Interaction of metal ions with 6-oxopurine nucleotides. Part 1. X-Ray structures of ternary cobalt(III) complexes with inosine 5'-monophosphate or guanosine 5'-monophosphate

The crystal structures of two ternary metal nucleotide complexes of cobalt, [Co(en)2(H2O)2]-[Co(5?-IMP)2(H2O)4]Cl2·4H2O (1) and [Co(en)2(H2O)2][Co(5?-GMP)2(H2O)4]Cl2·4H2O (2), have been analysed by X-ray diffraction (en = ethylenediamine, 5?-IMP = inosine 5?-monophosphate, and 5?-GMP = guanosine 5?-monophosphate). Both complexes crystallize in the orthorhombic space group C2221 with a= 8.725(1), b= 25.891(5), c= 21.212(5)Å, Z= 4 for (1) and a= 8.733(2), b= 26.169(4), c= 21.288(4)Å, Z= 4 for (2). The structure of (1) was solved by the heavy-atom method, while that of (2) was deduced from (1). The structures were refined to R values of 0.09 and 0.10 for 1 546 and 1 572 reflections for (1) and (2) respectively. The two structures are isomorphous. A novel feature is that the chelate ligand en and the nucleotide are not co-ordinated to the same metal ion. One of the metal ions lying on the two-fold a axis is octahedrally co-ordinated by two chelating en molecules and two water oxygens, while the other on the two-fold b axis is octahedrally co-ordinated by two N(7) atoms of symmetry-related nucleotides in a cis position and four water oxygens. The conformations of the nucleotides are C(2?)-endo, anti, and gauche�gauche. In both (1) and (2) the charge-neutralising chloride ions are disordered in the vacant space between the molecules. These structures bear similarities to the mode of nucleotide co-ordination to PtII complexes of 6-oxopurine nucleotides, which are the proposed models for intrastrand cross-linking in DNA by a metal complex.

Interaction of metal ions with 6-oxopurine nucleotides. Part 2. X-Ray structures of ternary nickel(II) complexes with 2'-deoxyguanosine 5'-monophosphate or guanosine 5'-monophosphate

The ternary metal nucleotide complexes [Ni(en)1.3(H2O)1.4(H2O)2][Ni(5?-dGMP)2(en)0.7-(H2O)0.6(H2O)2]·7H2O (1) and [Ni(en)2(H2O)2][Ni(5?-GMP)2(H2O)4]·6H2O (2)(en = ethylenediamine, 5?-dGMP = 2?-deoxyguanosine 5?-monophosphate, 5?-GMP = guanosine 5?-monophosphate) have been prepared and their structures analyzed by X-ray diffraction methods. Both compounds crystallise in the space group C2221 with a= 8.810(1), b= 25.090(4), c= 21.084(1)Å, and Z= 4 for (1) and a= 8.730(1), b= 25.691(4), c= 21.313(5)Å, and Z= 4 for (2). The structures were deduced from the analogous CoIII complexes and refined by full-matrix least-squares methods to final R values of 0.087 and 0.131 for 1 211 and 954 reflections for (1) and (2) respectively. An interesting feature of the deoxyribonucleotide complex (1) is that en is not totally labilized from the metal centre on nucleotide co-ordination, as observed in corresponding ribonucleotide complexes. Apart from extensive intra- and inter-molecular hydrogen bonding, the structures are stabilized by significant intracomplex base�base and base�sugar interactions. The nucleotides in both complexes have an anti base, C(2?)-endo sugar pucker, and gauche�gauche conformation about the C(4?)�C(5?) bond.

Jac. Ahrenberg ja historian perintö : Restaurointisuunnitelmat Viipurin ja Turun linnoihin 1800-luvun lopussa

Jac. Ahrenberg and Patrimony Restoration Plans for Viipuri and Turku Castles at the End of the 19th Century This dissertation examines the unrealized restoration plans for two castles in the Grand Duchy of Finland one located at Viipuri (Vyborg, nowadays in Russia), the other at Turku (in Swedish, Åbo) during the last decades of the 19th century. Both castles were used as prisons, barracks and warehouses. From the middle of the 19th century on, their restoration and transformation into museums and "national monuments" were demanded in the newspapers. The prison reform in the 1860s stimulated the documentation and debate concerning their future, but it was only at the beginning of the 1880s when their restoration became an official state-run project. The undertaking was carried out by Johan Jacob (Jac.) Ahrenberg (1847 1914), architect of the National Board of Public Buildings. By combining written sources with drawings and photographs, this dissertation examines the restoration projects, the two castles' significance and the ways in which they were investigated by scholars. The plans are analyzed in connection with restoration practices in France and Sweden and in the context of contemporary discussions concerning national art and patrimony. The thesis argues that these former castles of the Swedish crown were used to manifest the western roots of Finnish law and order, the lineage of power and the capacity of the nation to defend itself. However, because of their symbolism, their restoration became a politically delicate question concerning the role of the Swedish heritage in Finland's nation-building process. According to Jac. Ahrenberg's plans, the two castles were to be restored to their assumed appearance at the time of the Vasa dynasty. Consequently, the structures would have resembled castles in Sweden. It is suggested that one aim of the restoration plans was to transform the two buildings into monuments testifying to the common history of Sweden and Finland. They were meant to consolidate the Swedish basis of Finnish culture and autonomy and thus to secure them against the threatening implications of Russian imperialism. It seems that along with the changing ideals of architectural restoration and the need for an original Finnish architectural heritage, the political connotations associated with the castles were one reason why Jac. Ahrenberg's restoration plans were never realized.

Mixed Azide and 5-(Pyrimidyl)tetrazole Bridged Co(II)/Mn(II) Polymers: Synthesis, Crystal Structures, Ferroelectric and Magnetic Behavior

The reaction of pyrimidine-2-carbonitrile, NaN3 in the presence of Co(NO3)(2)center dot 6H(2)O or MnCl2 center dot 4H(2)O leads to the formation of complexes Co(pmtz)(mu(1,3)-N-3)(H2O)](n) (1) and Mn(pmtz)(mu(1,3)-N-3)(H2O)](n) (2) respectively, under hydrothermal condition pmtz =5-(pyrimidyl)tetrazolate]. These two complexes have been fully characterized by single crystal X-ray diffraction. Complex 1 crystallizes in a non-centrosymmetric space group Aba2 in the orthorhombic system and is found to exhibit ferroelectric behavior, whereas complex 2 crystallizes in the P2(1)/c space group in the monoclinic system. Variable temperature magnetic characterizations in the temperature range of 2-300 K indicate that complex 1 is a canted antiferromagnet (weak ferromagnet) with T-c = 15.9 K. Complex 1 represents a unique example of a multiferroic coordination polymer containing tetrazole as a co-ligand. Complex 2 is a one-dimensional chain of Mn(II) bridged by a well-known antiferromagnetic coupler end-to-end azido ligand. In contrast to the role played by the end-to-end azido pathway in most of the transition metal complexes, complex 2 showed unusual ferromagnetic behavior below 40 K because of spin canting.

Artificial Bee Colony (ABC) for multi-objective design optimization of composite structures

In this paper, we present a generic method/model for multi-objective design optimization of laminated composite components, based on Vector Evaluated Artificial Bee Colony (VEABC) algorithm. VEABC is a parallel vector evaluated type, swarm intelligence multi-objective variant of the Artificial Bee Colony algorithm (ABC). In the current work a modified version of VEABC algorithm for discrete variables has been developed and implemented successfully for the multi-objective design optimization of composites. The problem is formulated with multiple objectives of minimizing weight and the total cost of the composite component to achieve a specified strength. The primary optimization variables are the number of layers, its stacking sequence (the orientation of the layers) and thickness of each layer. The classical lamination theory is utilized to determine the stresses in the component and the design is evaluated based on three failure criteria: failure mechanism based failure criteria, maximum stress failure criteria and the tsai-wu failure criteria. The optimization method is validated for a number of different loading configurations-uniaxial, biaxial and bending loads. The design optimization has been carried for both variable stacking sequences, as well fixed standard stacking schemes and a comparative study of the different design configurations evolved has been presented. Finally the performance is evaluated in comparison with other nature inspired techniques which includes Particle Swarm Optimization (PSO), Artificial Immune System (AIS) and Genetic Algorithm (GA). The performance of ABC is at par with that of PSO, AIS and GA for all the loading configurations. (C) 2009 Elsevier B.V. All rights reserved.

Interaction of water molecules in non-identical protein structures

The interaction of the protein atoms with the surrounding water oxygen atoms has been computed for 392 protein chains from 369 protein structures belonging to 90% non-homologous high resolution (<= 1.5 angstrom) protein Structures with a crystallographic R-factor <= 20%. The percentage composition of the polar atoms is found to be 36.3%. An average of 82.55% of water oxygen atoms are found to be in the primary hydration shell and 15.12% in the secondary hydration shell. The average Percentage of interactions of water oxygen atoms with the polar atoms of the main chain and side chain are 54% and 46%. respectively. The interaction of the acidic residues, aspartate and glutamate, with the water oxygen atoms is more when compared to that of the other residues.

Structure-Reactivity Correlations of Benzoin Alkyl Ethers. Structures of 2-Methoxy-1,2-diphenylethanone (I) and 2-Isopropoxy-1,2-diphenylethanone (II)

(I): C15H1402, Mr---226.27, triclinic, Pi,a=8.441 (2), b= 10.276 (1), c= 15.342 (2)A, a=91.02 (2), ~ t= 79.26 (2), y= 105.88 (2) °, V=1256.8 (4)A 3, Z=4, D,,= 1.209 (flotation in KI),D x - 1.195 g cm -3, #(Mo, 2 = 0.7107/~) = 0.44 cm -~,F(000) = 480, T= 293 K, R -- 0.060 for 1793 significant reflections. (II): C~THlsO2, Mr= 254.83, orthorhombic, Pca21, a=8.476 (1); b= 16.098 (3), c=10.802(3)A, V=1473.9 (5) A s, Z=4, Dm=1.161 (flotation in KI), Dx= 1.148gem -3, /~(Mo, 2=0.7107 A) =0.41 cm -~, F(000) = 544, T= 293 K, R = 0.071 for 867 significant reflections. Both (I) and (II) crystallize in a cisoid conformation for the carbonyl group and alkoxy groups. Compounds (I) and (II) are photostable on irradiation in the solid state in spite of the favourable conformation of the functional groups for intramolecular H abstraction. Absence of photoreaction of (I)and (II) in the solid state is rationalized in the light of unfavourable intramolecular geometry.

From Habits to Social Structures : Pragmatism and Contemporary Social Theory

Pragmatism has sometimes been taken as a catchphrase for epistemological stances in which anything goes. However, other authors argue that the real novelty and contribution of this tradition has to do with its view of action as the context in which all things human take place. Thus, it is action rather than, for example, discourses that should be our starting point in social theory. The introductory section of the book situates pragmatism (especially the ideas of G. H. Mead and John Dewey) within the field and tradition of social theory. This introductory also contextualizes the main core of the book which consists of four chapters. Two of these chapters have been published as articles in scientific journals and one in an edited book. All of them discuss the core problem of social theory: how is action related to social structures (and vice versa)? The argument is that habitual action is the explanation for the emergence of social structures from our action. Action produces structures and social reproduction takes place when action is habitualized; that is, when we develop social dispositions to act in a certain manner in familiar environments. This also means that even though the physical environment is the same for all of us, our habits structure it into different kinds of action possibilities. Each chapter highlights these general insights from different angles. Practice theory has gained momentum in recent years and it has many commonalities with pragmatism because both highlight the situated and corporeal character of human activity. One famous proponent of practice theory is Margaret Archer who has argued that the pragmatism of G. H. Mead leads to an oversocialized conception of selfhood. Mead does indeed present a socialized view of selfhood but this is a meta-sociological argument rather than a substantial sociological claim. Accordingly, one can argue that in this general sense intersubjectivity precedes subjectivity and not the other way around. Such a view does not indicate that our social relation would necessarily "colonize" individual action because there is a place for internal conversations (in Archer s terminology); it is especially in those phases of action where it meets obstacles due to the changes of the environment. The second issue discussed has the background assumption that social structures can fruitfully be conceptualized as institutions. A general classification of different institution theories is presented and it is argued that there is a need for a habitual theory of institutions due to the problems associated with these other theories. So-called habitual institutionalism accounts for institutions in terms of established and prevalent social dispositions that structure our social interactions. The germs of this institution theory can be found in the work of Thorstein Veblen. Since Veblen s times, these ideas have been discussed for example, by the economist Geoffrey M. Hodgson. His ideas on the evolution of institutions are presented but a critical stance is taken towards his tendency of defining institutions with the help of rules because rules are not always present in institutions. Accordingly, habitual action is the most basic but by no means the only aspect of institutional reproduction. The third chapter deals with theme of action and structures in the context of Pierre Bourdieu s thought. Bourdieu s term habitus refers to a system of dispositions which structure social fields. It is argued that habits come close to the concept of habitus in the sense that the latter consists of particular kinds of habits; those that are related to the reproduction of socioeconomic positions. Habits are thus constituents of a general theory of societal reproduction whereas habitus is a systematic combination of socioeconomic habits. The fourth theme relates to issues of social change and development. The capabilities approach has been associated with the name of Amartya Sen, for example, and it underscores problems inhering in economistic ways of evaluating social development. However, Sen s argument has some theoretical problems. For example, his theory cannot adequately confront the problem of relativism. In addition, Sen s discussion lacks also a theory of the role of the public. With the help of arguments derived from pragmatism, one gets an action-based, socially constituted view of freedom in which the role of the public is essential. In general, it is argued that a socially constituted view of agency does not necessarily to lead to pessimistic conclusions about the freedom of action.

X-ray studies on crystalline complexes involving amino acids and peptides. XV. Crystal structures of L-lysine D-glutamate and L-lysine D-aspartate monohydrate and the effect of chirality on molecular aggregation

L-Lysine D-glutamate crystallizes in the monoclinic space group P2(1) with a = 4.902, b = 30.719, c = 9.679 A, beta = 90 degrees and Z = 4. The crystals of L-lysine D-aspartate monohydrate belong to the orthorhombic space group P2(1)2(1)2(1) with a = 5.458, b = 7.152, c = 36.022 A and Z = 4. The structures were solved by the direct methods and refined to R values of 0.125 and 0.040 respectively for 1412 and 1503 observed reflections. The glutamate complex is highly pseudosymmetric. The lysine molecules in it assume a conformation with the side chain staggered between the alpha-amino and the alpha-carboxylate groups. The interactions of the side chain amino groups of lysine in the two complexes are such that they form infinite sequences containing alternating amino and carboxylate groups. The molecular aggregation in the glutamate complex is very similar to that observed in L-arginine D-aspartate and L-arginine D-glutamate trihydrate, with the formation of double layers consisting of both types of molecules. In contrast to the situation in the other three LD complexes, the unlike molecules in L-lysine D-aspartate monohydrate aggregate into alternating layers as in the case of most LL complexes. The arrangement of molecules in the lysine layer is nearly the same as in L-lysine L-aspartate, with head-to-tail sequences as the central feature. The arrangement of aspartate ions in the layers containing them is, however, somewhat unusual. Thus the comparison between the LL and the LD complexes analyzed so far indicates that the reversal of chirality of one of the components in a complex leads to profound changes in molecular aggregation, but these changes could be of more than one type.

A numerical survey of relativistic rotating neutron star structures using the Hartle-Thorne formalism

A broad numerical survey of relativistic rotating neutron star structures was compiled using an exhaustive list of presently available equation of state models for neutron star matter. The structure parameters (spherical deformations in mass and radii, the moment of inertia and quadrupole moment, oblateness, and free precession) are calculated using the formalism proposed by Hartle and Thorne (1968). The results are discussed in relation to the relevant observational information. Binary pulsar data and X-ray burst sources provide information on the bulk properties of neutron stars, enabling the derivation of constraints that can be put on the structure of neutron stars and equation of state models.

Recent studies on the behaviour of interference fit pins in composite plates

Composites are finding increasing application in many advanced engineering fields like aerospace, marine engineering, hightech sports equipment, etc., due to their high specific strength and/or specific stiffness values. The use of composite components in complex situations like airplane wing root or locations of concentrated load transfer is limited due to the lack of complete understanding of their behaviour in the region of joints. Joints are unavoidable in the design and manufacture of complex structures. Pin joints are one of the most commonly used methods of connection. In regions of high stresses like airplane wing root joints interference fit pins are used to increase its fatigue life and thereby increase the reliability of the whole structure. The present contribution is a study on the behaviour of the interference fit pin in a composite plate subjected to both pull and push type of loads. The interference fit pin exhibits partial contact/separation under the loads and the contact region is a non-linear function of the load magnitude. This non-linear behaviour is studied by adopting the inverse technique and some new results are presented in this paper.

Prediction of protein-protein interactions in dengue virus coat proteins guided by low resolution cryoEM structures

Background: Dengue virus along with the other members of the flaviviridae family has reemerged as deadly human pathogens. Understanding the mechanistic details of these infections can be highly rewarding in developing effective antivirals. During maturation of the virus inside the host cell, the coat proteins E and M undergo conformational changes, altering the morphology of the viral coat. However, due to low resolution nature of the available 3-D structures of viral assemblies, the atomic details of these changes are still elusive. Results: In the present analysis, starting from C alpha positions of low resolution cryo electron microscopic structures the residue level details of protein-protein interaction interfaces of dengue virus coat proteins have been predicted. By comparing the preexisting structures of virus in different phases of life cycle, the changes taking place in these predicted protein-protein interaction interfaces were followed as a function of maturation process of the virus. Besides changing the current notion about the presence of only homodimers in the mature viral coat, the present analysis indicated presence of a proline-rich motif at the protein-protein interaction interface of the coat protein. Investigating the conservation status of these seemingly functionally crucial residues across other members of flaviviridae family enabled dissecting common mechanisms used for infections by these viruses. Conclusions: Thus, using computational approach the present analysis has provided better insights into the preexisting low resolution structures of virus assemblies, the findings of which can be made use of in designing effective antivirals against these deadly human pathogens.

Hierarchy of structures in the family of amine templated open-framework gallium arsenates

Five new gallium arsenate compounds C2N2H10]Ga(H2AsO4)(HAsO4)(2)]center dot H2O, I; C2N2H10]Ga(OH)(AsO4)](2), II; C2N2H10]GaF(AsO4)](2), III; C3N2H12]Ga(OH)(AsO4)](2), IV; Ga2F3(AsO4)(HAsO4)]center dot 2H(3)O, V, have been synthesized under hydrothermal conditions and the structures determined employing single crystal X-ray diffraction studies. All the structures consist of octahedral gallium and tetrahedral arsenate units connected together forming a hierarchy of structures. Thus, one- (I), two- (II and IV) and three-dimensionally (III and V) extended structures have been observed. The Ga-O(H)/F-Ga connectivity in some of the structures suggests the coordination requirements posed by the octahedral gallium in these compounds. The observation of only one type of secondary building unit in the structures of III (SBU-4) and V (spiro-5) is unique and noteworthy. All the compounds have been characterized by a variety of techniques that include powder XRD, IR, and TGA. (C) 2010 Elsevier B. V. All rights reserved.