Synthesis, structure, and electrochemical properties of a family of 2-(arylazo)phenolate complexes of ruthenium with unusual C-C coupling and N=Ncleavage

Reaction of 2-(4'-R-phenylazo)-4-methylphenols (R = OCH3, CH3, H, Cl, and NO2) with [Ru(dmso)(4)Cl-2] affords a family of five ruthenium(III) complexes, containing a 2-(arylazo)phenolate ligand forming a six-membered chelate ring and a tetradentate ligand formed from two 2-(arylazo) phenols via an unusual C-C coupling linki.ng the two ortho carbons of the phenyl rings in the arylazo fragment. A similar reaction with 2-(2'-methylphenylazo)-4-methylphenol with [Ru(dmso)(4)Cl-2] has afforded a similar complex, in which one 2-(2'-methylphenylazo)-4-methylphenolate ligand is coordinated forming a six-membered chelate ring, and the other two ligands have undergone the C-C coupling reaction, and the coupled species is coordinated as a tetradentate ligand forming a five-membered N,O-chelate ring, a nine-membered N,N-chelate ring, and another five-membered chelate ring. Reaction of 2-(2',6'-dimethylphenylazo)-4-methylphenol with [Ru(dmso)(4)Cl-2] has afforded a complex in which two 2-(2',6'-dimethylphenylazo)-4-methylphenols are coordinated as bidentate N,O-donors forming five- and six-membered chelate rings, while the third one has undergone cleavage across the N=N bond, and the phenolate fragment, thus generated, remains coordinated to the metal center in the iminosemiquinonate form. Structures of four selected complexes have been determined by X-ray crystallography. The first six complexes are one-electron paramagnetic and show rhombic ESR spectra. The last complex is diamagnetic and shows characteristic H-1 NMR signals. All the complexes show intense charge-transfer transitions in the visible region and a Ru(III)-Ru(IV) oxidation on the positive side of SCE and a Ru(III)-Ru(II) reduction on the negative side.

Morpholinone mediated oxazolone-free C-terminus amide coupling permitting a convergent strategy for peptide synthesis

3-Substituted-5-phenylmorpholinones have been demonstrated to act as N-protected C-terminus activated alpha-amino acids capable of undergoing solution phase N-terminus peptide extension following standard coupling procedures. The N-acylated morpholinones do not undergo epimerisation of the stereocentre of the C-terminus amino acid residue as oxazolone formation is sterically prevented, although C-terminus peptide coupling is still possible. This convergent approach to peptide synthesis is exemplified by the preparation of L-ala-L-ala-L-ala and L-ala-D-ala-L-ala. Copyright (c) 2008 European Peptide Society and John Wiley & Sons, Ltd.

Synthesis and properties of polyaromatic dendrimers possessing a repetitive amide-ester coupling sequence

A series of novel polyaromatic dendrimers that feature tris-(2-ethylamino)amine as the central core unit has been synthesized up to the third generation by employing a convergent growth strategy. The building blocks 1,3-diamino-2-hydroxypropane and 4-carboxybenzaldehyde were used for dendron construction, a process that involved the cyclic repetition of esterification, oxidation and selective amidation steps. Molecular modelling of this class of dendrimers has been used to predict potential solution state conformations employing molecular mechanics and molecular dynamic simulations. In addition, the results of preliminary metal binding studies using the first generation dendritic system are also outlined. (C) 2003 Elsevier Science Ltd. All rights reserved.

Solid-phase synthesis of an A-B loop mimetic of the C epsilon 3 domain of human IgE: macrocyclization by Sonogashira coupling

The solid-phase synthesis of a cyclic peptide containing the 21-residue epitope found in the A-B loop of the Cepsilon3 domain of human immunoglobulin E has been carried out. The key macrocyclization step to form the 65-membered ring is achieved in similar to15% yield via an "on-resin" Sonogashira coupling reaction which concomitantly installs a diphenylacetylene amino acid conformational constraint within the loop.

The integration of figurative language and static depictions: an eye movement study of fictive motion

Do we view the world differently if it is described to us in figurative rather than literal terms? An answer to this question would reveal something about both the conceptual representation of figurative language and the scope of top-down influences oil scene perception. Previous work has shown that participants will look longer at a path region of a picture when it is described with a type of figurative language called fictive motion (The road goes through the desert) rather than without (The road is in the desert). The current experiment provided evidence that such fictive motion descriptions affect eye movements by evoking mental representations of motion. If participants heard contextual information that would hinder actual motion, it influenced how they viewed a picture when it was described with fictive motion. Inspection times and eye movements scanning along the path increased during fictive motion descriptions when the terrain was first described as difficult (The desert is hilly) as compared to easy (The desert is flat); there were no such effects for descriptions without fictive motion. It is argued that fictive motion evokes a mental simulation of motion that is immediately integrated with visual processing, and hence figurative language can have a distinct effect on perception. (c) 2005 Elsevier B.V. All rights reserved.

The art of conversation is coordination: common ground and the coupling of eye movements during dialogue

When two people discuss something they can see in front of them, what is the relationship between their eye movements? We recorded the gaze of pairs of subjects engaged in live, spontaneous dialogue. Cross-recurrence analysis revealed a coupling between the eye movements of the two conversants. In the first study, we found their eye movements were coupled across several seconds. In the second, we found that this coupling increased if they both heard the same background information prior to their conversation. These results provide a direct quantification of joint attention during unscripted conversation and show that it is influenced by knowledge in the common ground.

Optokinetic stimulation induces illusory movement of both out-of-the-body and on-the-body hand-held visual objects

The coding of body part location may depend upon both visual and proprioceptive information, and allows targets to be localized with respect to the body. The present study investigates the interaction between visual and proprioceptive localization systems under conditions of multisensory conflict induced by optokinetic stimulation (OKS). Healthy subjects were asked to estimate the apparent motion speed of a visual target (LED) that could be located either in the extrapersonal space (visual encoding only, V), or at the same distance, but stuck on the subject's right index finger-tip (visual and proprioceptive encoding, V-P). Additionally, the multisensory condition was performed with the index finger kept in position both passively (V-P passive) and actively (V-P active). Results showed that the visual stimulus was always perceived to move, irrespective of its out- or on-the-body location. Moreover, this apparent motion speed varied consistently with the speed of the moving OKS background in all conditions. Surprisingly, no differences were found between V-P active and V-P passive conditions in the speed of apparent motion. The persistence of the visual illusion during the active posture maintenance reveals a novel condition in which vision totally dominates over proprioceptive information, suggesting that the hand-held visual stimulus was perceived as a purely visual, external object despite its contact with the hand.

Impairment in movement skills of children with autistic spectrum disorders

We undertook this study to explore the degree of impairment in movement skills in children with autistic spectrum disorders (ASD) and a wide IQ range. Movement skills were measured using the Movement Assessment Battery for Children (M-ABC) in a large, well defined, population-derived group of children (n=101: 89 males,12 females; mean age 11y 4mo, SD 10mo; range 10y-14y 3mo) with childhood autism and broader ASD and a wide range of IQ scores. Additionally, we tested whether a parent-completed questionnaire, the Developmental Coordination Disorder Questionnaire (DCDQ), was useful in identifying children who met criteria for movement impairments after assessment (n=97 with complete M-ABCs and DCDQs). Of the children with ASD, 79% had definite movement impairments on the M-ABC; a further 10% had borderline problems. Children with childhood autism were more impaired than children with broader ASD, and children with an IQ less than 70 were more impaired than those with IQ more than 70. This is consistent with the view that movement impairments may arise from a more severe neurological impairment that also contributes to intellectual disability and more severe autism. Movement impairment was not associated with everyday adaptive behaviour once the effect of IQ was controlled for. The DCDQ performed moderately well as a screen for possible motor difficulties. Movement impairments are common in children with ASD. Systematic assessment of movement abilities should be considered a routine investigation.

Involuntary inhibition of movement initiation alters oculomotor competition resolution

Identifying a stimulus as the target for a goal-directed movement involves inhibiting competing responses. Separable inhibitory interconnections bias local competition to ensure only one stimulus is selected and to alter movement initiation. Behavioural evidence of these inhibitory processes comes from the effects of distracters on oculomotor landing positions and saccade latencies. Here, we investigate the relationship between these two sources of inhibition. Targets were presented with or without close and remote distracters. In separate experiments the possible position and identity of the target and distracters were manipulated. In all cases saccade landing position was found to be less affected by the presence of the close distracter when remote distracters were also present. The involuntary increase in the latency of saccade initiation caused by the presence of the remote distracters alters the state of competitive processes involved in selecting the saccade target thus changing its landing position.

Attention processes in children with movement difficulties, reading difficulties or both

Reading difficulties (RD) and movement difficulties (MD) co-occur more often in clinical populations than expected for independent disorders. In this study, we investigated the pattern of association between attentional processes, RD and MD in a population of 9 year old school children. Children were screened to identify index groups with RD, MD or both, plus a control group. These groups were then tested on a battery of cognitive attention assessments (TEA-Ch). Results confirmed that the occurrence of RD and MD was greater than would be predicted for independent disorders. Additionally, children with MD, whether or not combined with RD, had poor performance on all attention measures when compared with typically developing children. Children with RD only, were no poorer on measures of attention than typical children. The results are discussed with respect to approaches proposed to account for the co-occurrence of disorders.

The perception of emotion from body movement in point-light displays of interpersonal dialogue

We examined whether it is possible to identify the emotional content of behaviour from point-light displays where pairs of actors are engaged in interpersonal communication. These actors displayed a series of emotions, which included sadness, anger, joy, disgust, fear, and romantic love. In experiment 1, subjects viewed brief clips of these point-light displays presented the right way up and upside down. In experiment 2, the importance of the interaction between the two figures in the recognition of emotion was examined. Subjects were shown upright versions of (i) the original pairs (dyads), (ii) a single actor (monad), and (iii) a dyad comprising a single actor and his/her mirror image (reflected dyad). In each experiment, the subjects rated the emotional content of the displays by moving a slider along a horizontal scale. All of the emotions received a rating for every clip. In experiment 1, when the displays were upright, the correct emotions were identified in each case except disgust; but, when the displays were inverted, performance was significantly diminished for some ernotions. In experiment 2, the recognition of love and joy was impaired by the absence of the acting partner, and the recognition of sadness, joy, and fear was impaired in the non-veridical (mirror image) displays. These findings both support and extend previous research by showing that biological motion is sufficient for the perception of emotion, although inversion affects performance. Moreover, emotion perception from biological motion can be affected by the veridical or non-veridical social context within the displays.

The effects of a pre-movement delay on the kinematics of prehension in middle childhood

The present study examined the effects of a pre-movement delay on the kinematics of prehension in middle childhood. Twenty-five children between the ages of 5 and 11 years made visually open-loop reaches to two different sized objects at two different distances along the midline. Reaches took place either (i) immediately, or (ii) 2 s after the occlusion of the stimulus. In all age groups, reaches following the pre-movement delay were characterised by longer movement durations, lower peak velocities, larger peak grip apertures and longer time spent in the final slow phase of the movement. This pattern of results suggests that the representations that control the transport and grasp component are affected similarly by delay, and is consistent with the results previously reported for adults. Such representations therefore appear to develop before the age of 5. (C) 2004 Elsevier B.V. All rights reserved.