Ruthenium complexes of C,C '-bis(ethynyl)carboranes: an investigation of electronic interactions mediated by spherical pseudo-aromatic spacers

The complexes [Ru(1-C=C-1,10-C2B8H9)(dppe)Cp*] (3a), [Ru(1-C C-1,12-C2B10H11)(dppe)-Cp*] (3b), [{Ru(dppe)Cp*}(2){mu-1,10-(C C)(2)-1,10-C2B8H8}] (4a) and [{Ru(dppe)Cp*}(2){mu-1,12-(C C)2- 1,12-C2B10-H-10}] (4b), which form a representative series of mono- and bimetallic acetylide complexes featuring 10- and 12-vertex carboranes embedded within the dethynyl bridging ligand, have been prepared and structurally characterized. In addition, these compounds have been examined spectroscopically (UV-is-NIR, IR) in all accessible redox states. The significant separation of the two, one-electron anodic waves observed in the cyclic voltammograms of the bimetallic complexes 4a and 4b is largely independent of the nature of the electrolyte and is attributed to stabilization of the intermediate redox products [4a](+) and [4b](+) through interactions between the metal centers across a distance of ca. 12.5 angstrom. The mono-oxidized bimetallic complexes (4a](+) and [4b](+) exhibit spectroscopic properties consistent with a description of these species in terms of valence-localized (class II) mixed-valence compounds, including a unique low-energy electronic absorption band, attributed to an, IVCT-type transition that tails into the IR region. DFT calculations with model systems [4a-H](+) and [4b-H](+) featuring simplified ligand sets reproduce the observed spectroscopic data and localized electronic structures for the mixed-valence cations [4a](+) and [4b](+).

Perceptual grouping and distance estimates in typical and atypical development: comparing performance across perception, drawing and construction tasks

Perceptual grouping is a pre-attentive process which serves to group local elements into global wholes, based on shared properties. One effect of perceptual grouping is to distort the ability to estimate the distance between two elements. In this study, biases in distance estimates, caused by four types of perceptual grouping, were measured across three tasks, a perception, a drawing and a construction task in both typical development (TD: Experiment 1) and in individuals with Williams syndrome (WS: Experiment 2). In Experiment 1, perceptual grouping distorted distance estimates across all three tasks. Interestingly, the effect of grouping by luminance was in the opposite direction to the effects of the remaining grouping types. We relate this to differences in the ability to inhibit perceptual grouping effects on distance estimates. Additive distorting influences were also observed in the drawing and the construction task, which are explained in terms of the points of reference employed in each task. Experiment 2 demonstrated that the above distortion effects are also observed in WS. Given the known deficit in the ability to use perceptual grouping in WS, this suggests a dissociation between the pre-attentive influence of and the attentive deployment of perceptual grouping in WS. The typical distortion in relation to drawing and construction points towards the presence of some typical location coding strategies in WS. The performance of the WS group differed from the TD participants on two counts. First, the pattern of overall distance estimates (averaged across interior and exterior distances) across the four perceptual grouping types, differed between groups. Second, the distorting influence of perceptual grouping was strongest for grouping by shape similarity in WS, which contrasts to a strength in grouping by proximity observed in the TD participants. (c) 2008 Elsevier Inc. All rights reserved.

The surface geometries of the medium and high coverage carbon monoxide structures c(2 × 4)–(2CO) and p(root7- x root7)R19°–(4CO) structure

The surface geometries of the p (root7- x root7)R19degrees-(4CO) and c(2 x 4)-(2CO) layers on Ni {111} and the clean Ni {111} surface were determined by low energy electron diffraction structure analysis. For the clean surface small but significant contractions of d(12) and d(23) (both 2.02 Angstrom) were found with respect to the bulk interlayer distance (2.03 Angstrom). In the c(2 x 4)-(2CO) structure these distances are expanded, with values of d(12) = 2.08 Angstrom and d(23) = 2.06 Angstrom and buckling of 0.08 and 0.02 Angstrom, respectively, in the first and second layer. CO resides near hcp and fcc hollow sites with relatively large lateral shifts away from the ideal positions leading to unequal C-Ni bond lengths between 1.76 and 1.99 Angstrom. For the p(root7- x root7-)R19'-(4CO) layer two best fit geometries were found, which agree in most of their atomic positions, except for one out of four CO molecules, which is either near atop or between bridge and atop. The remaining three molecules reside near hcp and fcc sites, again with large lateral deviations from their ideal positions. The average C Ni bond length for these molecules is, however, the same as for CO on hollow sites at low coverage. The average CNi bond length at hollow sites, the interlayer distances, and buckling in the first Ni layer are similar to the c(2 x 4)(2CO) geometry, only the buckling in the second layer (0.08 Angstrom) is significantly larger. Lateral and vertical shifts of the Ni atoms in the first layer lead to unsymmetric environments for the CO molecules, which can be regarded as an imprint of the chiral p(root7- x root7-)R19degrees lattice geometry onto the substrate.

Decreased accommodation during decompensation of distance exotropia

Objective. Disparity cues can be a major drive to accommodation via the CA/C (convergence accommodation to convergence) linkage but, on decompensation of exotropia, disparity cues are extinguished by suppression, so this drive is lost. This study investigated accommodation and vergence responses to disparity, blur and proximal cues in a group of distance exotropes aged between 4-11 years both during decompensation and when exotropic. Methods. 19 participants with distance exotropia were tested using a PlusoptiXSO4 photorefractor set in a remote haploscopic device which assessed simultaneous vergence and accommodation to a range of targets incorporating different combinations of blur, disparity and proximal cues at four fixation distances between 2m and 33cm. Responses on decompensation were compared to those from the same children when their deviation was controlled. Results. Manifest exotropia was more common in the more impoverished cue conditions. When decompensated for near, mean accommodation gain for the all-cue (naturalistic) target reduced significantly (p<0.0001), with resultant mean under-accommodation of 2.33D at 33cm. The profile of near cues usage changed after decompensation, with blur and proximity driving residual responses, but these remaining cues did not compensate for loss of accommodation caused by the removal of disparity. Conclusions. Accommodation often reduces on decompensation of distance exotropia as the drive from convergence is extinguished, providing a further reason to try to prevent decompensation for near.

Computer-mediated communication in distance MA programmes: the student's perspective

This paper reports on a study of computer-mediated communication within the context of a distance MA in TEFL programme which used an e-mail discussion list and then a discussion board. The study focused on the computer/Internet access and skills of the target population and their CMC needs and wants. Data were collected from 63 questionnaires and 6 in-depth interviews with students. Findings indicate that computer use and access to the Internet are widespread within the target population. In addition, most respondents indicated some competence in Internet use. No single factor emerged as an overriding inhibiting factor for lack of personal use. There was limited use of the CMC tools provided on the course for student–student interaction, mainly attributable to time constraints. However, most respondents said that they would like more CMC interaction with tutors. The main factor which would contribute to greater Internet use was training. The paper concludes with recommendations and suggestions for learner training in this area.

The anions [(ZrOH(CO3)3)2]6− and [(ZrOH(C2O4)3)2]6−: single crystal X-ray diffraction studies of the complexes guanidinium zirconium carbonate [(C(NH2)3)3ZrOH(CO3)3·H2O]2 and sodium zirconium oxalate Na6(ZrOH(C2O4)3)2·7H2O

The complex [(C(NH2)3)3ZrOH(CO3)3·H2O]2 (A) has been shown by means of a single crystal X-ray diffraction study to contain [C(NH2)3]+ cations and dimeric anions of formulation [(ZrOH(CO3)3)2]6−. The anion is centrosymmetric with each metal being bonded to two bridging OH groups and three chelating CO2−3 ions. The Zr atoms are thus eight coordinate with a dodecahedral environments. The ZrO distances formed by the bridgng OH groups are shorter than those formed through zirconiu carbonate interactions. The non-bonded Zr…Zr distance is 3.47(2) Å. An infrared spectroscopic investigation of A provides data which support the findings of the crystallographic study. Likewise the complex Na6(ZrOH(CO2O4)3)2·7H2O (B) contains the anion [(ZrOH(C2O4)3)2]6−. This anion is structurally related to the anion in A as each Zr atom has an eight-coordinate dodecahedral environment being bonded to two bridging OH groups and three chelating oxalate ligands, but has no imposed crysallographic symmetry. The Zr…Zr non-bonded distance is 3.50(1) Å. The OZrO bridge angles are 69.7(4)° and A and 67.4(3)° in B.

Evidence that convergence rather than accommodation controls intermittent distance exotropia

Purpose. This study considered whether vergence drives accommodation or accommodation drives vergence during the control of distance exotropia for near fixation. High accommodative convergence to accommodation (AC/A) ratios are often used to explain this control, but the role of convergence to drive accommodation (the CA/C relationship) is rarely considered. Atypical CA/C characteristics could equally, or better, explain common clinical findings. Methods. 19 distance exotropes, aged 4-11 years, were compared while controlling their deviation with 27 non-exotropic controls aged 5-9 years. Simultaneous vergence and accommodation responses were measured to a range of targets incorporating different combinations of blur, disparity and looming cues at four fixation distances between 2m and 33cm. Stimulus and response AC/A and CA/C ratios were calculated. Results. Accommodation responses for near targets (p=0.017) response gains (p=0.026) were greater in the exotropes than the controls. Despite higher clinical stimulus AC/A ratios, the distance exotropes showed lower laboratory response AC/A ratios (p=0.02), but significantly higher CA/C ratios (p=0.02). All the exotropes, whether the angle changed most with lenses (“controlled by accommodation”) or on occlusion (“controlled by fusion”), used binocular disparity not blur as their main cue to target distance. Conclusions. Increased vergence demand to control intermittent distance exotropia for near also drives significantly more accommodation. Minus lens therapy is more likely to act by correcting over-accommodation driven by controlling convergence, rather than by inducing blur-driven vergence. The use of convergence as a major drive to accommodation explains many clinical characteristics of distance exotropia, including apparently high near stimulus AC/A ratios.

The impact of added cultural distance and cultural diversity on international expansion patterns: a Penrosian perspective

International strategy research has identified a variety of multinational enterprise (MNE) expansion patterns. Some MNEs appear to expand internationally at a stable rate, whereas others expand rapidly in one period and then tend to experience slower growth. The latter pattern suggests the occurrence of the Penrose effect. We identified two determinants of these diverging patterns. First, we propose that high levels of added cultural distance (reflecting expansion into new local contexts) during one period, may negatively affect further international expansion because of dynamic adjustment costs. Second, we suggest that managing a network of subsidiaries operating in a set of local contexts with high cultural diversity, increases environmental and internal governance complexity. Extant cultural diversity of the local contexts where the MNE is active in a first period may therefore discourage adding further cultural distance. We test the hypothesized relationships using a panel of 91 German companies.

Distance from forest edge affects bee pollinators in oilseed rape fields

Wild pollinators have been shown to enhance the pollination of Brassica napus(oilseed rape) and thus increase its market value. Several studies have previously shown that pollination services are greater in crops adjoining forest patches or other seminatural habitats than in crops completely surrounded by other crops. In this study, we investigated the specific importance of forest edges in providing potential pollinators in B. napus fields in two areas in France. Bees were caught with yellow pan traps at increasing distances from both warm and cold forest edges into B. napus fields during the blooming period. A total of 4594 individual bees, representing six families and 83 taxa, were collected. We found that both bee abundance and taxa richness were negatively affected by the distance from forest edge. However, responses varied between bee groups and edge orientations. The ITD (Inter-Tegular distance) of the species, a good proxy for bee foraging range, seems to limit how far the bees can travel from the forest edge. We found a greater abundance of cuckoo bees (Nomada spp.) of Andrena spp. and Andrena spp. males at forest edges, which we assume indicate suitable nesting sites, or at least mating sites, for some abundant Andrena species and their parasites (Fig. 1). Synthesis and Applications. This study provides one of the first examples in temperate ecosystems of how forest edges may actually act as a reservoir of potential pollinators and directly benefit agricultural crops by providing nesting or mating sites for important early spring pollinators. Policymakers and land managers should take forest edges into account and encourage their protection in the agricultural matrix to promote wild bees and their pollination services.

Estimation of Gaussian process regression model using probability distance measures

A new class of parameter estimation algorithms is introduced for Gaussian process regression (GPR) models. It is shown that the integration of the GPR model with probability distance measures of (i) the integrated square error and (ii) Kullback–Leibler (K–L) divergence are analytically tractable. An efficient coordinate descent algorithm is proposed to iteratively estimate the kernel width using golden section search which includes a fast gradient descent algorithm as an inner loop to estimate the noise variance. Numerical examples are included to demonstrate the effectiveness of the new identification approaches.

The persistence of distance: a gravity model of European cross-border real estate development flows

Purpose – This paper aims to investigate the scale and drivers of cross-border real estate development in Western Europe and Central and Eastern Europe. Design/methodology/approach – Placing cross-border real estate development within the framework of foreign direct investment (FDI), conceptual complexities in characterizing the notional real estate developer are emphasized. Drawing upon a transaction database, this paper proxies cross-border real estate development flows with asset sales by developers. Findings – Much higher levels of market penetration by international real estate developers are found in the less mature markets of Central and Eastern Europe. Analysis suggests a complex range of determinants with physical distance remaining a consistent barrier to cross-border development flows. Originality/value – This analysis adds significant value in terms of understanding cross-border real estate development flows. In this study, a detailed examination of the issues based on a rigorous empirical analysis through gravity modelling is offered. The gravity framework is one of the most confirmed empirical regularities in international economics and commonly applied to trade, FDI, migration, foreign portfolio investment inter alia. This paper assesses the extent to which it provides useful insights into the pattern of cross-border real estate development flows.

Datasets related to in-land water for limnology and remote sensing applications: distance-to-land, distance-to-water, water-body identifier and lake-centre co-ordinates

Datasets containing information to locate and identify water bodies have been generated from data locating static-water-bodies with resolution of about 300 m (1/360 deg) recently released by the Land Cover Climate Change Initiative (LC CCI) of the European Space Agency. The LC CCI water-bodies dataset has been obtained from multi-temporal metrics based on time series of the backscattered intensity recorded by ASAR on Envisat between 2005 and 2010. The new derived datasets provide coherently: distance to land, distance to water, water-body identifiers and lake-centre locations. The water-body identifier dataset locates the water bodies assigning the identifiers of the Global Lakes and Wetlands Database (GLWD), and lake centres are defined for in-land waters for which GLWD IDs were determined. The new datasets therefore link recent lake/reservoir/wetlands extent to the GLWD, together with a set of coordinates which locates unambiguously the water bodies in the database. Information on distance-to-land for each water cell and the distance-to-water for each land cell has many potential applications in remote sensing, where the applicability of geophysical retrieval algorithms may be affected by the presence of water or land within a satellite field of view (image pixel). During the generation and validation of the datasets some limitations of the GLWD database and of the LC CCI water-bodies mask have been found. Some examples of the inaccuracies/limitations are presented and discussed. Temporal change in water-body extent is common. Future versions of the LC CCI dataset are planned to represent temporal variation, and this will permit these derived datasets to be updated.

SEM analysis of enamel surface treated by Er : YAG laser: Influence of irradiation distance

Background: Depending on the distance of laser tip to dental surface a specific morphological pattern should be expected. However, there have been limited reports that correlate the Er:YAG irradiation distance with dental morphology. Purpose: To assess the influence of Er:YAG laser irradiation distance on enamel morphology, by means of scanning electron microscopy (SEM). Methods: Sixty human third molars were employed to obtain discs (congruent to 1 mm thick) that were randomly assigned to six groups (n = 10). Five groups received Er:YAG laser irradiation (80 mJ/2 Hz) for 20 s, according to the irradiation distance: 11, 12, 14, 16, or 17 mm. and the control group was treated with 37% phosphoric acid for 15 s. The laser-irradiated discs were bisected. One hemi-disc was separated for superficial analysis without subsequent acid etching, and the other one, received the phosphoric acid for 15 s. Samples were prepared for SEM. Results: Laser irradiation at 11 and 12 min provided an evident ablation of enamel, with evident fissures and some fused areas. At 14, 16 and 17 mm the superficial topography was flatter than in the other distances. The subsequent acid etching on the lased-surface partially removed the disorganized tissue. Conclusions: Er:YAG laser in defocused mode promoted slight morphological alterations and seems more suitable for enamel conditioning than focused irradiation. The application of phosphoric acid on lased-enamel surface, regardless of the irradiation distance, decreased the superficial irregularities.