Nickel(II) complexes of whole set of the simple ethylenediaminetetracarboxylate ligands:DFT study of complexes invoking molecular orbital and configurational analysis

The whole set of the nickel(II) complexes with no derivatized edta-type hexadentate ligands has been investigated from their structural and electronic properties. Two more complexes have been prepared in order to complete the whole set: trans(O5)-[Ni(ED3AP)]2- and trans(O5O6)-[Ni(EDA3P)]2- complexes. trans(O5) geometry has been verified crystallographically and trans(O5O6) geometry of the second complex has been predicted by the DFT theory and spectral analysis. Mutual dependance has been established between: the number of the five-membered carboxylate rings, octahedral/tetrahedral deviation of metal-ligand/nitrogen-neighbour-atom angles and charge-transfer energies (CTE) calculated by the Morokuma’s energetic decomposition analysis; energy of the absorption bands and HOMO–LUMO gap.

The effect of complexes on combustion

The twin goals of low and efficient fuel use and minimum emissions are increasingly being addressed by research in both the motor and the catalyst industries of the world. This study was designed to attempt to investigate these goals. For diesel engine vehicles, this can be achieved by improving the efficiency of the fuel combustion in the combustion chamber. By having a suitable oxidation catalyst in the fuel one would expect the efficiency of the fuel combustion to be increased and fewer partial oxidation products to be formed. Also by placing a catalyst converter in the exhaust system partial oxidation products may be converted to more desirable final products. Finally, in this research the net catalytic effect of using an additive treated fuel and a blank ceramic monolith to trap the metal in the exhaust gases for potential use as catalytic converter was investigated. Suitable metal additives must yield a stable solution in the fuel tank. That is, they should not react with the air, water and rust that are always present. The research was targeted on the synthesis of hydrocarbon-soluble complexes that might exhibit unusually slow rates of ligand substitution. For materials containing metal ions, these properties are best met by using multi-dentate ligands that form neutral complexes. Metal complexes have been synthesised using acetylacetone derivatives, schiff base ligands and macrocyclic polyamine ligands, as potential pro-oxidant additives. Their thermal stabilities were also investigated using a differential thermal analysis instrument. The complexes were then investigated as potential additives for use in diesel fuel. The tests were conducted under controlled conditions using a diesel combustion bomb simulating the combustion process in the D.I. diesel engine, a test bed engine, and a vehicle engine.

Copper(II) complexes with unsymmetrical pentadentate ed3a-type diamino-tricarboxylate ligands. Crystal structures, configurational analysis and DFT study of complexes

The O–O–N–N–O-type pentadentate ligands H3ed3a, H3pd3a and H3pd3p (H3ed3a stands ethylenediamine-N,N,N′-triacetic acid; H3pd3a stands 1,3-propanediamine-N,N,N′-triacetic acid and H3pd3p stands 1,3-propanediamine-N,N,N′-tri-3-propionic acid) and the corresponding novel octahedral or square-planar/trigonal-bipyramidal copper(II) complexes have been prepared and characterized. H3ed3a, H3pd3a and H3pd3p ligands coordinate to copper(II) ion via five donor atoms (three deprotonated carboxylate atoms and two amine nitrogens) affording octahedral in case of ed3a3− and intermediate square-pyramidal/trigonal-bipyramidal structure in case of pd3a3− and pd3p3−. A six coordinate, octahedral geometry has been established crystallographically for the [Mg(H2O)6][Cu(ed3a)(H2O)]2 · 2H2O complex and five coordinate square-pyramidal for the [Mg(H2O)5Cu(pd3a)][Cu(pd3a)] · 2H2O. Structural data correlating similar chelate Cu(II) complexes have been used for the better understanding the pathway: octahedral → square-pyramidal ↔ trigonal- bipyramid geometry. An extensive configuration analysis is discussed in relation to information obtained for similar complexes. The infra-red and electronic absorption spectra of the complexes are discussed in comparison with related complexes of known geometries. Molecular mechanics and density functional theory (DFT) programs have been used to model the most stable geometric isomer yielding, at the same time, significant structural data. The results from density functional studies have been compared with X-ray data.

Polymer-phospholipid complexes for the solubilisation and delivery of drugs to the eye

Aim: Topical application of ophthalmic drugs is very inefficient; contact lenses used as drug delivery devices could minimize the drug loss and side effects. Styrene-maleic acid copolymers (PSMA) can form polymer-phospholipid complexes with dipalmitoyl phosphatidylcholine (DMPC) in the form of nanometric vesicles, which can easily solubilise hydrophobic drugs. They can be dispersed on very thin contact lens coatings to immobilize the drug on their surface. Methods: Two types of complexes stable at different pH values (5 and 7 respectively) where synthesized and loaded with drugs of different hydrophilicities during their formation process. The drug release was studied in vitro and compared to the free drug. Results: The mean sizes of the complexes obtained by light scattering were 50 nm and 450 nm respectively with low polydispersities. However, they were affected by the drugs load and release. An increase was observed in the duration of the release in the case of hydrophobic drugs, from days to weeks, avoiding initial “burst” and with a lesser amount of total drug released due to the interaction of the drug with the phospholipid core. The size and charge of the different drugs and the complexes nature also affected the release profile. Conclusions: Polymer-phospholipid complexes in the form of nanoparticles can be used to solubilise and release hydrophobic drugs in a controlled way. The drug load and release can be optimised to reach therapeutic values in the eye.

Synthetic, crystallographic, and computational study of copper(II) complexes of ethylenediaminetetracarboxylate ligands

Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands Heda3p and Heddadp (Heda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; H eddadp = ethylenediamine-N,N'-diacetic-N,N'-di-3- propionic acid) have been prepared. An octahedral trans(O) geometry (two propionate ligands coordinated in axial positions) has been established crystallographically for the Ba[Cu(eda3p)]·8HO compound, while Ba[Cu(eddadp)]·8HO is proposed to adopt a trans(O ) geometry (two axial acetates) on the basis of density functional theory calculations and comparisons of IR and UV-vis spectral data. Experimental and computed structural data correlating similar copper(II) chelate complexes have been used to better understand the isomerism and departure from regular octahedral geometry within the series. The in-plane O-Cu-N chelate angles show the smallest deviation from the ideal octahedral value of 90°, and hence the lowest strain, for the eddadp complex with two equatorial ß-propionate rings. A linear dependence between tetragonality and the number of five-membered rings has been established. A natural bonding orbital analysis of the series of complexes is also presented.

Category learning induces position invariance of pattern recognition across the visual field

Human object recognition is considered to be largely invariant to translation across the visual field. However, the origin of this invariance to positional changes has remained elusive, since numerous studies found that the ability to discriminate between visual patterns develops in a largely location-specific manner, with only a limited transfer to novel visual field positions. In order to reconcile these contradicting observations, we traced the acquisition of categories of unfamiliar grey-level patterns within an interleaved learning and testing paradigm that involved either the same or different retinal locations. Our results show that position invariance is an emergent property of category learning. Pattern categories acquired over several hours at a fixed location in either the peripheral or central visual field gradually become accessible at new locations without any position-specific feedback. Furthermore, categories of novel patterns presented in the left hemifield are distinctly faster learnt and better generalized to other locations than those learnt in the right hemifield. Our results suggest that during learning initially position-specific representations of categories based on spatial pattern structure become encoded in a relational, position-invariant format. Such representational shifts may provide a generic mechanism to achieve perceptual invariance in object recognition.

A cross-national comparison of cultural value orientations of Indian, Polish, Russian and American employees

This study examines the cultural value orientations (VOs) of employees (managerial and non-managerial) working in three categories of organizations (professional, technical and local services) in India, Poland, Russia and the USA. The analysis is conducted at both the national and organizational levels. The paper hypothesizes cultural differences at the country level and cultural similarities among employees working for professional and technical oriented organizations and divergence in the VOs of employees working for local services organizations. It also hypothesizes differences in the VOs of managerial and non-managerial employees in the four countries. The investigation has been conducted with the help of a questionnaire survey of 1,852 respondents. The outcomes of the analysis show that there are both cross-country cultural differences and similarities among the VOs of employees of the four nations. Further, significant cultural convergence emerges in the VOs of employees working for both professional and technical organizations, however, no significant cultural similarities or differences are observed for employees of service-based organizations in the four countries. There are some similarities emerging between managerial employees in the research countries. The research contributes to the fields of cross-cultural management, international management and international human resource management.

The impact of performance measurement in strategic planning

Purpose – To investigate the impact of performance measurement in strategic planning process. Design/methodology/approach – A large scale survey was conducted online with Warwick Business School alumni. The questionnaire was based on the Strategic Development Process model by Dyson. The questionnaire was designed to map the current practice of strategic planning and to determine its most influential factors on the effectiveness of the process. All questions were close ended and a seven-point Likert scale used. The independent variables were grouped into four meaningful factors by factor analysis (Varimax, coefficient of rotation 0.4). The factors produced were used to build regression models (stepwise) for the five assessments of strategic planning process. Regression models were developed for the totality of the responses, comparing SMEs and large organizations and comparing organizations operating in slowly and rapidly changing environments. Findings – The results indicate that performance measurement stands as one of the four main factors characterising the current practice of strategic planning. This research has determined that complexity coming from organizational size and rate of change in the sector creates variation in the impact of performance measurement in strategic planning. Large organizations and organizations operating in rapidly changing environments make greater use of performance measurement. Research limitations/implications – This research is based on subjective data, therefore the conclusions do not concern the impact of strategic planning process' elements on the organizational performance achievements, but on the success/effectiveness of the strategic planning process itself. Practical implications – This research raises a series of questions about the use and potential impact of performance measurement, especially in the categories of organizations that are not significantly influenced by its utilisation. It contributes to the field of performance measurement impact. Originality/value – This research fills in the gap literature concerning the lack of large scale surveys on strategic development processes and performance measurement. It also contributes in the literature of this field by providing empirical evidences on the impact of performance measurement upon the strategic planning process.

Marking high-technology market evolution through the foci of market stories:the case of local area networks

Previous research suggests that changing consumer and producer knowledge structures play a role in market evolution and that the sociocognitive processes of product markets are revealed in the sensemaking stories of market actors that are rebroadcasted in commercial publications. In this article, the authors lend further support to the story-based nature of market sensemaking and the use of the sociocognitive approach in explaining the evolution of high-technology markets. They examine the content (i.e., subject matter or topic) and volume (i.e., the number) of market stories and the extent to which content and volume of market stories evolve as a technology emerges. Data were obtained from a content analysis of 10,412 article abstracts, published in key trade journals, pertaining to Local Area Network (LAN) technologies and spanning the period 1981 to 2000. Hypotheses concerning the evolving nature (content and volume) of market stories in technology evolution are tested. The analysis identified four categories of market stories - technical, product availability, product adoption, and product discontinuation. The findings show that the emerging technology passes initially through a 'technical-intensive' phase whereby technology related stories dominate, through a 'supply-push' phase, in which stories presenting products embracing the technology tend to exceed technical stories while there is a rise in the number of product adoption reference stories, to a 'product-focus' phase, with stories predominantly focusing on product availability. Overall story volume declines when a technology matures as the need for sensemaking reduces. When stories about product discontinuation surface, these signal the decline of current technology. New technologies that fail to maintain the 'product-focus' stage also reflect limited market acceptance. The article also discusses the theoretical and managerial implications of the study's findings. © 2002 Elsevier Science Inc. All rights reserved.

Objects and the production of technological forms of life:understanding organisational arrangements from a postsocial perspective

Objects are produced within, and simultaneously affect, the process of organizing as a consequence of their interaction within social collectives. This paper discusses the impact and influences of the growth of post-social relations, between human and technological objects, on social and organisational arrangements. The paper presents a discussion largely at the conceptual level and draws from a variety of literatures, including the burgeoning sociology of science literature. The discussion in this paper is based on a view that posits the growth of intimate links with epistemic objects within organisations and society. Organising through networks of post-social relations increasingly comes to affect the manner in which differing groups of organisational participants, and particularly various categories of knowledge workers, experience time and spatial arrangements within organisations.

Ireland and immigration: explaining the absence of the far right

Garner seeks to explain the absence of far-right political formations in the history of the Republic of Ireland, especially in relation to immigration. He argues that the ‘mainstream’ nationalist parties have implemented a racialized governance of Ireland via the issue of citizenship (in the referendum of 2004). While hegemonic ideas on the racial purity of indigenous populations and the highly ambivalent attitudes and policies on immigration pursued over the last decade are characteristic of a broader European trend, this has not, in the Republic, been accompanied by meaningful far-right political mobilization. Ireland has frequently been seen as sui generis in political terms, and indeed emerges in some ways as a counter-case: increasing hostility towards Others has been identified in the midst of rapid economic growth and political stability. A variety of issues related to the country’s political development have given rise to an especially small left-wing vote, a nationalist centre ground and longlasting domination by a single populist party, Fianna Fa´ il. This party has been partnered in government since 1997 by a free-market party, the Progressive Democrats, who have contributed to Ireland’s movement towards neo-liberal policies and a highly functional approach to immigration. The transition from country of emigration to country of immigration has thus taken place against an ideological backdrop in which the imperatives of labour demand and consolidating domestic support for reform have made an uneasy match, resulting in the racialization of Irishness. The state has, however, amended the Constitution in order to qualify jus soli citizenship entitlement in the case of particular categories of people: those whose parents are not Irish nationals. The significant stakes of these changes are analysed in the context of state responses to Eire’s transition to a country of immigration, and the role of nationalist-populism in the country’s political culture.

The morphology of spray-dried particles

Samples of Various industrial or pilot plant spray-dried materials were obtained from manufacturers together with details of drying conditions and feed concentrations. The samples were subjected to qualitative and semi-quantitative examination to identify structural and morphological features. The results were related to measured bulk physical properties and to drying conditions. Single particles were produced in a convective drying process Analogous to spray drying, in which different solids or mixtures of solids were dried from solutions, slurries or pastes as single suspended droplets. The localized chemical and physical structures were analysed and in some cases the retention of volatiles monitored. The results were related to experimental conditions, viz.; air temperature, initial solids concentration and the degree of feed aeration. Three distinct categories of particle morphology were identified, i.e.; crystalline, skin-forming and agglomerate. Each category is evidence of a characteristic drying behaviour which is dependent on initial solids concentration. the degree of feed aeration, and drying temperature. Powder flow ability, particle and bulk density, particle-size, particle friability, and the retention of volatiles bear a direct relationship to morphological structure. Morphologies of multicomponent mixtures were complex, but the respective migration rates of the solutes were dependent on drying temperature. Gas-film heat and SDSS transfer coefficients of single pure liquid droplets were also measured over a temperature range of 50•C to 200•C under forced convection. Balanced transfer rates were obtained attributed to droplet instability or oscillation within the airflow, demonstrated in associated work with single free-flight droplets. The results are of relevance to drier optimisation and to the optimisation of product characteristics, e.g.; particle strength and essential volatiles-retention, in convective drying.

Management information:design of a system for change identification

This thesis deals with the problem of Information Systems design for Corporate Management. It shows that the results of applying current approaches to Management Information Systems and Corporate Modelling fully justify a fresh look to the problem. The thesis develops an approach to design based on Cybernetic principles and theories. It looks at Management as an informational process and discusses the relevance of regulation theory to its practice. The work proceeds around the concept of change and its effects on the organization's stability and survival. The idea of looking at organizations as viable systems is discussed and a design to enhance survival capacity is developed. It takes Ashby's theory of adaptation and developments on ultra-stability as a theoretical framework and considering conditions for learning and foresight deduces that a design should include three basic components: A dynamic model of the organization- environment relationships; a method to spot significant changes in the value of the essential variables and in a certain set of parameters; and a Controller able to conceive and change the other two elements and to make choices among alternative policies. Further considerations of the conditions for rapid adaptation in organisms composed of many parts, and the law of Requisite Variety determine that successful adaptive behaviour requires certain functional organization. Beer's model of viable organizations is put in relation to Ashby's theory of adaptation and regulation. The use of the Ultra-stable system as abstract unit of analysis permits developing a rigorous taxonomy of change; it starts distinguishing between change with in behaviour and change of behaviour to complete the classification with organizational change. It relates these changes to the logical categories of learning connecting the topic of Information System design with that of organizational learning.