Syntheses, structural analyses, and magneto-structural correlations of three polymeric Fe(II) complexes with azide ligand

Three new metal-organic polymeric complexes, [Fe(N-3)(2)(bPP)(2)] (1), [Fe(N-3)(2)(bpe)] (2), and [Fe(N-3)(2)(phen)] (3) [bpp = (1,3-bis(4-pyridyl)-propane), bpe = (1,2-bis(4-pyridyl)-ethane), phen = 1,10-phenanthroline], have been synthesized and characterized by single-crystal X-ray diffraction studies and low-temperature magnetic measurements in the range 300-2 K. Complexes 1 and 2 crystallize in the monoclinic system, space group C2/c, with the following cell parameters: a = 19.355(4) Angstrom, b = 7.076(2) Angstrom, c = 22.549(4) Angstrom, beta = 119.50(3)degrees, Z = 4, and a = 10.007(14) Angstrom, b = 13.789(18) Angstrom, c = 10.377(14) Angstrom, beta = 103.50(1)degrees, Z = 4, respectively. Complex 3 crystallizes in the triclinic system, space group P (1) over bar, with a = 7.155(12) Angstrom, b = 10.066(14) Angstrom, c = 10.508(14) Angstrom, alpha = 109.57(1)degrees, beta = 104.57(1)degrees, gamma = 105.10(1)degrees, and Z = 2. All coordination polymers exhibit octahedral Fe(II) nodes. The structural determination of 1 reveals a parallel interpenetrated structure of 2D layers of (4,4) topology, formed by Fe(II) nodes linked through bpp ligands, while mono-coordinated azide anions are pendant from the corrugated sheet. Complex 2 has a 2D arrangement constructed through 1D double end-to-end azide bridged iron(11) chains interconnected through bpe ligands. Complex 3 shows a polymeric arrangement where the metal ions are interlinked through pairs of end-on and end-to-end azide ligands exhibiting a zigzag arrangement of metals (Fe-Fe-Fe angle of 111.18degrees) and an intermetallic separation of 3.347 Angstrom (through the EO azide) and of 5.229 Angstrom (EE azide). Variable-temperature magnetic susceptibility data suggest that there is no magnetic interaction between the metal centers in 1, whereas in 2 there is an antiferromagnetic interaction through the end-to-end azide bridge. Complex 3 shows ferro- as well as anti-ferromagnetic interactions between the metal centers generated through the alternating end-on and end-to-end azide bridges. Complex I has been modeled using the D parameter (considering distorted octahedral Fe(II) geometry and with any possible J value equal to zero) and complex 2 has been modeled as a one-dimensional system with classical and/or quantum spin where we have used two possible full diagonalization processes: without and with the D parameter, considering the important distortions of the Fe(II) ions. For complex 3, the alternating coupling model impedes a mathematical solution for the modeling as classical spins. With quantum spin, the modeling has been made as in 2.

Ditopic hexaazamacrocycles containing pyridine: synthesis, protonation and complexation studies

Structural studies of metal complexes of five ditopic hexaazamacrocycles containing two pyridine rings ([n] py(2)N(4) n = 18, 20, 22, 24 and 26) have been carried out. The synthesis of macrocycles [22]- to [26]- py(2)N(4) are also reported. The protonation constants of the last three compounds and the stability constants of their complexes with Ni2+, Cu2+, Zn2+, and Pb2+ were determined at 25 degreesC in 0.10 mol dm(-3) KNO3 in aqueous solution. Our results with [22] py(2)N(4) show significant differences from those described previously, while [24] py(2)N(4) has not been studied before and [ 26] py2N4 is a new compound. Mononuclear and dinuclear complexes of the divalent metal ions studied with [ 22]- to [26]- py(2)N(4) were found in solution. The stability constants for the ML complexes of the three ligands follow the Irving - Williams order: NiL2+ < CuL2+ >> ZnL2+ > PbL2+, however for the dinuclear complexes the values for Pb2+ complexes are higher than the corresponding values for the Ni2+ and the Zn2+ complexes. The X-ray single crystal structures of the supramolecular aggregates [Cu-2([20] py(2)N(4))(H2O)(4)][Cu(H2O)(6)](SO4)(3) . 3H(2)O ( 1) and [Cu-2([20] py(2)N(4))(CH3CN)(4)][Ni([20] py(2)N(4))](2)(ClO4)(8) . H2O (2), which are composed of homodinuclear [Cu-2([20] py(2)N(4)])(H2O)(4)](4+) ( 1a) and [Cu-2([20] py(2)N(4)])(CH3CN))(4)](4+) (2a), and mononuclear species, [Cu(H2O)(6)](2+) (1b) and [Ni([20] py(2)N(4))](2+) ( 2b), respectively, assembled by an extensive network of hydrogen bonds, are also reported. In both homodinuclear complexes the copper centres are located at the end of the macrocycle and display distorted square pyramidal coordination environments with the basal plane defined by three consecutive nitrogen donors and one solvent molecule, water in 1a and acetonitrile in 2a. The macrocycle adopts a concertina-type conformation leading to the formation of macrocyclic cavities with the two copper centres separated by intramolecular distances of 5.526(1) and 5.508(7) Angstrom in 1a and 2a, respectively. The mononuclear complex [Ni([20] py(2)N(4)])](2+) displays a distorted octahedral co-ordination environment with the macrocycle wrapping the metal centre in a helical shape. EPR spectroscopy of the copper complexes indicated the presence of mono- and dinuclear species.

Clinical trial: the effects of a trans-galactooligosaccharide prebiotic on faecal microbiota and symptoms in irritable bowel syndrome

Gut microflora-mucosal interactions may be involved in the pathogenesis of irritable bowel syndrome (IBS). To investigate the efficacy of a novel prebiotic trans-galactooligosaccharide in changing the colonic microflora and improve the symptoms in IBS sufferers. In all, 44 patients with Rome II positive IBS completed a 12-week single centre parallel crossover controlled clinical trial. Patients were randomized to receive either 3.5 g/d prebiotic, 7 g/d prebiotic or 7 g/d placebo. IBS symptoms were monitored weekly and scored according to a 7-point Likert scale. Changes in faecal microflora, stool frequency and form (Bristol stool scale) subjective global assessment (SGA), anxiety and depression and QOL scores were also monitored. The prebiotic significantly enhanced faecal bifidobacteria (3.5 g/d P < 0.005; 7 g/d P < 0.001). Placebo was without effect on the clinical parameters monitored, while the prebiotic at 3.5 g/d significantly changed stool consistency (P < 0.05), improved flatulence (P < 0.05) bloating (P < 0.05), composite score of symptoms (P < 0.05) and SGA (P < 0.05). The prebiotic at 7 g/d significantly improved SGA (P < 0.05) and anxiety scores (P < 0.05). The galactooligosaccharide acted as a prebiotic in specifically stimulating gut bifidobacteria in IBS patients and is effective in alleviating symptoms. These findings suggest that the prebiotic has potential as a therapeutic agent in IBS.

Tests of syntactic comprehension in aphasia: an investigation of task effects

Background: Consistency of performance across tasks that assess syntactic comprehension in aphasia has clinical and theoretical relevance. In this paper we add to the relatively sparse previous work on how sentence comprehension abilities are influenced by the nature of the assessment task. Aims: Our aims are: (1) to compare linguistic performance across sentence-picture matching, enactment, and truth-value judgement tasks; (2) to investigate the impact of pictorial stimuli on syntactic comprehension. Methods Procedures: We tested a group of 10 aphasic speakers (3 with fluent and 7 with non-fluent aphasia) in three tasks (Experiment 1): (i) sentence-picture matching with four pictures, (ii) sentence-picture matching with two pictures, and (iii) enactment. A further task of truth-value judgement was given to a subgroup of those speakers (n=5, Experiment 2). Similar sentence types across all tasks were used and included canonical (actives, subject clefts) and non-canonical (passives, object clefts) sentences. We undertook two types of analyses: (a) we compared canonical and non-canonical sentences in each task; (b) we compared performance between (i) actives and passives, (ii) subject and object clefts in each task. We examined the results of all participants as a group and as case-series. Outcomes Results: Several task effects emerged. Overall, the two-picture sentence-picture matching and enactment tasks were more discriminating than the four-picture condition. Group performance in the truth-value judgement task was similar to two-picture sentence-picture matching and enactment. At the individual level performance across tasks contrasted to some group results. Conclusions: Our findings revealed task effects across participants. We discuss reasons that could explain the diverse profiles of performance and the implications for clinical practice.

Verb retrieval in fluent aphasia: a clinical study

Background: Problems with lexical retrieval are common across all types of aphasia but certain word classes are thought to be more vulnerable in some aphasia types. Traditionally, verb retrieval problems have been considered characteristic of non-fluent aphasias but there is growing evidence that verb retrieval problems are also found in fluent aphasia. As verbs are retrieved from the mental lexicon with syntactic as well as phonological and semantic information, it is speculated that an improvement in verb retrieval should enhance communicative abilities in this population as in others. We report on an investigation into the effectiveness of verb treatment for three individuals with fluent aphasia. Methods & Procedures: Multiple pre-treatment baselines were established over 3 months in order to monitor language change before treatment. The three participants then received twice-weekly verb treatment over approximately 4 months. All pre-treatment assessments were administered immediately after treatment and 3 months post-treatment. Outcome & Results: Scores fluctuated in the pre-treatment period. Following treatment, there was a significant improvement in verb retrieval for two of the three participants on the treated items. The increase in scores for the third participant was statistically nonsignificant but post-treatment scores moved from below the normal range to within the normal range. All participants were significantly quicker in the verb retrieval task following treatment. There was an increase in well-formed sentences in the sentence construction test and in some samples of connected speech. Conclusions: Repeated systematic treatment can produce a significant improvement in verb retrieval of practised items and generalise to unpractised items for some participants. An increase in well-formed sentences is seen for some speakers. The theoretical and clinical implications of the results are discussed.

Multiple PID mapping using neural networks in a MIMO steam generator system

A neural network was used to map three PID operating regions for a two-input two-output steam generator system. The network was used in stand alone feedforward operation to control the whole operating range of the process, after being trained from the PID controllers corresponding to each control region. The network inputs are the plant error signals, their integral, their derivative and a 4-error delay train.

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.

Emotion processing in infancy: specificity in risk for social anxiety and associations with two year outcomes

The current study examined the specificity of patterns of responding to high and low intensity negative emotional expressions of infants of mothers with social phobia, and their association with child outcomes at two years of age. Infants of mothers with social phobia, generalised anxiety disorder (GAD) or no history of anxiety were shown pairs of angry and fearful emotional expressions at 10 weeks of age. Symptoms of social withdrawal, anxiety and sleep problems were assessed at two years of age. Only infants of mothers with social phobia showed a tendency to look away from high intensity fear faces; however infants of mothers with both social phobia and GAD showed a bias towards high intensity angry faces. Among the offspring of mothers with social phobia, anxiety symptoms at two years of age were associated with a preference for high intensity fear faces in infancy. The reverse pattern was found amongst the offspring of non-anxious mothers. These findings suggest a possible specific response to emotional expressions among the children of mothers with social phobia.

Dealing with complexity: an autopoietic view of the People's Planning Campaign, Kerala

Complexity is integral to planning today. Everyone and everything seem to be interconnected, causality appears ambiguous, unintended consequences are ubiquitous, and information overload is a constant challenge. The nature of complexity, the consequences of it for society, and the ways in which one might confront it, understand it and deal with it in order to allow for the possibility of planning, are issues increasingly demanding analytical attention. One theoretical framework that can potentially assist planners in this regard is Luhmann's theory of autopoiesis. This article uses insights from Luhmann's ideas to understand the nature of complexity and its reduction, thereby redefining issues in planning, and explores the ways in which management of these issues might be observed in actual planning practice via a reinterpreted case study of the People's Planning Campaign in Kerala, India. Overall, this reinterpretation leads to a different understanding of the scope of planning and planning practice, telling a story about complexity and systemic response. It allows the reinterpretation of otherwise familiar phenomena, both highlighting the empirical relevance of the theory and providing new and original insight into particular dynamics of the case study. This not only provides a greater understanding of the dynamics of complexity, but also produces advice to help planners implement structures and processes that can cope with complexity in practice.

Measuring societal awareness of the rural agrarian landscape: indicators and scale issues

The work presented in this report is part of the effort to define the landscape state and diversity indicator in the frame of COM (2006) 508 “Development of agri-environmental indicators for monitoring the integration of environmental concerns into the common agricultural policy”. The Communication classifies the indicators according to their level of development, which, for the landscape indicator is “in need of substantial improvements in order to become fully operational”. For this reason a full re-definition of the indicator has been carried out, following the initial proposal presented in the frame of the IRENA operation (“Indicator Reporting on the Integration of Environmental Concerns into Agricultural Policy”). The new proposal for the landscape state and diversity indicator is structured in three components: the first concerns the degree of naturalness, the second landscape structure, the third the societal appreciation of the rural landscape. While the first two components rely on a strong bulk of existing literature, the development of the methodology has made evident the need for further analysis of the third component, which is based on a newly proposed top-down approach. This report presents an in-depth analysis of such component of the indicator, and the effort to include a social dimension in large scale landscape assessment.