Deprotection, tethering, and activation of a one-legged metalloporphyrin on a chemically active metal surface: NEXAFS, Synchrotron XPS, and STM study of [SAc]P-Mn(III)Cl on Ag(100)

The structural and reactive properties of the acetyl-protected "one-legged" manganese porphyrin [SAc]P-Mn(III)Cl on Ag(100) have been studied by NEXAFS, synchrotron XPS and STM Spontaneous surface-mediated deprotection occurs at 300 K accompanied by spreading of the resulting thio-tethered porphyrin across the metal surface Loss of the axial chlorine ligand occurs at 498 K, without any demetalation of the macrocycle, leaving the Mn center in a low co-ordination state At low coverages the macrocycle is markedly tilted toward the silver surface, as is the phenyl group that forms part of the tethering "leg". In the monolayer region a striking transition occurs whereby the molecule rolls over, preserving the tilt angle of the phenyl group, strongly increasing that of the macrocycle, decreasing the apparent height of the molecule and decreasing its footprint, thus enabling closer packing These findings are in marked contrast with those previously reported for the corresponding more rigidly bound four-legged porphyrin [Turner, M., Vaughan, O. P. H., Kyriakou, G., Watson, D. J., Scherer, L. J; Davidson, G J. E, Sanders, J. K. M.; Lambert, R. M J. Am. Chem Soc 2009, 131, 1910] suggesting that the physicochemical :)properties and potential applications of these versatile systems should be strongly dependent on the mode of tethering to the surface.

Reach & grasp therapy: Design and control of a 9-DOF robotic neuro-rehabilitation system

This paper presents the Gentle/G integrated system for reach & grasp therapy retraining following brain injury. The design, control and integration of an experimental grasp assistance unit is described for use in robot assisted stroke rehabilitation. The grasp assist unit is intended to work with the hardware and software of the Gentle/S robot although the hardware could be adapted to other rehabilitation applications. When used with the Gentle/S robot a total of 6 active and 3 passive degrees of freedom are available to provide active, active assist or passive grasp retraining in combination with reaching movements in a reach-grasp-transfer-release sequence.

Sub-agent elements for control methods in multi-agent energy management system

Increased penetration of generation and decentralised control are considered to be feasible and effective solution for reducing cost and emissions and hence efficiency associated with power generation and distribution. Distributed generation in combination with the multi-agent technology are perfect candidates for this solution. Pro-active and autonomous nature of multi-agent systems can provide an effective platform for decentralised control whilst improving reliability and flexibility of the grid.

Military doctrine, command philosophy and the generation of fighting power: genesis and theory

Military doctrine is one of the conceptual components of war. Its raison d’être is that of a force multiplier. It enables a smaller force to take on and defeat a larger force in battle. This article’s departure point is the aphorism of Sir Julian Corbett, who described doctrine as ‘the soul of warfare’. The second dimension to creating a force multiplier effect is forging doctrine with an appropriate command philosophy. The challenge for commanders is how, in unique circumstances, to formulate, disseminate and apply an appropriate doctrine and combine it with a relevant command philosophy. This can only be achieved by policy-makers and senior commanders successfully answering the Clausewitzian question: what kind of conflict are they involved in? Once an answer has been provided, a synthesis of these two factors can be developed and applied. Doctrine has implications for all three levels of war. Tactically, doctrine does two things: first, it helps to create a tempo of operations; second, it develops a transitory quality that will produce operational effect, and ultimately facilitate the pursuit of strategic objectives. Its function is to provide both training and instruction. At the operational level instruction and understanding are critical functions. Third, at the strategic level it provides understanding and direction. Using John Gooch’s six components of doctrine, it will be argued that there is a lacunae in the theory of doctrine as these components can manifest themselves in very different ways at the three levels of war. They can in turn affect the transitory quality of tactical operations. Doctrine is pivotal to success in war. Without doctrine and the appropriate command philosophy military operations cannot be successfully concluded against an active and determined foe.

Coping with delays for real-time gaze control (The Fall and Rise of the Smiths Regulator)

In this paper we describe how to cope with the delays inherent in a real time control system for a steerable stereo head/eye platform. A purposive and reactive system requires the use of fast vision algorithms to provide the controller with the error signals to drive the platform. The time-critical implementation of these algorithms is necessary, not only to enable short latency reaction to real world events, but also to provide sufficiently high frequency results with small enough delays that controller remain stable. However, even with precise knowledge of that delay, nonlinearities in the plant make modelling of that plant impossible, thus precluding the use of a Smith Regulator. Moreover, the major delay in the system is in the feedback (image capture and vision processing) rather than feed forward (controller) loop. Delays ranging between 40msecs and 80msecs are common for the simple 2D processes, but might extend to several hundred milliseconds for more sophisticated 3D processes. The strategy presented gives precise control over the gaze direction of the cameras despite the lack of a priori knowledge of the delays involved. The resulting controller is shown to have a similar structure to the Smith Regulator, but with essential modifications.

Effect of pair interactions on transition probabilities between inactive and active states: achieving collective behaviour via pair interactions in social insects

To understand the evolution of well-organized social behaviour, we must first understand the mechanism by which collective behaviour establishes. In this study, the mechanisms of collective behaviour in a colony of social insects were studied in terms of the transition probability between active and inactive states, which is linked to mutual interactions. The active and inactive states of the social insects were statistically extracted from the velocity profiles. From the duration distributions of the two states, we found that 1) the durations of active and inactive states follow an exponential law, and 2) pair interactions increase the transition probability from inactive to active states. The regulation of the transition probability by paired interactions suggests that such interactions control the populations of active and inactive workers in the colony.

Subseasonal extremes of precipitation and active-break cycles of the Indian summer monsoon in a climate-change scenario

Changes to the behaviour of subseasonal precipitation extremes and active-break cycles of the Indian summer monsoon are assessed in this study using pre-industrial and 2 × CO2 integrations of the Hadley Centre coupled model HadCM3, which is able to simulate the monsoon seasonal cycle reasonably. At 2 × CO2, mean summer rainfall increases slightly, especially over central and northern India. The mean intensity of daily precipitation during the monsoon is found to increase, consistent with fewer wet days, and there are increases to heavy rain events beyond changes in the mean alone. The chance of reaching particular thresholds of heavy rainfall is found to approximately double over northern India, increasing the likelihood of damaging floods on a seasonal basis. The local distribution of such projections is uncertain, however, given the large spread in mean monsoon rainfall change and associated extremes amongst even the most recent coupled climate models. The measured increase of the heaviest precipitation events over India is found to be broadly in line with the degree of atmospheric warming and associated increases in specific humidity, lending a degree of predictability to changes in rainfall extremes. Active-break cycles of the Indian summer monsoon, important particularly due to their effect on agricultural output, are shown to be reasonably represented in HadCM3, in particular with some degree of northward propagation. We note an intensification of both active and break events, particularly when measured against the annual cycle, although there is no suggestion of any change to the duration or likelihood of monsoon breaks. Copyright © 2009 Royal Meteorological Society

Roman barrows and their landscape context: a GIS case study at Bartlow, Cambridgeshire

This paper examines the landscape context of the Bartlow Hills, a group of large Romano-British barrows that were excavated in the 1840s but have been largely neglected since. GIS is employed to test whether it was possible to view the mounds from nearby roads, barrows and villas. Existing research on provincial barrows, and especially their landscape context, and some recent relevant applications of GIS are reviewed. We argue that barrows are active and symbolically charged statements about power and identity. The most striking pattern to emerge from the GIS analysis is a focus on display to a local rather than a transient audience.

‘We are managing our own lives...’: life transitions and care in sibling-headed households affected by AIDS in Tanzania and Uganda

This paper explores the ways that young people express their agency and negotiate complex lifecourse transitions according to gender, age and inter- and intra-generational norms in sibling-headed households affected by AIDS in East Africa. Based on findings from a qualitative and participatory pilot study in Tanzania and Uganda, I examine young people's socio-spatial and temporal experiences of heading the household and caring for their siblings following their parent's/relative's death. Key dimensions of young people's caring pathways and life transitions are discussed: transitions into sibling care; the ways young people manage changing roles within the family; and the ways that young people are positioned and seek to position themselves within the community. The research reveals the relational and embodied nature of young people's life transitions over time and space. By living together independently, young people constantly reproduce and reconfigure gendered, inter- and intra-generational norms of ‘the family’, transgressing the boundaries of ‘childhood’, ‘youth’ and ‘adulthood’. Although young people take on ‘adult’ responsibilities and demonstrate their competencies in ‘managing their own lives’, this does not necessarily translate into more equal power relations with adults in the community. The research reveals the marginal ‘in-between’ place that young people occupy between local and global discourses of ‘childhood’ and ‘youth’ that construct them as ‘deviant’. Although young people adopt a range of strategies to resist marginalisation and harassment, I argue that constraints of poverty, unequal gender and generational power relations and the emotional impacts of sibling care, stigmatisation and exclusion can undermine their ability to exert agency and control over their sexual relationships, schooling, livelihood strategies and future lifecourse transitions.

Saturated salt solutions for humidity control and the survival of dry powder and oil formulations of Beauveria bassiana conidia

Oil-based formulated conidia sprayed on steel plates and conidia powder (control) of Beauveria bassiana isolate IMI 386243 were stored at temperatures from 10 to 40 degrees C in desiccators over saturated salt solutions providing relative humidities from 32 to 88%, or in hermetic storage at 40 degrees C, and moisture contents in equilibrium with 33 or 77% relative humidity. The negative semi-logarithmic relation (P < 0.005) between conidia longevity (at 40 degrees C) and equilibrium relative humidity did not differ (P > 0.25) between formulated conidia and conidia powder. Despite this, certain saturated salts provided consistently greater longevity (NaCl) and others consistently shorter longevity (KCl) for formulated conidia compared to conidia powder. These results, analysis of previous data, and comparison with hermetic storage, indicate that storage of conidia over saturated salt solutions provides inconsistent responses to environment and so may be problematic for bio-pesticide research. In hermetic storage, oil formulation was not deleterious to longevity and in the more moist environment enhanced survival periods. (c) 2005 Elsevier Inc. All rights reserved.

Field evaluation of systemic inducing resistance chemicals at different growth stages for the control of apple (Venturia inaequalis) and pear (Venturia pirina) scab

Two field trials were conducted using established apple (Malus cv. Golden Delicious) and pear (Pyrus communis 'Williams' Bon Chretien') to assess the efficacy of three commercially available systemic inducing resistance (SIR) products, Messenger (a.i. Harpin protein), Phoenix (a.i. Potassium phosphite) and Rigel (a.i. Salicylic acid derivative) applied at four different growth stages of tree development (bud break, green cluster, 90% petal fall, early fruitlet) against the foliar pathogens Venturia inaequalis and Venturia pirina which cause apple and pear scab respectively. A conventional synthetic fungicide (penconazole) used within the UK for apple and pear scab control was included for comparison. Little efficacy as scab protectants was demonstrated when each SIR product and penconazole was applied at only two growth stages (bud break, green cluster). However when the above compounds were applied at three or more growth stages efficacy as scab protectants was confirmed. The synthetic fungicide penconazole provided greatest protection against apple and pear scab in both the 2006 and 2007 field trials. There was little difference in the magnitude of scab protection conferred by each SIR agent. Results suggest application of at least three sprays during bud break to early fruitlet formation with an appropriate SIR agent may provide a useful addition to existing methods of apple and pear scab management under field conditions. (C) 2009 Published by Elsevier Ltd.

Annexins: multifunctional components of growth and adaptation

Plant annexins are ubiquitous, soluble proteins capable of Ca2+-dependent and Ca2+-independent binding to endomembranes and the plasma membrane. Some members of this multigene family are capable of binding to F-actin, hydrolysing ATP and GTP, acting as peroxidases or cation channels. These multifunctional proteins are distributed throughout the plant and throughout the life cycle. Their expression and intracellular localization are under developmental and environmental control. The in vitro properties of annexins and their known, dynamic distribution patterns suggest that they could be central regulators or effectors of plant growth and stress signalling. Potentially, they could operate in signalling pathways involving cytosolic free calcium and reactive oxygen species.

Impedance mismatch: some differences between the way humans and robots control interaction forces

In over forty years of research robots have made very little progress still largely confined to industrial manufacture and cute toys, yet in the same period computing has followed Moores Law where the capacity double roughly every two years. So why is there no Moores Law for robots? Two areas stand out as worthy of research to speedup progress. The first is to get a greater understanding of how human and animal brains control movement, the second to build a new generation of robots that have greater haptic sense, that is a better ability to adapt to the environment as it is encountered. A remarkable property of the cognitive-motor system in humans and animals is that it is slow. Recognising an object may take 250 mS, a reaction time of 150 mS is considered fast. Yet despite this slow system we are well designed to allow contact with the world in a variety of ways. We can anticipate an encounter, use the change of force as a means of communication and ignore sensory cues when they are not relevant. A better understanding of these process has allowed us to build haptic interfaces to mimic the interaction. Emerging from this understanding are new ways to control the contact between robots, the user and the environment. Rehabilitation robotics has all the elements in the subject to not only enable and change the lives of people with disabilities, but also to facilitate revolution change in classic robotics.