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.

On the use of a coordinate transformation for analysis of axisymmetric vibration of polar orthotropic annular plates

Estimates of natural frequencies corresponding to axisymmetric modes of flexural vibration of polar orthotropic annular plates have been obtained for various combinations of clamped, simply supported and free edge conditions. A coordinate transformation in the radial direction has been used to obtain effective solutions by the classical Rayleigh-Ritz method. The analysis with this transformation has been found to be advantageous in computations, particularly for large hole sizes, over direct analysis. Numerical results have been obtained for various values of hole sizes and rigidity ratio. The eigenvalue parameter has been found to vary more or less linearly with the rigidity ratio. A comparison with the results for isotropic plates has brought out some interesting features.

Phonon-mediated two-magnon light scattering from ferromagnetic insulators

An indirect mechanism of light scattering from spin-waves in ferromagnetic insulators via two-magnon one-phonon process is proposed. Following linear response theory, an expression has been derived for the differential scattering cross-section in the mean-field-approximation.

Essential role of PI3-kinase pathway in p53-mediated transcription: Implications in cancer chemotherapy

The PI3-kinase pathway is the target of inactivation in achieving better cancer chemotherapy. Here, we report that p53-mediated transcription is inhibited by pharmacological inhibitors and a dominant-negative mutant of PI3-kinase, and this inhibition was relieved by a constitutively active mutant of PI3-kinase. Akt/PKB and mTOR, the downstream effectors of PI3-kinase, were also found to be essential. LY294002 (PI3-kinase inhibitor) pre-treatment altered the post-translational modifications and the sub-cellular localization of p53. Although LY294002 increased the chemosensitivity of cells to low concentrations of adriamycin (adriamycin-low), it protected the cells from cytotoxicity induced by high concentrations of adriamycin (adriamycin-high) in a p53-dependent manner. Further, we found that LY294002 completely abolished the activation of p53 target genes (particularly pro-apoptotic) under adriamycin-high conditions, whereas it only marginally repressed the p53 target genes under adriamycin-low conditions; in fact, it further activated the transcription of NOXA, HRK, APAF1 and CASP5 genes. Thus, the differential effect of PI3-kinase on p53 functions seems to be responsible for the differential regulation of DNA damage-induced cytotoxicity and cell death by PI3-kinase. Our finding becomes relevant in the light of ongoing combination chemotherapy trials with the PI3-kinase pathway inhibitors and underscores the importance of p53 status in the careful formulation of combination chemotherapies. Oncogene (2010) 29, 3605-3618; doi: 10.1038/onc.2010.123; published online 26 April 2010

A Relationship Mediated Theory of Internal Marketing (summary section only)

This report presents a new theory of internal marketing. The thesis has developed as a case study in retrospective action research. This began with the personal involvement of the author in an action research project for customer service improvement at a large Australian retail bank. In other words, much of the theory generating ‘research’ took place after the original project ‘action’ had wound down. The key theoretical proposition is that internal marketing is a relationship development strategy for the purpose of knowledge renewal. In the banking case, exchanges of value between employee participants emerged as the basis for relationship development, with synergistic benefits for customers, employees and the bank. Relationship development turned out to be the mediating variable between the learning activity of employee participants at the project level and success in knowledge renewal at the organisational level. Relationship development was also a pivotal factor in the motivation and customer consciousness of employees. The conclusion reached is that the strength of relationship-mediated internal marketing is in combining a market focused commitment and employee freedom in project work to achieve knowledge renewal. The forgotten truth is that organisational knowledge can be renewed through dialogue and learning, through being trustworthy, and by gaining the trust of employees in return.

Service Productivity: Toward a Conceptualisation of the Transformation of inputs

The productivity of a process is related to how effectively input resources are transformed into value for customers. For the needs of manufacturers of physical products there are widely used productivity concepts and measurements instruments. However, in service processes the underlying assumptions of these concepts and models do not hold. For example, manufacturing-based productivity models assume that an altered configuration of input resources in the production process does not lead to quality changes in outputs (the constant-quality assumption). However, in a service context changes in the production resources and productions systems do affect the perceived quality of services. Therefore, using manufacturing-oriented productivity models in service contexts are likely to give managers wrong directions for action. Research into the productivity of services is still scarce, because of the lack of viable models. The purpose of the present article is to analyse the requirements for the development of a productivity concept for service operations. Based on the analysis, a service productivity model is developed. According to this model, service productivity is a function of 1) how effectively input resources into the service (production) process are transformed to outputs in the form of services (internal or cost efficiency), 2) how well the quality of the service process and its outcome is perceived (external or revenue efficiency), and 3) how effectively the capacity of the service process is utilised (capacity efficiency). In addition, directions for developing measurement models for service productivity are discussed.

Low Temperature Synthesis of Nano-Crystalline CaCu3Ti4O12 Through aFuel Mediated Auto-Combustion Pathway

A novel, cost effective,environment-friendly and energetically beneficial alternative method for the synthesis of giant dielectric pseudo-perovskite material CaCu3Ti4O12 (CCTO) is presented. The method involved auto-combustion of an aqueous precursor solution in oxygen atmosphere with the help of external fuels and is capable of producing high amount of CCTO at ultra-low temperature, in the combustion residue itself. The amount of phase generated was observed to be highly dependent on the combustion process i.e. on the nature and amount of external-fuels added for combustion. Two successful fuel combinations capable of producing reasonably higher amount of the desired compound were investigated. On a structural characterization grain size was observed to decrease drastically to nano-dimension compared to submicron-size that was obtained in a traditional sol-gel combustion and subsequent cacination method. Therefore, the method reported can produce nano-crystalline CaCu3Ti4O12 ceramic matrix at an ultra-low temperature and is expected to be applicable for other multifunctional perovskite oxide materials.

An unusual C-H center dot center dot center dot O hydrogen bond mediated reversal of polypeptide chain direction in a synthetic peptide helix

An unusual C-terminal conformation has been detected in a synthetic decapeptide designed to analyze the stereochemistry of helix termination in polypeptides. The crystal structure of the decapeptide Boc-Leu-Aib-Val-Ala-Leu-Aib-Val-(D)Ala-(D)Leu-Aib-OMe reveals a helical segment spanning residues 1-7 and helix termination by formation of a Schellman motif, generated by (D)Ala(8) adopting the left-handed helical (alpha(L)) conformation. The extended conformation at (D)Leu(9) results in a compact folded structure, stabilized by a potentially strong C-H ... O hydrogen bond between Ala(4) (CH)-H-alpha and (D)Leu(9)CO. The parameters for C-H ... O interaction are Ala(4) (CH)-H-alpha .. O=C (D)Leu(9) distance 3.27 Angstrom C-alpha-H .. O angle 176 degrees, and O .. H-alpha distance 2.29 Angstrom. This structure suggests that insertion of contiguous D-residues may provide a handle for the generation of designed structures containing more than one helical segment folded in a compact manner. (C) 2000 Academic Press.

Narratives of Travel and the Travelling Concept of Narrative: Genre Blending and the Art of Transformation

In this article I shall argue that understandings of what constitutes narrative, how it functions, and the contexts in which it applies have broadened in line with cultural, social and intellectual trends which have seen a blurring, if not the dissolution, of boundaries between ‘fact’ and ‘fiction’; ‘literary’ and ‘non-literary’ narrative spaces; history and story; concepts of time and space, text and image, teller and tale, representation and reality.To illustrate some of the ways in which the concept of narrative has travelled across disciplinary and generic boundaries, I shall look at The Art of Travel (de Botton 2003), with a view to demonstrating how the blending of genres works to produce a narrative that is at once personal and philosophical; visual and verbal; didactic and poetic. I shall show that such a text constitutes a site of interrogation of concepts of narrative, even as it depends on the reader’s ability to narrativize experience.

pH mediated delamination of anionic clay-like nickel-zinc hydroxysalt in water through intercalation of zwitterionic p-aminobenzoate ions

p-aminobenzoate could be intercalated into the anionic clay, Ni3Zn2(OH)(8)(OAc)(2)center dot 2H(2)O at a high pH (similar to 10). When the pH was reduced to similar to 7 while washing colloidal dispersion due to delamination was observed. The development of partial positive charge on the amine end of the intercalated anion causes repulsion between the layers leading to delamination and colloidal dispersion of monolayers in water. The layers could be restacked from the colloid to form the parent solid either by increasing the pH or by evaporation.

Tetrathiomolybdate Mediated Rearrangement of Aziridinemethanol Tosylates: A Thia-Aza-Payne Rearrangement

Aziridinemethanol sulfonate esters react with tetrathiomolybdate 1 to give thiirane derivatives as the major product and cyclic disulfides as minor product under mild reaction conditions via an unprecedented thia-aza-Payne-type rearrangement. Interestingly, when the reaction of I was carried out with 2-aziridino-cyclohexanol derivatives it resulted in the formation of thia-bicyclo[3.1.1]heptane or dithia-bicyclo[3.2.1]octane derivatives.

Manganese-mediated ferromagnetism in La2Fe1-xMn2xCr1-xO6 perovskite oxides

We have investigated the structure and magnetic properties of the perovskite oxides of the formula La2Fe1-xMn2xCr1-xO6 (0 < x < 1.0). For 0 < x <= 0.5, the members adopt the orthorhombic (Pbnm) structure, where the transition metal atoms are disordered at the 4b sites and the MO6 (M = Fe, Mn, Cr) octahedra become increasingly distorted with increasing x. For 0.65 <= x < 1.0, the members adopt the rhombohedral (R-3c) structure that is similar to LaMnO3+delta (delta >= 0.1) where the MO6 octahedra are undistorted. While the magnetic properties of the latter series are largely similar to the parent LaMnO3+delta arising from the double-exchange (DE) between mixed valent Mn-III/Mn-IV, the magnetic properties of the orthorhombic members show a distinct (albeit weak) ferromagnetism (T-C similar to 200 K) that seems to arise from a Mn-III-mediated superexchange (SE) between Fe-III/Cr-III in the disordered perovskite structure containing Fe-III, Mn-III and Cr-III.