Synthesis of strained macrocyclic biaryls for enthalpy-driven ring-opening polymerization

Polymerizable macrocyclic biarylene-ether-ketones and biarylene-ether-sulfones are accessible from linear, bis(chloro)-terminated oligomers via nickel-catalyzed, intramolecular coupling under pseudo-high-dilution conditions. Single-crystal X-ray analyses of the resulting cyclo-oligomers reveal extremely distorted and highly strained geometries, with 4,4 '-biphenylene units showing deviations of up to 70 degrees from linearity.

Recent work on entropically-driven ring-opening polymerizations: some potential applications

The entropically-driven ring-opening polymerization of macrocyclic monomers (> ca. 14 ring atoms per repeat unit) and/or macrocyclic oligomers is a relatively new method of polymer synthesis that exploits the well-known phenomenon of ring-chain equilibria. It attracts interest because of its novel features. For example, these ring-opening polymerizations emit no volatiles and little or no heat. This review considers the principles of entropically-driven ring-opening polymerizations, gives selected examples and discusses potential applications. The latter include micromolding, high throughput syntheses and the synthesis of supramolecular polymers. Copyright (c) 2005 John Wiley T Sons, Ltd.

4,4 '-Dipyridyl-N,N '-dioxide complexes of metal-thiocyanate/selenocyanate: pi-stacked molecular rods as three-dimensional support for two-dimensional polymeric sheets and intra/interchain S center dot center dot center dot S interaction dependent architecture of the R-2(2)(8) synthon driven assembly of one-dimensional polymeric chains

Three supramolecular complexes of Co(II) using SCN-/SeCN- in combination with 4,4'-dipyridyl-N,N'-dioxide (dpyo), i.e., {[Co(SCN)(2)(dpyo)(2)].(dpyo)}(n) ( 1), {[Co(SCN)(2)(dpyo)(H2O)(2)].(H2O)}(n) ( 2), {[Co(SeCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 3), have been synthesized and characterized by single-crystal X-ray analysis. Complex 1 is a rare example of a dpyo bridged two-dimensional (2D) coordination polymer, and pi-stacked dpyo supramolecular rods are generated by the lattice dpyo, passing through the rhombic grid of stacked layers, resulting in a three-dimensional (3D) superstructure. Complexes 2 and 3 are isomorphous one-dimensional (1D) coordination polymers [-Co-dpyo-Co-] that undergo self-assembly leading to a bilayer architecture derived through an R-2(2)(8) H-bonding synthon between coordinated water and dpyo oxygen. A reinvestigation of coordination polymers [Mn(SCN)(2)(dpyo)( H2O)(MeOH)](n) ( 4) and {[Fe(SCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 5) reported recently by our group [ Manna et al. Indian J. Chem. 2006, 45A, 1813] reveals brick wall topology rather than bilayer architecture is due to the decisive role of S center dot center dot center dot S/Se center dot center dot center dot Se interactions in determining the helical nature in 4 and 5 as compared to zigzag polymeric chains in 2 and 3, although the same R-2(2)(8) synthon is responsible for supramolecular assembly in these complexes.

Coordination-driven self-assembly of a novel carbonato-bridged heteromolecular neutral nickel(II) triangle by atmospheric CO2 fixation

Formation of a quasi-symmetrical mu(3)-carbonato-bridged self-assembled heteromolecular triangle of Ni(II), [(mu(3)-CO3){Ni-2(salmeNH)(2)(NCS)(2)}[Ni(salmeNH(2))(2)]center dot Et2O center dot H2O (HsalmeNH = 2-[(3-methylamino-propylimino)-methyl]-phenol) involves atmospheric CO2 uptake in a neutral medium, by spontaneous self-reorganization of the starting mononuclear Ni(II)-Schiff-base complex, [Ni(salmeNH)(2)]. The environment around Ni(II) in two of the subunits is different from the third one. The starting complex, (Ni(salmeNH)(2)], and one of the possible intermediate species, [Ni(salmeNH(2))(2)(NCS)(2)], which has a very similar coordination environment to that in the third Ni(II) center, have been characterized structurally. A plausible mechanism for the formation of such a triangle has also been proposed. The compound shows a very strong antiferromagnetic coupling. Fit as a regular triangular arrangement gave J = -53.1, g = 2.24, and R = 1.5 x 10(-4).

A knowledge-driven management approach to environmental-conscious construction

This paper aims to introduce a knowledge-based managemental prototype entitled Eþ for environmental-conscious construction relied on an integration of current environmental management tools in construction area. The overall objective of developing the Eþ prototype is to facilitate selectively reusing the retrievable knowledge in construction engineering and management areas assembled from previous projects for the best practice in environmental-conscious construction. The methodologies adopted in previous and ongoing research related to the development of the Eþ belong to the operations research area and the information technology area, including literature review, questionnaire survey and interview, statistical analysis, system analysis and development, experimental research and simulation, and so on. The content presented in this paper includes an advanced Eþ prototype, a comprehensive review of environmental management tools integrated to the Eþ prototype, and an experimental case study of the implementation of the Eþ prototype. It is expected that the adoption and implementation of the Eþ prototype can effectively facilitate contractors to improve their environmental performance in the lifecycle of projectbased construction and to reduce adverse environmental impacts due to the deployment of various engineering and management processes at each construction stage.

Velocity profiles and frictional pressure drop for shear thinning materials in lid-driven cavities with fully developed axial flow

A finite element numerical study has been carried out on the isothermal flow of power law fluids in lid-driven cavities with axial throughflow. The effects of the tangential flow Reynolds number (Re-U), axial flow Reynolds number (Re-W), cavity aspect ratio and shear thinning property of the fluids on tangential and axial velocity distributions and the frictional pressure drop are studied. Where comparison is possible, very good agreement is found between current numerical results and published asymptotic and numerical results. For shear thinning materials in long thin cavities in the tangential flow dominated flow regime, the numerical results show that the frictional pressure drop lies between two extreme conditions, namely the results for duct flow and analytical results from lubrication theory. For shear thinning materials in a lid-driven cavity, the interaction between the tangential flow and axial flow is very complex because the flow is dependent on the flow Reynolds numbers and the ratio of the average axial velocity and the lid velocity. For both Newtonian and shear thinning fluids, the axial velocity peak is shifted and the frictional pressure drop is increased with increasing tangential flow Reynolds number. The results are highly relevant to industrial devices such as screw extruders and scraped surface heat exchangers. (c) 2006 Elsevier Ltd. All rights reserved.

A little learning is a dangerous thing: an experimental demonstration of ignorance-driven inference

Studies of ignorance-driven decision making have been employed to analyse when ignorance should prove advantageous on theoretical grounds or else they have been employed to examine whether human behaviour is consistent with an ignorance-driven inference strategy (e. g., the recognition heuristic). In the current study we examine whether-under conditions where such inferences might be expected-the advantages that theoretical analyses predict are evident in human performance data. A single experiment shows that, when asked to make relative wealth judgements, participants reliably use recognition as a basis for their judgements. Their wealth judgements under these conditions are reliably more accurate when some of the target names are unknown than when participants recognize all of the names (a "less-is-more effect"). These results are consistent across a number of variations: the number of options given to participants and the nature of the wealth judgement. A basic model of recognition-based inference predicts these effects.

Semantic-driven context-aware visual information indexing and retrieval: applied in the film post-production domain

A large volume of visual content is inaccessible until effective and efficient indexing and retrieval of such data is achieved. In this paper, we introduce the DREAM system, which is a knowledge-assisted semantic-driven context-aware visual information retrieval system applied in the film post production domain. We mainly focus on the automatic labelling and topic map related aspects of the framework. The use of the context- related collateral knowledge, represented by a novel probabilistic based visual keyword co-occurrence matrix, had been proven effective via the experiments conducted during system evaluation. The automatically generated semantic labels were fed into the Topic Map Engine which can automatically construct ontological networks using Topic Maps technology, which dramatically enhances the indexing and retrieval performance of the system towards an even higher semantic level.

A design for business intelligence service in demand driven supply chain management

This paper discusses the problems inherent within traditional supply chain management's forecast and inventory management processes arising when tackling demand driven supply chain. A demand driven supply chain management architecture developed by Orchestr8 Ltd., U.K. is described to demonstrate its advantages over traditional supply chain management. Within this architecture, a metrics reporting system is designed by adopting business intelligence technology that supports users for decision making and planning supply activities over supply chain health.