Spectro-electrochemical and DFT studies of a planar Cu(II)–phenolate complex active in the aerobic oxidation of primary alcohols

A square-planar compound [Cu(pyrimol)Cl] (pyrimol = 4-methyl-2-N-(2-pyridylmethylene)aminophenolate) abbreviated as CuL–Cl) is described as a biomimetic model of the enzyme galactose oxidase (GOase). This copper(II) compound is capable of stoichiometric aerobic oxidation of activated primary alcohols in acetonitrile/water to the corresponding aldehydes. It can be obtained either from Hpyrimol (HL) or its reduced/hydrogenated form Hpyramol (4-methyl-2-N-(2-pyridylmethyl)aminophenol; H2L) readily converting to pyrimol (L-) on coordination to the copper(II) ion. Crystalline CuL–Cl and its bromide derivative exhibit a perfect square-planar geometry with Cu–O(phenolate) bond lengths of 1.944(2) and 1.938(2) Å. The cyclic voltammogram of CuL–Cl exhibits an irreversible anodic wave at +0.50 and +0.57 V versus ferrocene/ferrocenium (Fc/Fc+) in dry dichloromethane and acetonitrile, respectively, corresponding to oxidation of the phenolate ligand to the corresponding phenoxyl radical. In the strongly donating acetonitrile the oxidation path involves reversible solvent coordination at the Cu(II) centre. The presence of the dominant CuII–L. chromophore in the electrochemically and chemically oxidised species is evident from a new fairly intense electronic absorption at 400–480 nm ascribed to a several electronic transitions having a mixed pi-pi(L.) intraligand and Cu–Cl -> L. charge transfer character. The EPR signal of CuL–Cl disappears on oxidation due to strong intramolecular antiferromagnetic exchange coupling between the phenoxyl radical ligand (L.) and the copper(II) centre, giving rise to a singlet ground state (S = 0). The key step in the mechanism of the primary alcohol oxidation by CuL–Cl is probably the alpha-hydrogen abstraction from the equatorially bound alcoholate by the phenoxyl moiety in the oxidised pyrimol ligand, Cu–L., through a five-membered cyclic transition state.

Bottom-up planning and the future of planning education in India

The article discusses normative guidelines for reorienting planning education in India within the context of the immensely influential Constitutional Amendment Act of 1993. First, it briefly sketches the status of planning education at present in India, in relation to the role of planners in planning practice. It then descibes the changes that have taken place in general, following the Constitutional Amendment Act, dwelling more on the specific changes within the State of Kerala. The implications of these for planning education in general are then discussed normatively, highlighting three areas that need immediate attention from the planning academic community.

A survey of primary homology assessment: different botanists perceive and define characters in different ways

Cladistic analyses begin with an assessment of variation for a group of organisms and the subsequent representation of that variation as a data matrix. The step of converting observed organismal variation into a data matrix has been considered subjective, contentious, under-investigated, imprecise, unquantifiable, intuitive, as a black-box, and at the same time as ultimately the most influential phase of any cladistic analysis (Pimentel and Riggins, 1987; Bryant, 1989; Pogue and Mickevich, 1990; de Pinna, 1991; Stevens, 1991; Bateman et al., 1992; Smith, 1994; Pleijel, 1995; Wilkinson, 1995; Patterson and Johnson, 1997). Despite the concerns of these authors, primary homology assessment is often perceived as reproducible. In a recent paper, Hawkins et al. (1997) reiterated two points made by a number of these authors: that different interpretations of characters and coding are possible and that different workers will perceive and define characters in different ways. One reviewer challenged us: did we really think that two people working on the same group would come up with different data sets? The conflicting views regarding the reproducibility of the cladistic character matrix provoke a number of questions. Do the majority of workers consistently follow the same guidelines? Has the theoretical framework informing primary homology assessment been adequately explored? The objective of this study is to classify approaches to primary homology assessment, and to quantify the extent to which different approaches are found in the literature by examining variation in the way characters are defined and coded in a data matrix.

The contribution of primary and secondary somatosensory cortices to the representation of body parts and body sides: an fMRI adaptation study

Although the somatosensory homunculus is a classically used description of the way somatosensory inputs are processed in the brain, the actual contributions of primary (SI) and secondary (SII) somatosensory cortices to the spatial coding of touch remain poorly understood. We studied adaptation of the fMRI BOLD response in the somatosensory cortex by delivering pairs of vibrotactile stimuli to the finger tips of the index and middle fingers. The first stimulus (adaptor) was delivered either to the index or to the middle finger of the right or left hand, whereas the second stimulus (test) was always administered to the left index finger. The overall BOLD response evoked by the stimulation was primarily contralateral in SI and was more bilateral in SII. However, our fMRI adaptation approach also revealed that both somatosensory cortices were sensitive to ipsilateral as well as to contralateral inputs. SI and SII adapted more after subsequent stimulation of homologous as compared with nonhomologous fingers, showing a distinction between different fingers. Most importantly, for both somatosensory cortices, this finger-specific adaptation occurred irrespective of whether the tactile stimulus was delivered to the same or to different hands. This result implies integration of contralateral and ipsilateral somatosensory inputs in SI as well as in SII. Our findings suggest that SI is more than a simple relay for sensory information and that both SI and SII contribute to the spatial coding of touch by discriminating between body parts (fingers) and by integrating the somatosensory input from the two sides of the body (hands).

Glimpsing regular lattice arrangements of primary rat hippocampal astrocytes on ultra-thin nodes of Parylene-C

In our seminal work, we reported how the biomaterial Parylene-C has the unique ability to coerce neurons and glial cells to migrate to and then grow in straight lines along serum coated rectangular parylene-C structures mounted on an oxidised silicon substrate. In this brief communication, we report how astrocyte cell bodies, from the dissociated postnatal rat hippocampus, can now to be successfully localised on an ultra-thin 13nm layer of parylene-C mounted on oxidised silicon (Figure 1). What is extremely interesting about this finding is that the astrocyte processes extended mainly in horizontal and vertical directions from the cell body thus creating a regular lattice network of individual cells. In addition, they comfortably extended a 50μm gap (equivalent to ~ 10 cell body diameters) to connect to adjacent astrocytes on neighbouring Parylene-C structures. This was found to occur repeatedly on circular geometries of 20μm diameter. In comparison to our previous work [1], we have decreased the thickness of the parylene-C structures by a factor of 10, to allow such technology to be able to be utilised for passive electrode design that requires extremely thin structures such as these. Thus, being able to culture astrocytes in regular lattice networks will pave the way for precise monitoring and stimulation of such ensembles via multi-electrode arrays, allowing a closer insight into their dynamic behaviour and their network properties.

HMEF: framework to evaluate merging of Higher Education Institutions – application of Enterprise Architecture

Mergers of Higher Education Institutions (HEIs) are organisational processes requiring tremendous amount of resources, in terms of time, work, and money. A number of mergers have been seen on previous years and more are to come. Several studies on mergers have been conducted, revealing some crucial factors that affect the success of mergers. Based on literature review on these studies, factors are: the initiator of merger, a reason for merger, geographical distance of merging institutions, organisational culture, the extend of overlapping course portfolio, and Quality Assurance Systems (QASs). Usually these kind of factors are not considered on mergers, but focus is on financial matters. In this paper, a framework (HMEF) for evaluating merging of HEIs is introduced. HMEF is based on Enterprise Architecture (EA), focusing on factors found to be affecting the success of mergers. By using HMEF, HEIs can focus on matters that crucial for merging.

Coupled versus uncoupled hindcast simulations of the Madden-Julian oscillation in the Year of Tropical Convection

This study investigates the impact of a full interactive ocean on daily initialised 15 day hindcasts of the Madden-Julian oscillation (MJO), measured against a Met Office Unified Model (MetUM) atmosphere control simulation (AGCM) during a 3 month period of the Year of Tropical Convection (YOTC). Results indicated that the coupled configuration (CGCM) extends MJO predictability over that of the AGCM, by up to 3-5 days. Propagation is improved in the CGCM, which we partly attribute to a more realistic phase relationship between sea surface temperature (SST) and convection. In addition, the CGCM demonstrates skill in representing downwelling oceanic Kelvin and Rossby waves which warm SSTs along their trajectory, with the potential to feed back on the atmosphere. These results imply that an ocean model capable of simulating internal ocean waves may be required to capture the full effect of air-sea coupling for the MJO.

Bizzy Break! The effect of a classroom-based activity break on in-school physical activity levels of primary school children

The school has been identified as a key setting to promote physical activity. The purpose of this study was to evaluate the effect of a classroom-based activity break on in-school step counts of primary school children. Data for 90 children (49 boys, 41 girls, 9.3 ± 1.4 years) from three Irish primary schools is presented. In each school one class was randomly assigned as the intervention group and another as controls. Children's step counts were measured for five consecutive days during school hours at baseline and follow-up. Teachers of the intervention classes led a 10 min activity break in the classroom each day (Bizzy Break!). Mean daily in-school steps for the intervention at baseline and follow-up were 5351 and 5054. Corresponding values for the control group were 5469 and 4246. There was a significant difference in the change in daily steps from baseline to follow-up between groups (p < .05). There was no evidence that girls and boys responded differently to the intervention (p > .05). Children participating in a daily 10 min classroom-based activity break undertake more physical activity during school hours than controls.

Evidence for interplay between genes and parenting on infant temperament in the first year of life: monoamine oxidase A polymorphism moderates effects of maternal sensitivity on infant anger proneness

Background The low expression polymorphism of the MAOA gene in interaction with adverse environments (G × E) is associated with antisocial behaviour disorders. These have their origins in early life, but it is not known whether MAOA G × E occurs in infants. We therefore examined whether MAOA G × E predicts infant anger proneness, a temperamental dimension associated with later antisocial behaviour disorders. In contrast to previous studies, we examined MAOA G × E prospectively using an observational measure of a key aspect of the infant environment, maternal sensitivity, at a specified developmental time point. Methods In a stratified epidemiological cohort recruited during pregnancy, we ascertained MAOA status (low vs. high expression alleles) from the saliva of 193 infants, and examined specific predictions to maternal report of infant temperament at 14 months from maternal sensitivity assessed at 29 weeks of age. Results Analyses, weighted to provide general population estimates, indicated a robust interaction between MAOA status and maternal sensitivity in the prediction of infant anger proneness (p = .003) which became stronger once possible confounders for maternal sensitivity were included in the model (p = .0001). The interaction terms were similar in males (p = .010) and females (p = .016), but the effects were different as a consequence of an additional sex of infant by maternal sensitivity interaction. Conclusions This prospective study provides the first evidence of moderation by the MAOA gene of effects of parenting on infant anger proneness, an important early risk for the development of disruptive and aggressive behaviour disorders.