Synthesis, structure, transformation studies and catalytic properties of open-framework cadmium thiosulfate compounds

Five new thiosulfate based inorganic-organic hybrid open-framework compounds have been synthesized employing mild reaction conditions. Of the five compounds, [Na-2(H2O)(8)][Cd(C10H8N2)( S2O3)(2)]center dot 2H(2)O, I and [Cd-2(C10H8N2)(2)(HS2O3)(2)(S2O3)(2)][(C10H9N2)(2)(C10H8N2)(2)]center dot 8H(2)O, II have one-dimensional (1D) structures and [Cd(C10H8N2)(H2O)(2)(S2O3)]center dot 2H(2)O, III, [Cd-2(C10H8N2)(3)(S2O3)(2)], IV and [Cd-2(C10H8N2)(2.5)(S2O3)(2)], V have three- dimensional (3D) structures. The 1D structures are somewhat related, formed by the bonding between tetrahedral Cd centers (CdN2S2) and 4,4'-bipyridine (bpy) units. The inter-chain spaces are occupied by the hanging thiosulfate units in both the cases along with Na(H2O)(6) chains in I and free bpy units in II. The three 3D structures have one-dimensional cadmium thiosulfate chains linked by bpy units. Interpenetration has been observed in all the 3D structures. The 3D structures appear to be related and can be derived from fgs net. Transformation studies on the 1D compound, [Na-2(H2O)(8)][Cd(C10H8N2)(S2O3)(2)]center dot 2H(2)O, I, indicated a facile formation of [Cd(C10H8N2)(H2O)(2)(S2O3)]center dot 2H(2)O, III. Prolonged heating of I gave rise to a 3D cadmium sulfate phase, [Cd-2(C10H8N2)(2)(H2O)(3)(SO4)(2)]center dot 2H(2)O, VI. Compound VI has one-dimensional cadmium sulfate chains formed by six-membered rings connected by bpy units to form a 3D structure, which appears to resemble the topological arrangement of III. Transformation studies of III indicates the formation of IV and V, and at a higher temperature a new 3D cadmium sulfate, [Cd(C10H8N2)(SO4)], VII. Compound VII has a 4 x 4 grid cadmium sulfate layers pillared by bpy units. All the compounds were characterized by PXRD, TGA, IR and UV-visible studies. Preliminary studies on the possible use of the 3D compounds (III-VII) in heterogeneous cyanosilylation of imines appear to be promising.

Multiple support excitations of open-plane frames by a filtered white noise and soil-structure interaction

Seismic structural design is essentially the estimation of structural response to a forced motion, which may be deterministic or stochastic, imposed on the ground. The assumption that the same ground motion acts at every point of the base of the structure (or at every support) is not always justifiable; particularly in case of very large structures when considerable spatial variability in ground motion can exist over significant distances example long span bridges. This variability is partly due to the delay in arrival of the excitation at different supports (which is called the wave passage effect) and due to heterogeneity in the ground medium which results in incoherency and local effects. The current study examines the influence of the wave passage effect (in terms of delay in arrival of horizontal ground excitation at different supports and neglecting transmission through the structure) on the response of a few open-plane frame building structures with soil-structure interaction. The ground acceleration has been modeled by a suitably filtered white noise. As a special case, the ground excitation at different supports has also been treated as statistically independent to model the extreme case of incoherence due to local effects and due to modifications to the ground motion resulting from wave reflections and refractions in heterogeneous soil media. The results indicate that, even for relatively short spanned building frames, wave passage effect can be significant. In the absence of soil-structure interaction, it can significantly increase the root mean square (rms) value of the shear in extreme end columns for the stiffer frames but has negligible effect on the flexible frames when total displacements are considered. It is seen that pseudo-static displacements increasingly contribute to the rms value of column shear as the time delay increases both for the stiffer and for the more flexible frames. When soil-structure interaction is considered, wave passage effect (in terms of total displacements) is significant only for low soil shear modulus, G. values (where soil-structure interaction significantly lowers the fundamental frequency) and for stiff frames. The contribution of pseudo-static displacement to these rms values is found to decrease with increase in G. In general, wave passage effect for most interactive frames is insignificant compared to the attenuating effect a decrease in G, has on the response of the interactive structure to uniform support excitation. When the excitations at different supports are statistically independent, it is seen that for both the stiff and flexible frames, the rms value of the column shear in extreme end columns is several times larger (more for the stiffer frames) than the value corresponding to uniform base excitation with the pseudo-static displacements contributing over 99% of the rms value of column shear. Soil-structure interaction has an attenuating effect on the rms value of the column shear, the effect decreasing with increase in G,. Here too, the pseudo-static displacements contribute very largely to the column shear. The influence of the wave passage effect on the response of three 2-bay frames with and without soil-structure interaction to a recorded horizontal accelerogram is also examined. (C) 2010 Elsevier Ltd. All rights reserved.

Open manifolds, Ozsvath-Szabo invariants and exotic R-4 ` S

We construct an invariant of certain open four-manifolds using the Heegaard Floer theory of Ozsvath and Szabo. We show that there is a manifold X homeomorphic to R-4 for which the invariant is non-trivial,showing that X is an exotic R-4. This is the first invariant that detects exotic R-4' s. (C) 2009 Published by Elsevier GmbH.

Comparison of promoter-specific events during transcription initiation in mycobacteria

DNA protein interactions that occur during transcription initiation play an important role in regulating gene expression. To initiate transcription, RNA polymerase (RNAP) binds to promoters in a sequence-specific fashion. This is followed by a series of steps governed by the equilibrium binding and kinetic rate constants, which in turn determine the overall efficiency of the transcription process. We present here the first detailed kinetic analysis of promoter RNAP interactions during transcription initiation in the sigma(A)-dependent promoters P-rrnAPCL1, P-rrnB and P-gyr of Mycobacterium smegmatis. The promoters show comparable equilibrium binding affinity but differ significantly in open complex formation, kinetics of isomerization and promoter clearance. Furthermore, the two rrn promoters exhibit varied kinetic properties during transcription initiation and appear to be subjected to different modes of regulation. In addition to distinct kinetic patterns, each one of the housekeeping promoters studied has its own rate-limiting step in the initiation pathway, indicating the differences in their regulation.

Ecology of the Asian Elephant in Southern India. I. Movement and Habitat Utilization Patterns

The movement and habitat utilization patterns were studied in an Asian elephant population during 1981-83 within a 1130 km2 area in southern India (110 30' N to 120 0' N and 760 50' E to 770 15' E). The study area encompasses a diversity of vegetation types from dry thorn forest (250-400 m) through deciduous forest (400-1400 m) to stunted evergreen shola forest and grassland (1400-1800 m). Home range sizes of some identified elephants were between 105 and 320 km2. Based on the dry season distribution, five different elephant clans, each consisting of between 50 and 200 individuals and having overlapping home ranges, could be defined within the study area. Seaso- nal habitat preferences were related to the availability of water and the palatability of food plants. During the dry months (January-April) elephants congregated at high densities of up to five individuals kM-2 in river valleys where browse plants had a much higher protein content than the coarse tall grasses on hill slopes. With the onset of rains of the first wet season (May- August) they dispersed over a wider area at lower densities, largely into the tall grass forests, to feed on the fresh grasses, which then had a high protein value. During the second wet season (September-December), when the tall grasses became fibrous, they moved into lower elevation short grass open forests. The normal movement pattern could be upset during years of adverse environmental con- ditions. However, the movement pattern of elephants in this region has not basically changed for over a century, as inferred from descriptions recorded during the nineteenth century.

A building-up process in open-framework metal carboxylates that involves a progressive increase in dimensionality

Extensive research work has been carried out in the last few years on the synthesis and characterization of several families of open-framework materials, including aluminosilicates,[1] phosphates,[2] and carboxylates.[3] These studies have shown the occurrence of a variety of three dimensional (3D) architectures containing channels and other features.

A singularity-free cosmological model in ECSK theory

In the framework of the ECSK [Einstein-Cartan-Sciama-Kibble] theory of cosmology, a scalar field nonminimally coupled to the gravitational field is considered. For a Robertson-Walker open universe (k=0) in the radiation era, the field equations admit a singularity-free solution for the scale factor. In theory, the torsion is generated through nonminimal coupling of a scalar field to the gravitation field. The nonsingular nature of the cosmological model automatically solves the flatness problem. Further absence of event horizon and particle horizon explains the high degree of isotropy, especially of 2.7-K background radiation.

Effect of Prestrain on Fracture Toughness of Rolled Mild Steel with Significant Inclusion Content

The basic method of JIc calculation using a single specimen is discussed. Dokouipil's approach for evaluating the JIc value is extended further and the effect of prestrain on rolled mild steel with significant inclusions is studied using this modified approach. Although this method does not give an accurate value of JIc, it is quite effective for a comparative study. While the fracture toughness of annealed and 7% prestrained materials are about the same, the fracture toughness of 3% prestrained material is significantly lower.

Nonsingular cosmological models: the massive scalar field case

The nonminimal coupling of a massive self-interacting scalar field with a gravitational field is studied. Spontaneous symmetry breaking occurs in the open universe even when the sign on the mass term is positive. In contrast to grand unified theories, symmetry breakdown is more important for the early universe and it is restored only in the limit of an infinite expansion. Symmetry breakdown is shown to occur in flat and closed universes when the mass term carries a wrong sign. The model has a naturally defined effective gravitational coupling coefficient which is rendered time-dependent due to the novel symmetry breakdown. It changes sign below a critical value of the cosmic scale factor indicating the onset of a repulsive field. The presence of the mass term severely alters the behaviour of ordinary matter and radiation in the early universe. The total energy density becomes negative in a certain domain. These features make possible a nonsingular cosm

Microstructure and Properties of the Spray-Formed and Extruded 7075 Al Alloy

In the present investigation, a very good combination of strength and ductility, 630MPa 0.2% proof stress and 14.8% elongation to fracture in tensile test, has been obtained for the 7075 Al alloy after optimizing the processing parameters for spray forming, hot extruding the spray deposit, and peak aging the samples taken from the extruded rod. The spray deposits contained some porosity but it was almost eliminated on hot extrusion. Electron probe microanalysis revealed that even though spray forming was carried out in an open atmosphere, it did not affect the oxygen content and its distribution in the material on spray forming, because the atomizing argon gas provided a protective cover to molten droplets and prevented their oxidation. The chemical composition of the spray-formed material was found to be almost the same as the raw material, and the major alloying elements were found to be uniformly distributed in the extruded rod.

Spin and mass content of linearized Poincaré gauge theories

A unified gauge theory of massless and massive spin-2 fields is of considerable current interest. The Poincaré gauge theories with quadratic Lagrangian are linearized, and the conditions on the parameters are found which will lead to viable linear theories with massive gauge particles. As well as the 2+ massless gravitons coming from the translational gauge potential, the rotational gauge potentials, in the linearized limit, give rise to 2+ and 2− particles of equal mass, as well as a massive pseudoscalar.

Use of the Nasicon/Na2SO4 couple in a solid state sensor for SOx (x=2,3)

The e.m.f. of a concentration cell for SO x (x=2,3)-O2 incorporating Nasicon as the main solid electrolyte has been measured in the temperature range 720 to 1080 K. The cell arrangement can be represented as,$$Pt, O'_2 + SO'_2 + SO'_3 \left| {Na_2 SO_4 \left\| {\left. {Nasicon} \right\|} \right.} \right.\left. {Na_2 SO_4 } \right|SO''_3 + SO''_2 + O''_2 , Pt$$ The Na2SO4 acts both as an auxiliary electrode, converting chemical potentials of SO x and O2 to equivalent sodium potentials, and as an electrolyte. The presence of Na2SO4 provides partial protection of Nasicon from chemical reaction with gas mixtures containing SO x . The open circuit e.m.f. of the cell is in close agreement with values given by the Nernst equation. For certain fixed inlet gas compositions of SO2+O2, the e.m.f. varies non-linearly with temperature. The intrinsic response time of the cell to step changes in gas composition is estimated to vary from sim2.0 ksec at 723K to sim 0.2 ksec at 1077K. The cell functions well for large differences in partial pressures of SO3(pPrimeSO 3/pprimeSO 3ap104) at the electrodes.

Crystal Structure of Staphylococcus aureus Metallopeptidase (Sapep) Reveals Large Domain Motions between the Manganese-bound and Apo-states

Proteases belonging to the M20 family are characterized by diverse substrate specificity and participate in several metabolic pathways. The Staphylococcus aureus metallopeptidase, Sapep, is a member of the aminoacylase-I/M20 protein family. This protein is a Mn2+-dependent dipeptidase. The crystal structure of this protein in the Mn2+-bound form and in the open, metal-free state suggests that large interdomain movements could potentially regulate the activity of this enzyme. We note that the extended inactive conformation is stabilized by a disulfide bond in the vicinity of the active site. Although these cysteines, Cys(155) and Cys(178), are not active site residues, the reduced form of this enzyme is substantially more active as a dipeptidase. These findings acquire further relevance given a recent observation that this enzyme is only active in methicillin-resistant S. aureus. The structural and biochemical features of this enzyme provide a template for the design of novel methicillin-resistant S. aureus-specific therapeutics.

Efficient algorithms for domination and Hamilton circuit problems on permutation graphs

The domination and Hamilton circuit problems are of interest both in algorithm design and complexity theory. The domination problem has applications in facility location and the Hamilton circuit problem has applications in routing problems in communications and operations research.The problem of deciding if G has a dominating set of cardinality at most k, and the problem of determining if G has a Hamilton circuit are NP-Complete. Polynomial time algorithms are, however, available for a large number of restricted classes. A motivation for the study of these algorithms is that they not only give insight into the characterization of these classes but also require a variety of algorithmic techniques and data structures. So the search for efficient algorithms, for these problems in many classes still continues.A class of perfect graphs which is practically important and mathematically interesting is the class of permutation graphs. The domination problem is polynomial time solvable on permutation graphs. Algorithms that are already available are of time complexity O(n2) or more, and space complexity O(n2) on these graphs. The Hamilton circuit problem is open for this class.We present a simple O(n) time and O(n) space algorithm for the domination problem on permutation graphs. Unlike the existing algorithms, we use the concept of geometric representation of permutation graphs. Further, exploiting this geometric notion, we develop an O(n2) time and O(n) space algorithm for the Hamilton circuit problem.