Structural and equilibrium studies on mixed ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) with N-(2-benzimidazolyl)methyliminodiacetic acid and typical N,N donor ligands

Mixed ligand complexes: [Co(L)(bipy)] (.) 3H(2)O (1), [Ni(L)(phen)] (.) H2O (2), [Cu(L)(phen)] (.) 3H(2)O (3) and [Zn(L)(bipy)] (.) 3H(2)O (4), where L2- = two -COOH deprotonated dianion of N-(2-benzimidazolyl)methyliminodiacetic acid (H(2)bzimida, hereafter, H,L), bipy = 2,2' bipyridine and phen = 1,10-phenanthroline have been isolated and characterized by elemental analysis, spectral and magnetic measurements and thermal studies. Single crystal X-ray diffraction studies show octahedral geometry for 1, 2 and 4 and square pyramidal geometry for 3. Equilibrium studies in aqueous solution (ionic strength I = 10(-1) mol dm(-3) (NaNO3), at 25 +/- 1 degrees C) using different molar proportions of M(II):H2L:B, where M = Co, Ni, Cu and Zn and B = phen, bipy and en (ethylene diamine), however, provides evidence of formation of mononuclear and binuclear binary and mixed ligand complexes: M(L), M(H-1L)(-), M(B)(2+), M(L)(B), M(H-1L)(B)(-), M-2(H-1L)(OH), (B)M(H-1L)M(B)(+), where H-1L3- represents two -COOH and the benzimidazole NI-H deprotonated quadridentate (O-, N, O-, N), or, quinquedentate (O-, N, O-, N, N-) function of the coordinated ligand H,L. Binuclear mixed ligand complex formation equilibria: M(L)(B) + M(B)(2+) = (B)M(H-1L)M(B)(+) + H+ is favoured with higher pi-acidity of the B ligands. For Co(II), Ni(II) and Cu(II), these equilibria are accompanied by blue shift of the electronic absorption maxima of M(II) ions, as a negatively charged bridging benzimidazolate moiety provides stronger ligand field than a neutral one. Solution stability of the mixed ligand complexes are in the expected order: Co(II) < Ni(II) < Cu(II) > Zn(II). The Delta logK(M) values are less negetive than their statistical values, indicating favoured formation of the mixed ligand complexes over the binary ones. (c) 2005 Elsevier B.V. All rights reserved.

Equilibrium studies on mixed ligand complex formation of Co(II), Ni(II), Cu(II) and Zn(II) with N-(2-hydroxybenzyl)-L-histidine (H(2)hb-L-his) and typical N,N donor ligands: Crystal structure of [Ni(hb-L-his)(bipyridine)]center dot H2O complex

Equilibrium study on complex formation of Co(II), Ni(II), Cu(II) and Zn(II), hereafter M(II), with the quadridentate (O-, N, O-, N) donor ligand, N-(2-hydroxybenzyl)-L-histidine (H(2)hb-L-his, hereafter H2L), in the absence and in the presence of typical (N, N) donor bidentate ligands, 1,10 phenanthroline(phen), 2, 2'-bipyridine(bipy), ethylenediamine(en), hereafter B, in aqueous solution at 25 +/- 1 degrees C was done at a fixed ionic strength, I = 0.1 mol dm(-3) (NaNO3) by combined pH-metric, UV-Vis and EPR measurements provide evidence for the formation of mononuclear and dinuclear binary and mixed ligand complexes of the types: M(L), M(L)(2)(2-), M-2(L)(2+), M-2(H-1L)(+), M(L)(B), (B)M(H-1L)M(B)(+). The imidazole moiety of the ligand is found to act as a bridging bidentate ligand in the dinuclear M-2(L)(2+), M-2(H-1L)(+) and (B)M(H-1L)M(B)(+) complexes, using its N-3 atom and N1-H deprotonated moiety. Stability constants of the complexes provide evidence of discrimination of Cu(II) from the other M(II) ions by this ligand. Solid complexes: [Ni(L)(H2O)(2)] (1), [Cu(L)(H2O)] (2), and [Ni(L)(bipy)] (.) H2O (3) have been isolated and characterized by various physicochemical studies. Single crystal X-ray diffraction of the ternary complex, 3, shows an octahedral [(O-,N,N,O-)(N,N)] geometry with extensive pi-pi stacking of the aromatic rings and H-bonding with imidazole (N1-H), secondary amino N-atom, the lattice H2O molecule, and the carboxylate and phenolate O-atoms. (c) 2006 Elsevier B.V. All rights reserved.

A novel experimental method for measuring vergence and accommodation responses to the main near visual cues in typical and atypical groups

Binocular disparity, blur, and proximal cues drive convergence and accommodation. Disparity is considered to be the main vergence cue and blur the main accommodation cue. We have developed a remote haploscopic photorefractor to measure simultaneous vergence and accommodation objectively in a wide range of participants of all ages while fixating targets at between 0.3 and 2 m. By separating the three main near cues, we can explore their relative weighting in three-, two-, one-, and zero-cue conditions. Disparity can be manipulated by remote occlusion; blur cues manipulated by using either a Gabor patch or a detailed picture target; looming cues by either scaling or not scaling target size with distance. In normal orthophoric, emmetropic, symptom-free, naive visually mature participants, disparity was by far the most significant cue to both vergence and accommodation. Accommodation responses dropped dramatically if disparity was not available. Blur only had a clinically significant effect when disparity was absent. Proximity had very little effect. There was considerable interparticipant variation. We predict that relative weighting of near cue use is likely to vary between clinical groups and present some individual cases as examples. We are using this naturalistic tool to research strabismus, vergence and accommodation development, and emmetropization.

Can misalignments in typical infants be used as a model for infantile esotropia?

PURPOSE. To investigate the nature of early ocular misalignments in human infants to determine whether they can provide insight into the etiology of esotropia and, in particular, to examine the correlates of misalignments. METHODS. A remote haploscopic photorefraction system was used to measure accommodation and vergence in 146 infants between 0 and 12 months of age. Infants underwent photorefraction immediately after watching a target moving between two of five viewing distances (25, 33, 50, 100, and 200 cm). In some instances, infants were tested in two conditions: both eyes open and one eye occluded. The resultant data were screened for instances of large misalignments. Data were assessed to determine whether accommodative, retinal disparity, or other cues were associated with the occurrence of misalignments. RESULTS. The results showed that there was no correlation between accommodative behavior and misalignments. Infants were more likely to show misalignments when retinal disparity cues were removed through occlusion. They were also more likely to show misalignments immediately after the target moved from a near to a far position in comparison to far-to-near target movement. DISCUSSION. The data suggest that the prevalence of misalignments in infants of 2 to 3 months of age is decreased by the addition of retinal disparity cues to the stimulus. In addition, target movement away from the infant increases the prevalence of misalignments. These data are compatible with the notion that misalignment are caused by poor sensitivity to targets moving away from the infant and support the theory that some forms of strabismus could be related to failure in a system that is sensitive to the direction of motion.

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.

Typical control curricula and using software for teaching/assessment: a UK perspective

This paper describes some of the preliminary outcomes of a UK project looking at control education. The focus is on two aspects: (i) the most important control concepts and theories for students doing just one or two courses and (ii) the effective use of software to improve student learning and engagement. There is also some discussion of the correct balance between teaching theory and practise. The paper gives examples from numerous UK universities and some industrial comment.

Decision making for HVAC&R system selection for a typical office building in the UK

Demands for thermal comfort, better indoor air quality together with lower environmental impacts have had ascending trends in the last decade. In many circumstances, these demands could not be fully covered through the soft approach of bioclimatic design like optimisation of the building orientation and internal layout. This is mostly because of the dense urban environment and building internal energy loads. In such cases, heating, ventilation, air-conditioning and refrigeration (HVAC&R) systems make a key role to fulfill the requirements of indoor environment. Therefore, it is required to select the most proper HVAC&R system. In this study, a robust decision making approach for HVAC&R system selection is proposed. Technical performance, economic aspect and environmental impacts of 36 permutations of primary and secondary systems are taken into account to choose the most proper HVAC&R system for a case study office building. The building is a representative for the dominant form of office buildings in the UK. Dynamic performance evaluation of HVAC&R alternatives using TRNSYS package together with life cycle energy cost analysis provides a reliable basis for decision making. Six scenarios broadly cover the decision makers' attitudes on HVAC&R system selection which are analysed through Analytical Hierarchy Process (AHP). One of the significant outcomes reveals that, despite both the higher energy demand and more investment requirements associated with compound heating, cooling and power system (CCHP); this system is one of the top ranked alternatives due to the lower energy cost and C02 emissions. The sensitivity analysis reveals that in all six scenarios, the first five top ranked alternatives are not changed. Finally, the proposed approach and the results could be used by researchers and designers especially in the early stages of a design process in which all involved bodies face the lack of time, information and tools for evaluation of a variety of systems.

Natural ventilation assessment in typical open an semi-open urban environments under various wind directions

Semi-open street roofs protect pedestrians from intense sunshine and rains. Their effects on natural ventilation of urban canopy layers (UCL) are less understood. This paper investigates two idealized urban models consisting of 4(2×2) or 16(4×4) buildings under a neutral atmospheric condition with parallel (0°) or non-parallel (15°,30°,45°) approaching wind. The aspect ratio (building height (H) / street width (W)) is 1 and building width is B=3H. Computational fluid dynamic (CFD) simulations were first validated by experimental data, confirming that standard k-ε model predicted airflow velocity better than RNG k-ε model, realizable k–ε model and Reynolds stress model. Three ventilation indices were numerically analyzed for ventilation assessment, including flow rates across street roofs and openings to show the mechanisms of air exchange, age of air to display how long external air reaches a place after entering UCL, and purging flow rate to quantify the net UCL ventilation capacity induced by mean flows and turbulence. Five semi-open roof types are studied: Walls being hung above street roofs (coverage ratio λa=100%) at z=1.5H, 1.2H, 1.1H ('Hung1.5H', 'Hung1.2H', 'Hung1.1H' types); Walls partly covering street roofs (λa=80%) at z=H ('Partly-covered' type); Walls fully covering street roofs (λa=100%) at z=H ('Fully-covered' type).They basically obtain worse UCL ventilation than open street roof type due to the decreased roof ventilation. 'Hung1.1H', 'Hung1.2H', 'Hung1.5H' types are better designs than 'Fully-covered' and 'Partly-covered' types. Greater urban size contains larger UCL volume and requires longer time to ventilate. The methodologies and ventilation indices are confirmed effective to quantify UCL ventilation.

Clinical test responses to different orthoptic exercise regimes in typical young adults

Purpose The relative efficiency of different eye exercise regimes is unclear, and in particular the influences of practice, placebo and the amount of effort required are rarely considered. This study measured conventional clinical measures after different regimes in typical young adults. Methods 156 asymptomatic young adults were directed to carry out eye exercises 3 times daily for two weeks. Exercises were directed at improving blur responses (accommodation), disparity responses (convergence), both in a naturalistic relationship, convergence in excess of accommodation, accommodation in excess of convergence, and a placebo regime. They were compared to two control groups, neither of which were given exercises, but the second of which were asked to make maximum effort during the second testing. Results Instruction set and participant effort were more effective than many exercises. Convergence exercises independent of accommodation were the most effective treatment, followed by accommodation exercises, and both regimes resulted in changes in both vergence and accommodation test responses. Exercises targeting convergence and accommodation working together were less effective than those where they were separated. Accommodation measures were prone to large instruction/effort effects and monocular accommodation facility was subject to large practice effects. Conclusions Separating convergence and accommodation exercises seemed more effective than exercising both systems concurrently and suggests that stimulation of accommodation and convergence may act in an additive fashion to aid responses. Instruction/effort effects are large and should be carefully controlled if claims for the efficacy of any exercise regime are to be made.

Change in convergence and accommodation after two weeks of eye exercises in typical young adults

Abstract: Introduction Although eye exercises appear to help heterophoria, convergence insufficiency and intermittent strabismus, true treatment effects can be confounded by placebo, practice and encouragement factors. This study assessed objective changes in vergence and accommodation responses in typical naïve young adults after two weeks of exercises compared to control conditions to assess the extent of treatment effects occur above other factors. Methods 156 asymptomatic young adults were randomly assigned to 6 exercise groups or 2 no-treatment groups. Treatment targeted i) accommodation, ii)vergence, iii) both, iv) convergence>accommodation, v)accommodation>convergence, or vi) a placebo. All were re-tested under identical conditions, except for the second control group who were additionally encouraged during testing. Objective accommodation and vergence were assessed to a range of targets moving in depth containing combinations of blur, disparity and proximity/looming cues. Results Response gain improved more for less naturalistic targets where more improvement was possible. Convergence exercises improved vergence for near across all targets (P=.035). Mean accommodation changed similarly,but non-significantly. No other treatment group differed significantly from the non-encouraged control group, while encouraging effort produced significantly increased vergence (P=.004) and accommodation (P=.005) gains in the other control group. Conclusions True treatment effects were small, only significantly better after vergence exercises to a non-accommodative target, and were rarely related to response they were designed to improve. Exercising accommodation without convergence made no difference to accommodation to cues containing detail. Additional effort improved objective responses the most, so should be controlled carefully in research, and considered when auditing treatment.

Visual search for basic emotional expressions in autism; impaired processing of anger, fear and sadness, but a typical happy face advantage

Facial expression recognition was investigated in 20 males with high functioning autism (HFA) or Asperger syndrome (AS), compared to typically developing individuals matched for chronological age (TD CA group) and verbal and non-verbal ability (TD V/NV group). This was the first study to employ a visual search, “face in the crowd” paradigm with a HFA/AS group, which explored responses to numerous facial expressions using real-face stimuli. Results showed slower response times for processing fear, anger and sad expressions in the HFA/AS group, relative to the TD CA group, but not the TD V/NV group. Reponses to happy, disgust and surprise expressions showed no group differences. Results are discussed with reference to the amygdala theory of autism.

Syntactic complexity in the comprehension of wh-questions and relative clauses in typical language development and autism

This study investigates effects of syntactic complexity operationalised in terms of movement, intervention and (NP) feature similarity in the development of A’ dependencies in 4-, 6-, and 8-year old typically developing (TD) French children and children with Autism Spectrum Disorders (ASD). Children completed an off-line comprehension task testing eight syntactic structures classified in four levels of complexity: Level 0: No Movement; Level 1: Movement without (configurational) Intervention; Level 2: Movement with Intervention from an element which is maximally different or featurally ‘disjoint’ (mismatched in both lexical NP restriction and number); Level 3: Movement with Intervention from an element similar in one feature or featurally ‘intersecting’ (matched in lexical NP restriction, mismatched in number). The results show that syntactic complexity affects TD children across the three age groups, but also indicate developmental differences between these groups. Movement affected all three groups in a similar way, but intervention effects in intersection cases were stronger in younger than older children, with NP feature similarity affecting only 4-year olds. Complexity effects created by the similarity in lexical restriction of an intervener thus appear to be overcome early in development, arguably thanks to other differences of this intervener (which was mismatched in number). Children with ASD performed less well than the TD children although they were matched on non-verbal reasoning. Overall, syntactic complexity affected their performance in a similar way as in their TD controls, but their performance correlated with non-verbal abilities rather than age, suggesting that their grammatical development does not follow the smooth relation to age that is found in TD children.