation and experimental data appears reasonable, with 90% reliability in predicting the correct sign.

Theoretical and Experimental Studies on an Ammonia-Based Loop Heat Pipe With a Flat Evaporator

An ammonia loop heat pipe (LHP) with a flat plate evaporator is developed and tested. The device uses a nickel wick encased in an aluminum-stainless steel casing. The loop is tested for various heat loads and different sink temperatures, and it demonstrated reliable startup characteristics. Results with the analysis of the experimental observation indicate that the conductance between the compensation chamber and the heater plate can significantly influence the operating temperatures of the LHP. A mathematical model is also presented which is validated against the experimental observations.

Do Households Have Rational Expectations on Future Consumption? Evidence from the Finnish Consumer Survey

Ever since its initial introduction some fifty years ago, the rational expectations paradigm has dominated the way economic theory handles uncertainty. The main assertion made by John F. Muth (1961), seen by many as the father of the paradigm, is that expectations of rational economic agents should essentially be equal to the predictions of relevant economic theory, since rational agents should use information available to them in an optimal way. This assumption often has important consequences on the results and interpretations of the models where it is applied. Although the rational expectations assumption can be applied to virtually any economic theory, the focus in this thesis is on macroeconomic theories of consumption, especially the Rational Expectations–Permanent Income Hypothesis proposed by Robert E. Hall in 1978. The much-debated theory suggests that, assuming that agents have rational expectations on their future income, consumption decisions should follow a random walk, and the best forecast of future consumption level is the current consumption level. Then, changes in consumption are unforecastable. This thesis constructs an empirical test for the Rational Expectations–Permanent Income Hypothesis using Finnish Consumer Survey data as well as various Finnish macroeconomic data. The data sample covers the years 1995–2010. Consumer survey data may be interpreted to directly represent household expectations, which makes it an interesting tool for this particular test. The variable to be predicted is the growth of total household consumption expenditure. The main empirical result is that the Consumer Confidence Index (CCI), a balance figure computed from the most important consumer survey responses, does have statistically significant predictive power over the change in total consumption expenditure. The history of consumption expenditure growth itself, however, fails to predict its own future values. This indicates that the CCI contains some information that the history of consumption decisions does not, and that the consumption decisions are not optimal in the theoretical context. However, when conditioned on various macroeconomic variables, the CCI loses its predictive ability. This finding suggests that the index is merely a (partial) summary of macroeconomic information, and does not contain any significant private information on consumption intentions of households not directly deductible from the objective economic variables. In conclusion, the Rational Expectations–Permanent Income Hypothesis is strongly rejected by the empirical results in this thesis. This result is in accordance with most earlier studies conducted on the topic.

Stereochemically constrained peptides. Theoretical and experimental studies on the conformations of peptides containing 1-aminocyclohexane carboxylic acid

Conformational energy calculations on the model system N-acetyl- 1 -aminocyclohexanecarboxylic acid N'methylamide (Ac-Acc6-NHMe), using an average geometry derived from 13 crystallographic observations, establish that the Acc6 residue is constrained to adopt conformations in the helical regions of In contrast, the a,a-dialkylated residue with linear hydrocarbon side chains, a,a-di-n-propylglycine favors fully extended backbone structures (6 1= $ = 180'). The crystal structures of two model peptides, Boc-(Acc6),-OMe (type 111 @-turn at -Acc6(1)-Acc6(2)-) and Boc-Pro-Acc6-Ala-OMe (type I1 P-turn at -Pro-Acc6-), establish that Acc6 residues can occupy either position of type 111 P-turns and the i + 2 position of type I1 @-turns. The stereochemical rigidity of these peptides is demonstrated in solution by NMR studies, which establish the presence of one intramolecular hydrogen bond in each peptide in CDCI, and (CDJ2S0. Nuclear Overhauser effects permit characterization of the @-turn conformations in solution and establish their similarity to the solid-state structures. The implications for the use of Acc6 residues in conformational design are considered.

Use of 2-pyrimidineamidoxime to generate polynuclear homo-/heterometallic assemblies: synthesis, crystal structures and magnetic study with theoretical investigations on the exchange mechanism

Three new transition metal complexes using 2-pyrimidineamidoxime (pmadH(2)) as multidentate chelating and/or bridging ligand have been synthesized and characterized. The ligand pmadH(2) has two potential bridging functional groups mu-O and mu-(N-O)] and consequently shows several coordination modes. While a polymeric 1D Cu-II complex Cu(pmadH(2))(2)(NO3)](NO3) (1) was obtained upon treatment of Cu(NO3)(2)center dot 3H(2)O with pmadH(2) at room temperature in the absence of base, a high temperature reaction in the presence of base yielded a tetranuclear Cu-II-complex Cu-4(pmad)(2)(pmadH)(2)(NO3)](NO3)(H2O) (2). One of the Cu-II centers is in a square pyramidal environment while the other three are in a square planar geometry. Reaction of the same ligand with an equimolar mixture of both Cu(NO3)(2)center dot 3H(2)O and NiCl2 center dot 6H(2)O yielded a tetranuclear heterometallic (Cu2Ni2II)-Ni-II complex Cu2Ni2(pmad)(2)(pmadH)(2)Cl-2]center dot H2O (3) containing both square planar (Ni-II) and square pyramidal (Cu-II) metal centers. Complexes 1-3 represent the first examples of polynuclear metal complexes of 2-pyrimidineamidoxime. The analysis of variable temperature magnetic susceptibility data of 2 reveals that both ferromagnetic and antiferromagnetic interactions exist in this complex (J(1) = +10.7 cm(-1) and J(2) = -2.7 cm(-1) with g = 2.1) leading to a resultant ferromagnetic behavior. Complex 3 shows expected antiferromagnetic interaction between two Cu-II centers through -N-O- bridging pathway with J(1) = -3.4 cm(-1) and g = 2.08. DFT calculations have been used to corroborate the magnetic results.

Global Processes, Local Strategies : migration of educated Dominicans.

The aim of this thesis is to examine migration of educated Dominicans in light of global processes. Current global developments have resulted in increasingly global movements of people, yet people tend to come from certain places in large numbers rather than others. At the same time, international migration is increasingly selective, which shows in the disproportional number of educated migrants. This study discovers individual and societal motivations that explain why young educated Dominicans decide to migrate and return. The theoretical framework of this thesis underlines that migration is a dynamic process rooted in other global developments. Migratory movements should be seen as a result of interacting macro- and microstructures, which are linked by a number of intermediate mechanisms, meso-structures. The way individuals perceive opportunity structures concretises the way global developments mediate to the micro-level. The case of the Dominican Republic shows that there is a diversity of local responses to the world system, as Dominicans have produced their own unique historical responses to global changes. The thesis explains that Dominican migration is importantly conditioned by socioeconomic and educational background. Migration is more accessible for the educated middle class, because of the availability of better resources. Educated migrants also seem less likely to rely on networks to organize their migrations. The role of networks in migration differs by socioeconomic background on the one hand, and by the specific connections each individual has to current and previous migrants on the other hand. The personal and cultural values of the migrant are also pivotal. The central argument of this thesis is that a veritable culture of migration has evolved in the Dominican Republic. The actual economic, political and social circumstances have led many Dominicans to believe that there are better opportunities elsewhere. The globalisation of certain expectations on the one hand, and the development of the specifically Dominican feeling of ‘externalism’ on the other, have for their part given rise to the Dominican culture of migration. The study also suggests that the current Dominican development model encourages migration. Besides global structures, local structures are found to ve pivotal in determining how global processes are materialised in a specific place. The research for this thesis was conducted by using qualitative methodology. The focus of this thesis was on thematic interviews that reveal the subject’s point of view and give a fuller understanding of migration and mobility of the educated. The data was mainly collected during a field research phase in Santo Domingo, the Dominican Republic in December 2009 and January 2010. The principal material consists of ten thematic interviews held with educated Dominican current or former migrants. Four expert interviews, relevant empirical data, theoretical literature and newspaper articles were also comprehensively used.

Heating values of mature trees.

The effective heating values of the above and below ground biomass components of mature Scots pine (Pinus sylvestris), Norway spruce (Picea abies), downy birch (Betula pubescens), silver birch (Betula pendula), grey alder (Alnus incana), black alder (Alnus glutinosa) and trembling aspen (Populus tremula) were studied. Each sample tree was divided into wood, bark and foliage components. Bomb calorimetry was used to determine the calorimetric heating values. The species is a significant factor in the heating value of individual tree components. The heating value of the wood proper is highest in conifers. Broad-leaved species have a higher heating value of bark than conifers. The species factor diminishes when the weighted heating value of crown, whole stems or stump-root-system are considered. The crown material has a higher heating value per unit weight in comparison with fuelwood from small-sized stems or wholetrees. The additional advantages of coniferous crown material are that it is a non-industrial biomass resource and is readily available. The variability of both the chemical composition and the heating value is small in any given tree component of any species. However, lignin, carbohydrate and extractive content were found to vary from one part of the tree to another and to correlate with the heating value.

Arvojen markkinat : Oikeuttavat arvomaailmat suomalaisten suuryritysten yritysvastuupuheessa

The research in this thesis addresses the question of corporate legitimation and values. It studies moral speech in Finnish companies' social responsibility reports and annual reports. The managerial rhetoric has been examined as a means of building and maintaining legitimacy. The companies studyed are the ten biggest companies that repordted on social responsibility in 2004, and the analysed data consists of the companie's reporting from 1998 to 2008. The theoretical and analytical framework is provided by Luc Boltanski's and Laurent Thévenot's theory of justification. The theory is focused on systems of moral thinking and argumentation, so called "orders of worth". The study shows how these moral schemes were used in the legitimation process. Special attention is paid on the ways that compromises are made between different orders of worth, such as the market, civic and green order. The study shows that the focus of legitimation has shifted towards societal and environmental themes. The values of market and industry, profits and efficiency, however, remain the strongest basis for organizational legitimation in Finnish companies. The economic crisis of 2008 had a visible impact on the moral rhetoric, especially in the Finnish forestry sector. Large layoffs questionned the companies' traditional role and made companies adopt a more market-centered and project-based moral rhetoric. New inspirational and project-centered moral speech emerged as the companies were less able to present themselves as nation-based, traditional actors in the Finnish society.

b-Turn conformations in crystal structures of model peptides containing a,a-di-n-propylglycine (Dpg) and a,a-di-n-butyl-glycine (Dbg).

The crystal state conformations of three peptides containing the a,a-dialkylated residues, a,adi n-propylglycine (Dpg) and a,@-di-n-butylglycine (Dbg), have been established by x-ray diffraction. Boc-Ala-Dpg-Ala-OMe ( I ) and Boc-Ala-Dbg-Ala-OMe (III) adopt distorted type II @-turn conformations with Ala ( I ) and Dpg/Dbg (2) as the corner residues. In both peptides the conformational angles at the Dxg residue (I: 4 = 66.23 J/ = 19.3'; III: 4 = 66S0, J. = 21 .la)deviate appreciablyfrom ideal values for the i + 2 residue in a type II @-turn. In both peptides the observed(N. 0) distances between the Boc CO andAla(3) NHgroups are far too long (I:3.44 k; III: 3.63 k) for an intramolecular 4 + 1 hydrogen bond. Boc-Ala-Dpg-Ala-NHMe (II)crystallizes with two independent molecules in the asymmetric unit. Both molecules IIA and IIB adopt consecutive @-turn (type III-III in IIA and type III-I in IIB) or incipient 3,,,-helical structures, stabilized by two intramolecular 4 --t I hydrogen bonds. In all four molecules the bond angle N-C"-C' ( T ) at the Dxg residues are 2 1109 The observation of conformational angles in the helical region of 4,J/ space at these residues is consistent with theoretical predictions

Theoretical gain‐optimization studies in CO2–N2 gasdynamic lasers. I. Theory

Based on a method proposed by Reddy and Daum, the equations governing the steady inviscid nonreacting gasdynamic laser (GDL) flow in a supersonic nozzle are reduced to a universal form so that the solutions depend on a single parameter which combines all the other parameters of the problem. Solutions are obtained for a sample case of available data and compared with existing results to validate the present approach. Also, similar solutions for a sample case are presented.