Induced-fit binding of π-electron donor substrates to macrocyclic aromatic ether-imide-sulfones: a versatile approach to molecular assembly

Novel macrocyclic receptors which bind electron-donor aromatic substrates via π-stacking donor- acceptor interactions are obtained by cyclo-imidization of an amine-functionalized arylether-sulfone with pyromellitic- and 1,4,5,8-naphthalene-tetracarboxylic dianhydrides. These macrocycles complex with a wide variety of π-donor substrates including tetrathiafulvalene, naphthalene, anthracene, pyrene, perylene, and functional derivatives of these polycyclic hydrocarbons. The resulting supramolecular assemblies range from simple 1:1 complexes, to [2]- and [3]-pseudorotaxanes, and even (as a result of crystallographic disorder) an apparent polyrotaxane. Direct, five-component self-assembly of a metal-centred [3]pseudorotaxane is also observed, on complexation of a macrocyclic ether-imide with 8-hydroxyquinoline in the presence of palladium(II) ions. Binding studies in solution were carried out by 1H NMR and UV-visible spectroscopy, and the stoichiometries of binding were confirmed by Job plots based on charge-transfer absorption bands. The highest association constants are found for strong π-donor guests with large surface-areas, notably perylene and 1-hydroxypyrene, for which Ka values of 1.4 x 103 and 2.3 x 103 M-1 respectively are found. Single crystal X-ray analyses of the receptors and their derived complexes reveal large, induced-fit distortions of the macrocyclic frameworks as a result of complexation. These structures provide compelling evidence for the existence of strong, attractive forces between the electronically-complementary aromatic π-systems of host and guest.

Fit for planning? An evaluation of the application of development viability appraisal models in the UK planning system

The aim of this paper is to critically examine the application of development appraisal to viability assessment in the planning system. This evaluation is of development appraisal models in general and also their use in particular applications associated with estimating planning obligation capacity. The paper is organised into four themes: · The context and conceptual basis for development viability appraisal · A review of development viability appraisal methods · A discussion of selected key inputs into a development viability appraisal · A discussion of the applications of development viability appraisals in the planning system It is assumed that readers are familiar with the basic models and information needs of development viability appraisal rather than at the cutting edge of practice and/or academe

Fit for policy? Some evidence on the application of development viability models in the UK planning system

This paper investigates the application and use of development viability models in the formation of planning policies in the UK. Particular attention is paid to three key areas; the assumed development scheme in development viability models, the use of forecasts and the debate concerning Threshold Land Value. The empirical section reports on the results of an interview survey involving the main producers of development viability models and appraisals. It is concluded that, although development viability models have intrinsic limitations associated with model composition and input uncertainties, the most significant limitations are related to the ways that they have been adapted for use in the planning system. In addition, it is suggested that the contested nature of Threshold Land Value is an example of calculative practices providing a façade of technocratic rationality in the planning system.

Comparative analysis of the fit of 3-unit implant-supported frameworks cast in nickel-chromium and cobalt-chromium alloys and commercially pure titanium after casting, laser welding, and simulated porcelain firings

This study compared the vertical misfit of 3-unit implant-supported nickel-chromium (Ni-Cr) and cobalt-chromium (Co-Cr) alloy and commercially pure titanium (cpTi) frameworks after casting as 1 piece, after sectioning and laser welding, and after simulated porcelain firings. The results on the tightened side showed no statistically significant differences. On the opposite side, statistically significant differences were found for Co-Cr alloy (118.64 mu m [SD: 91.48] to 39.90 mu m [SD: 27.13]) and cpTi (118.56 mu m [51.35] to 27.87 mu m [12.71]) when comparing 1-piece to laser-welded frameworks. With both sides tightened, only Co-Cr alloy showed statistically significant differences after laser welding. Ni-Cr alloy showed the lowest misfit values, though the differences were not statistically significantly different. Simulated porcelain firings revealed no significant differences.

Leader-organization fit: comparing the effectiveness of paternalistic and transformational leadership in different organizational cultures

Research on paternalistic leadership (PL) has been based exclusively on national cultures´ differences. However there are cues that other contextual variables can add to the explanation of this construct. Due to its capacity to influence expectations of individuals in organizations, organizational culture can contribute to fill this gap. To test if organizational culture influences the effectiveness of leadership style, we conducted two experimental studies using Amazon’s Mechanical Turk, comparing effects of paternalistic and transformational leadership on followers’ outcomes. Using video clips and vignettes, we found that PL is better related to followers´ outcomes in cultures oriented to people than outcome, and that TL has a better relationship in cultures oriented to innovation than stability. The results suggest that organizational culture helps in explaining PL endorsement, and that further analysis of the influence of this variable to PL can provide a better understanding of the expression of this leadership style in organizations.

On paternalistic leadership fit: exploring cross-cultural endorsement, leader-follower fit, and the boundary role of organizational culture

Although cross-cultural leadership research has thrived in international business literature, little attention has been devoted to understanding the effectiveness of non-western theories beyond their original contexts. The purpose of this study is to examine the cross-cultural endorsement of paternalistic leadership, an emerging non-western leadership theory, using data from GLOBE project. Using multigroup confirmatory factor analyses we found measurement equivalence of a scale derived from GLOBE’s data, which enabled us to compare the endorsement of paternalistic leadership dimensions across 10 cultural clusters and 55 societies. Our study revealed that there are significant differences in the importance societies give to each dimension, suggesting that paternalism as leadership style is not universally nor homogeneously endorsed. Furthermore, results suggest that different patterns of endorsement of each of these dimensions give rise to idiosyncratic shades of paternalistic leadership across societies. Implications for theory and future research on international business are discussed.

Comparison of logistic and neural network models to fit to the egg production curve of White Leghorn hens

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of Passive Fit Absence in the Prosthesis/Implant/Retaining Screw System: A Two-Dimensional Finite Element Analysis

The misfit between prostheses and implants is a clinical reality, but the level that can be accepted without causing mechanical or biologic problem is not well defined. This study investigates the effect of different levels of unilateral angular misfit prostheses in the prosthesis/implant/retaining screw system and in the surrounding bone using finite element analysis. Four models of a two-dimensional finite element were constructed: group I (control), prosthesis that fit the implant; groups 2 to 4, prostheses with unilateral angular misfit of 50, 100, and 200 mu m, respectively. A load of 133 N was applied with a 30-degree angulation and off-axis at 2 mm from the long axis of the implant at the opposite direction of misfit on the models. Taking into account the increase of the angular misfit, the stress maps showed a gradual increase of prosthesis stress and uniform stress in the implant and trabecular bone. Concerning the displacement, an inclination of the system due to loading and misfit was observed. The decrease of the unilateral contact between prosthesis and implant leads to the displacement of the entire system, and distribution and magnitude alterations of the stress also occurred.

IMPROVEMENT TO THE MARGINAL COPING FIT of COMMERCIALLY PURE TITANIUM CAST IN PHOSPHATE-BONDED INVESTMENT BY USING A SIMPLE PATTERN COATING TECHNIQUE

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)