Podmiotowość a zmiana społeczna w pismach teoretycznych Margaret S. Archer. Analiza, porównania, rekonceptualizacja pojęć

Wydział Nauk Społecznych: Instytut Socjologii

Phase mixing and phase separation accompanying the catalytic oxidation of CO on Ir{100}

The co-adsorption of CO and O on the unreconstructed (1 x 1) phase of Ir {100} was examined by low energy electron diffraction (LEED) and temperature programmed desorption (TPD). When CO is adsorbed at 188 K onto the Ir{100} surface precovered with 0.5 ML O, a mixed c(4 x 2)-(2O + CO) overlayer is formed. All CO is oxidised upon heating and desorbs as CO2 in three distinct stages at 230 K, 330 K and 430 K in a 2:1:2 ratio. The excess oxygen left on the surface after all CO has reacted forms an overlayer with a LEED pattern with p(2 x 10) periodicity. This overlayer consists of stripes with a local p(2 x 1)-O arrangement of oxygen atoms separated by stripes of uncovered It. When CO is adsorbed at 300 K onto the surface precovered with 0.5 ML O an apparent (2 x 2) LEED pattern is observed. LEED IV analysis reveals that this pattern is a superposition of diffraction patterns from islands of c(2 x 2)-CO and p(2 x 1)-O structures on the surface. Heating this co-adsorbed overlayer leads to the desorption of CO, in two stages at 330 K and 430 K; the excess CO (0.1 ML) desorbs at 590 K. LEED IV structural analysis of the mixed c(4 x 2) O and CO overlayer shows that both the CO molecules and the O atoms occupy bridge sites. The O atoms show significant lateral displacements of 0.14 angstrom away from the CO molecules; the C-O bond is slightly expanded with respect to the gas phase (1.19 angstrom); the modifications of the Ir substrate with respect to the bulk-terminated surface are very small. (c) 2006 Elsevier B.V. All rights reserved.

Synthesis and crystal structure characterization of iron(II), cobalt(II) and nickel(II) complexes with 1,3-bis(2-pyridylmethylthio)propane

Three new mononuclear complexes of nitrogen-sulfur donor sets, formulated as (Fe-II(L)Cl-2] (1), [Co-II(L)Cl-2] (2) and [Ni-II(L)Cl-2] (3) where L = 1,3-bis(2-pyridylmethylthio)propane, were synthesized and isolated in their pure form. All the complexes were characterized by physicochemical and spectroscopic methods. The solid state structures of complexes I and 3 have been established by single crystal X-ray crystallography. The structural analysis evidences isomorphous crystals with the metal ion in a distorted octahedral geometry that comprises NSSN ligand donors with trans located pyridine rings and chlorides in cis positions. In dimethylformamide solution, the complexes were found to exhibit Fe-II/Fe-III, co(II)/co(III) and Ni-II/Ni-III quasi-reversible redox couples in cyclic voltammograms with E-1/2 values (versus Ag/AgCl at 298 K) of +0.295, +0.795 and +0.745 V for 1, 2 and 3, respectively. (C) 2009 Elsevier Ltd. All rights reserved.

Guanine specific binding at a DNA junction formed by d[CG(5-BrU)ACG]2 with a topoisomerase poison in the presence of Co2+Ions†,‡

The structure of the duplex d[CG(5-BrU)ACG]2 bound to 9-bromophenazine-4-carboxamide has been solved through MAD phasing at 2.0 Å resolution. It shows an unexpected and previously unreported intercalation cavity stabilized by the drug and novel binding modes of Co2+ ions at certain guanine N7 sites. For the intercalation cavity the terminal cytosine is rotated to pair with the guanine of a symmetry-related duplex to create a pseudo-Holliday junction geometry, with two such cavities linked through the minor groove interactions of the N2/N3 guanine sites at an angle of 40°, creating a quadruplex-like structure. The mode of binding of the drug is shown to be disordered, with the major conformations showing the side chain bound to the N7 position of adjacent guanines. The other end of the duplex exhibits a terminal base fraying in the presence of Co2+ ions linking symmetry-related guanines, causing the helices to intertwine through the minor groove. The stabilization of the structure by the intercalating drug shows that this class of compound may bind to DNA junctions as well as duplex DNA or to strand-nicked DNA (‘hemi-intercalated'), as in the cleavable complex. This suggests a structural basis for the dual poisoning of topoisomerase I and II enzymes by this family of drugs.

Metal cluster expansion by addition of low valent group 14 reagents: III. Reaction of bis[bis(trimethylsilyl)methyl]tin with M3(CO)12 or its derivatives (M = Fe, Ru, or Os): the crystal and molecular structures of M3(μ-SnR2)2(CO)10(R = CH(SiMe3)2; M = Ru or Os)

The stannylene [SnR2] (R = CH(SiMe3)2) reacts in different ways with the three dodecacarbonyls of the iron triad: [Fe3(CO)12] gives [Fe2(CO)8(μ-SnR2)], [Ru3(CO)12] gives the planar pentametallic cluster [Ru3(CO)10(μ-SnR2)2], for which a full structural analysis is reported, while [Os3(CO)12] fails to react. Different products are also obtained from three nitrile derivatives: [Fe3-(CO)11(MeCN)] gives [Fe2(CO)6(μ-SnR2)2], which has a structure significantly different from that of known Fe2Sn2 clusters, [Ru3(CO)10(MeCN)2] gives the pentametallic cluster described above, while [Os3(CO)10(MeCN)2] gives the isostructural osmium analogue, which shows the unusual feature of a CO group bridging two osmium atoms.

Iterative Methods for Equality-Constrained Least Squares Problems

We consider the linear equality-constrained least squares problem (LSE) of minimizing ${\|c - Gx\|}_2 $, subject to the constraint $Ex = p$. A preconditioned conjugate gradient method is applied to the Kuhn–Tucker equations associated with the LSE problem. We show that our method is well suited for structural optimization problems in reliability analysis and optimal design. Numerical tests are performed on an Alliant FX/8 multiprocessor and a Cray-X-MP using some practical structural analysis data.

Crystal structures of Λ-[Ru(phen)2dppz]2+ with oligonucleotides containing TA/TA and AT/AT steps show two intercalation modes

The ruthenium complex [Ru(phen)2(dppz)] (where phen is a phenanthroline and dppz a dipyridyl–phenazine ligand) is known as a ‘light switch’ complex because its luminescence in solution is significantly enhanced in the presence of DNA. This property is poised to serve in diagnostic and therapeutic applications, but its binding mode with DNA needs to be elucidated further. Here, we describe the crystal structures of the L enantiomer bound to two oligonucleotide duplexes. The dppz ligand intercalates symmetrically and perpendicularly from the minor groove of the d(CCGGTACCGG)2 duplex at the central TA/TA step, but not at the central AT/AT step of d(CCGGATCCGG)2. In both structures, however, a second ruthenium complex links the duplexes through the combination of a shallower angled intercalation into the C1C2/G9G10 step at the end of the duplex, and semi-intercalation into the G3G4 step of an adjacent duplex. The TA/TA specificity of the perpendicular intercalation arises from the packing of phenanthroline ligands against the adenosine residue.

Mesomorphic behaviour in copoly(ester-imide)s of poly(butylene-2,6-naphthalate) (PBN)

Copolycondensation of N,N’-bis(4-hydroxybutyl)-biphenyl-3,4,3',4'-tetracarboxylic diimide at 20 and 25 mol% with bis(4-hydroxybutyl)-2,6-naphthalate produces PBN-based copoly(ester-imide)s that not only crystallise but also form a (smectic) mesophase upon cooling from the melt. Incorporation of 25 mol% imide in PBN causes the glass transition temperature (measured by DSC) to rise from 51 to 74 °C, a significant increase relative to PBN. Furthermore, increased storage- (G'), loss- (G'') and elastic (E) moduli are observed for both copoly(ester-imide)s when compared to PBN itself. Structural analysis of the 20 mol% copolymer by X-ray powder and fibre diffraction, interfaced to computational modelling, suggests a crystal structure related to that of α-PBN, in space group P-1, with cell dimensions a = 4.74, b = 6.38, c = 14.45 Å, α = 106.1, β = 122.1, γ = 97.3°, ρ = 1.37 g cm-3.

Premature germination of resting spores as a means of Protecting brassica crops from Plasmodiophora brassicae Wor., (clubroot)

Premature germination of resting spores as a means of protecting brassica crops from Plasmodiphora brassicae Wor., (Clubroot). Crop Protection. Clubroot disease causes substantial yield and quality losses in broadacre oil seed and intensive vegetable brassica crops worldwide. The causal microbe Plasmodiophora brassicae Wor., perennates as soil-borne dormant resting spores. Their germination is triggered by exudates from host roots. A valuable addition to sustainable integrated control strategies could be developed by identifying and synthesising the molecules responsible for stimulating resting spore germination. This paper reports experiments in which stimulatory exudates were collected from brassica roots following exposure to infective stages of P. brassicae. Analyses identified a germination signalling molecule of circa 1 kDa formed of glucose sub-units. Mass spectral analyses showed this to be a complex hexasaccharide carbohydrate with structural similarities to the components of plant cell walls. This is the first report of a host generated hexasaccharide which is capable of stimulating the germination of resting spores of P. brassicae. The implications for environmentally benign control of clubroot are discussed briefly.

Compositional control of the electrical transport properties in the new series of thiospinels Ga1-xGexV4S8-delta (0 <=x<=1)

A new series of non-stoichiometric sulfides Ga1−xGexV4S8−δ (0≤x≤1; δ≤0.23) has been synthesized at high temperatures by heating stoichiometric mixtures of the elements in sealed quartz tubes. The samples have been characterized by powder X-ray diffraction, SQUID magnetometry and electrical transport-property measurements. Structural analysis reveals that a solid solution is formed throughout this composition range, whilst thermogravimetric data reveal sulfur deficiency of up to 2.9% in the quaternary phases. Magnetic measurements suggest that the ferromagnetic behavior of the end-member phase GaV4S8 is retained at x≤0.7; samples in this composition range showing a marked increase in magnetization at low temperatures. By contrast Ga0.25Ge0.75V4S8−δ appears to undergo antiferromagnetic ordering at ca. 15 K. All materials with x≠1 are n-type semiconductors whose resistivity falls by almost six orders of magnitude with decreasing Ga content, whilst the end-member phase GeV4S8−δ is a p-type semiconductor. The results demonstrate that the physical properties are determined principally by the degree of electron filling of narrow-band states arising from intracluster V–V interactions.

Quantitative structure of an acetate dye molecule analogue at the TiO2- acetic acid interface

The positions of atoms in and around acetate molecules at the rutile TiO2(110) interface with 0.1 M acetic acid have been determined with a precision of ±0.05 Å. Acetate is used as a surrogate for the carboxylate groups typically employed to anchor monocarboxylate dye molecules to TiO2 in dye-sensitised solar cells (DSSC). Structural analysis reveals small domains of ordered (2 x 1) acetate molecules, with substrate atoms closer to their bulk terminated positions compared to the clean UHV surface. Acetate is found in a bidentate bridge position, binding through both oxygen atoms to two five-fold titanium atoms such that the molecular plane is along the [001] azimuth. Density functional theory calculations provide adsorption geometries in excellent agreement with experiment. The availability of these structural data will improve the accuracy of charge transport models for DSSC.

Influence of ceria addition on thermal properties and local structure of bismuth germanate glasses

Bismuth germanate glasses are interesting materials due to their physical properties and their unique structural characteristics caused by the coordination changes of bismuth and germanium atoms. Glasses of the bismuth germanate system were prepared by melting/molding method and were investigated concerning their thermal and structural properties. The structural analysis of the samples was carried out by micro-Raman and Fourier transform infrared spectroscopes. It was observed that the glass structure is formed basically by GeO(4) tetrahedral units also having the formation of the GeO(6) octahedral units. BiO(2) was considered a network former by observing the presence of octahedral BiO(6) and pyramidal BiO(3) groups in the local structure of the samples. An absorption band observed at 1103 cm(-1) in the IR spectrum of the undoped glass was attributed to the Bi-O-Ge and/or Bi-O-Bi linkage vibration. The said band shifted to lower wavenumbers after the CeO(2) addition thus reflecting changes in the glass network. Cerium oxide was an efficient oxidant agent to prevent the darkening of the glasses which was probably associated to the reduction of Bi ions. However, CeO(2) was incorporated as a local network modifier in the glass structure even at concentrations of 0.2 mol%. (C) 2010 Elsevier B.V. All rights reserved.

Contribution of SHRIMP U-Pb zircon geochronology to unravelling the evolution of Brazilian Neoproterozoic fold belts

The South-American continent is constituted of three major geologic-geotectonic entities the homonym platform (consolidated at the end of the Cambrian) the Andean chain (essentially Meso-Cenozoic) and the Patagonian terrains affected by tectonism and magmatism through almost all of the Phanerozoic The platform is constituted by a series of cratonic nuclei (pre-Tonian fragments of the Rodinia fission) surrounded by a complex fabric of Neoproterozoic structural provinces Two major groups of orogenic processes (plate interaction cycles) constitute the evolution of these provinces the older occurred in the Tonian (smaller in area) and the younger Brasiliano that is present in all provinces The Tonian cycles (pre-Rodinia fission?) are still being sorted out and many questions still need to be answered The Brasiliano orogenic collage events (post-Rodinia fission?) developed in three main stages in part coeval from a province to another and are 650-600 580-560 and 540-500 Ma respectively (the late event reaching the Ordovician) The first group of orogenies is recorded in practically all provinces The third group is restricted to part of the Mantiqueira Province (southeast of the platform Buzios Orogeny) and present in the Pampean province (SW of the platform) For all these groups of orogenic events there are considerable records of rock assemblages related to processes of convergent plate interaction opening accretion collision and further extrusion There is a good correlation between the geologic and geotectonic data and geochemical and isotopic data The late tectonic processes (post-orogenic magmatism foreland basins etc) of the first two groups compete in time in distinct spaces with the peak of orogenic processes in the third group The introduction of the SHRIMP U-Pb methodology was fundamental to separate the Tonian and post-Tonian orogenic groups and their respective divisions in time and space Thus there are still many open points/problems which lead to expectations of addressing these issues in the near future with the more Intense use of this methodology (C) 2010 Elsevier B V All rights reserved

Novel immunoadjuvants based on cationic lipid: Preparation, characterization and activity in vivo

The interactions between three different protein antigens and dioctadecyldimethylammonium bromide (DODAB) dispersed in aqueous solutions from probe sonication or adsorbed its one bilayer onto particles was comparatively investigated. The three model proteins were bovine serum albumin (BSA), purified 18 kDa/14 kDa antigens from Taenia crassiceps (18/14-Tcra) and a recombinant, heat-shock protein hsp-18 kDa from Mycobacterium leprae. Protein-DODAB complexes in water solution were characterized by dynamic light scattering for sizing and zeta-potential analysis. Cationic complexes (80-100 nm of mean hydrodynamic diameter) displayed sizes similar to those of DODAB bilayer fragments (BF) in aqueous solution and good colloid stability over a range of DODAB and protein concentrations. The amount of cationic lipid required for attaining zero of zeta-potential at a given protein amount depended on protein nature being smaller for 18 kDa/14 kDa antigens than for BSA. Mean diameters for DODAB/protein complexes increased, whereas zeta-potentials decreased with NaCl or protein concentration. In mice, weak IgG production but significant cellular immune responses were induced by the complexes in comparison to antigens alone or carried by aluminum hydroxide as shown from IgG in serum determined by ELISA, delayed type hypersensitivity reaction from footpad swelling tests and cytokines analysis. The novel cationic adjuvant/protein complexes revealed good colloid stability and potential for vaccine design at a reduced DODAB concentration. (C) 2009 Elsevier Ltd. All rights reserved.