Two macrocyclic pentaaza compounds containing pyridine evaluated as novel chelating agents in copper(II) and nickel(II) overload

Two pentaaza macrocycles containing pyridine in the backbone, namely 3,6,9,12,18-pentaazabicyclo[12.3.1] octadeca-1(18),14,16-triene ([15]pyN(5)), and 3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),15,17-triene ([16]pyN(5)), were synthesized in good yields. The acid-base behaviour of these compounds was studied by potentiometry at 298.2 K in aqueous solution and ionic strength 0.10 M in KNO3. The protonation sequence of [15]pyN(5) was investigated by H-1 NMR titration that also allowed the determination of protonation constants in D2O. Binding studies of the two ligands with Ca2+, Ni2+, Cu2+, Zn2+, Cd2+, and Pb2+ metal ions were performed under the same experimental conditions. The results showed that all the complexes formed with the 15-membered ligand, particularly those of Cu2+ and especially Ni2+, are thermodynamically more stable than with the larger macrocycle. Cyclic voltammetric data showed that the copper(II) complexes of the two macrocycles exhibited analogous behaviour, with a single quasi-reversible one-electron transfer reduction process assigned to the Cu(II)/Cu(I) couple. The UV-visible-near IR spectroscopic and magnetic moment data of the nickel(II) complexes in solution indicated a tetragonal distorted coordination geometry for the metal centre. X-band EPR spectra of the copper(II) complexes are consistent with distorted square pyramidal geometries. The crystal structure of [Cu([15]pyN(5))](2+) determined by X-ray diffraction showed the copper(II) centre coordinated to all five macrocyclic nitrogen donors in a distorted square pyramidal environment.

Motion planning of autonomous vehicles in a non-autonomous vehicle environment without speed lanes

Planning is one of the key problems for autonomous vehicles operating in road scenarios. Present planning algorithms operate with the assumption that traffic is organised in predefined speed lanes, which makes it impossible to allow autonomous vehicles in countries with unorganised traffic. Unorganised traffic is though capable of higher traffic bandwidths when constituting vehicles vary in their speed capabilities and sizes. Diverse vehicles in an unorganised exhibit unique driving behaviours which are analysed in this paper by a simulation study. The aim of the work reported here is to create a planning algorithm for mixed traffic consisting of both autonomous and non-autonomous vehicles without any inter-vehicle communication. The awareness (e.g. vision) of every vehicle is restricted to nearby vehicles only and a straight infinite road is assumed for decision making regarding navigation in the presence of multiple vehicles. Exhibited behaviours include obstacle avoidance, overtaking, giving way for vehicles to overtake from behind, vehicle following, adjusting the lateral lane position and so on. A conflict of plans is a major issue which will almost certainly arise in the absence of inter-vehicle communication. Hence each vehicle needs to continuously track other vehicles and rectify plans whenever a collision seems likely. Further it is observed here that driver aggression plays a vital role in overall traffic dynamics, hence this has also been factored in accordingly. This work is hence a step forward towards achieving autonomous vehicles in unorganised traffic, while similar effort would be required for planning problems such as intersections, mergers, diversions and other modules like localisation.

Multi-level planning for semi-autonomous vehicles in traffic scenarios based on separation maximization

The planning of semi-autonomous vehicles in traffic scenarios is a relatively new problem that contributes towards the goal of making road travel by vehicles free of human drivers. An algorithm needs to ensure optimal real time planning of multiple vehicles (moving in either direction along a road), in the presence of a complex obstacle network. Unlike other approaches, here we assume that speed lanes are not present and that different lanes do not need to be maintained for inbound and outbound traffic. Our basic hypothesis is to carry forward the planning task to ensure that a sufficient distance is maintained by each vehicle from all other vehicles, obstacles and road boundaries. We present here a 4-layer planning algorithm that consists of road selection (for selecting the individual roads of traversal to reach the goal), pathway selection (a strategy to avoid and/or overtake obstacles, road diversions and other blockages), pathway distribution (to select the position of a vehicle at every instance of time in a pathway), and trajectory generation (for generating a curve, smooth enough, to allow for the maximum possible speed). Cooperation between vehicles is handled separately at the different levels, the aim being to maximize the separation between vehicles. Simulated results exhibit behaviours of smooth, efficient and safe driving of vehicles in multiple scenarios; along with typical vehicle behaviours including following and overtaking.

Planning autonomous vehicles in the absence of speed lanes using lateral potentials

Chaotic traffic, prevalent in many countries, is marked by a large number of vehicles driving with different speeds without following any predefined speed lanes. Such traffic rules out using any planning algorithm for these vehicles which is based upon the maintenance of speed lanes and lane changes. The absence of speed lanes may imply more bandwidth and easier overtaking in cases where vehicles vary considerably in both their size and speed. Inspired by the performance of artificial potential fields in the planning of mobile robots, we propose here lateral potentials as measures to enable vehicles to decide about their lateral positions on the road. Each vehicle is subjected to a potential from obstacles and vehicles in front, road boundaries, obstacles and vehicles to the side and higher speed vehicles to the rear. All these potentials are lateral and only govern steering the vehicle. A speed control mechanism is also used for longitudinal control of vehicle. The proposed system is shown to perform well for obstacle avoidance, vehicle following and overtaking behaviors.

Understanding the effects of anesthetic agents on the EEG through neural field theory

Anesthetic and analgesic agents act through a diverse range of pharmacological mechanisms. Existing empirical data clearly shows that such "microscopic" pharmacological diversity is reflected in their "macroscopic" effects on the human electroencephalogram (EEG). Based on a detailed mesoscopic neural field model we theoretically posit that anesthetic induced EEG activity is due to selective parametric changes in synaptic efficacy and dynamics. Specifically, on the basis of physiologically constrained modeling, it is speculated that the selective modification of inhibitory or excitatory synaptic activity may differentially effect the EEG spectrum. Such results emphasize the importance of neural field theories of brain electrical activity for elucidating the principles whereby pharmacological agents effect the EEG. Such insights will contribute to improved methods for monitoring depth of anesthesia using the EEG.

Understanding the transition to seizure by modeling the epileptiform activity of general anesthetic agents

A central difficulty in modeling epileptogenesis using biologically plausible computational and mathematical models is not the production of activity characteristic of a seizure, but rather producing it in response to specific and quantifiable physiologic change or pathologic abnormality. This is particularly problematic when it is considered that the pathophysiological genesis of most epilepsies is largely unknown. However, several volatile general anesthetic agents, whose principle targets of action are quantifiably well characterized, are also known to be proconvulsant. The authors describe recent approaches to theoretically describing the electroencephalographic effects of volatile general anesthetic agents that may be able to provide important insights into the physiologic mechanisms that underpin seizure initiation.

Multi-agent based modeling and simulation of complex system in hospital

This study puts forward a method to model and simulate the complex system of hospital on the basis of multi-agent technology. The formation of the agents of hospitals with intelligent and coordinative characteristics was designed, the message object was defined, and the model operating mechanism of autonomous activities and coordination mechanism was also designed. In addition, the Ontology library and Norm library etc. were introduced using semiotic method and theory, to enlarge the method of system modelling. Swarm was used to develop the multi-agent based simulation system, which is favorable for making guidelines for hospital's improving it's organization and management, optimizing the working procedure, improving the quality of medical care as well as reducing medical charge costs.

Planning autonomous vehicles in the absence of speed lanes using an elastic strip

Planning of autonomous vehicles in the absence of speed lanes is a less-researched problem. However, it is an important step toward extending the possibility of autonomous vehicles to countries where speed lanes are not followed. The advantages of having nonlane-oriented traffic include larger traffic bandwidth and more overtaking, which are features that are highlighted when vehicles vary in terms of speed and size. In the most general case, the road would be filled with a complex grid of static obstacles and vehicles of varying speeds. The optimal travel plan consists of a set of maneuvers that enables a vehicle to avoid obstacles and to overtake vehicles in an optimal manner and, in turn, enable other vehicles to overtake. The desired characteristics of this planning scenario include near completeness and near optimality in real time with an unstructured environment, with vehicles essentially displaying a high degree of cooperation and enabling every possible(safe) overtaking procedure to be completed as soon as possible. Challenges addressed in this paper include a (fast) method for initial path generation using an elastic strip, (re-)defining the notion of completeness specific to the problem, and inducing the notion of cooperation in the elastic strip. Using this approach, vehicular behaviors of overtaking, cooperation, vehicle following,obstacle avoidance, etc., are demonstrated.

Ancillary narratives: maids, sleepwalking, and agency in nineteenth-century literature and culture

The limited coverage of servants in nineteenth-century literature may plausibly be ascribed to the tenuous nature of the roles they play in primary texts, and especially to the problematic nature of their agency. This idea is implicit in the arguments of Bruce Robbins, whose The Servant’s Hand remains the most cogent approach to giving servants a palpable role in critical narrative: for Robbins, the agency that acts through the servant ‘prosthesis’ rebounds on the master, granting the servant figure a sometimes exorbitant textual agency. The figure of the sleepwalking maid, and the analogies between sleepwalking and domestic service implicit in it, will help to complicate this picture. In anecdotes of spontaneous sleepwalking, and their subsequent appropriation by mesmerists, maids are cast as non-agents in terms of ownership of narrative: their subjectivity is immaterial to the public fate of the story which their acts generate. But this apparent non-agency is itself derived from their spontaneity; from an autonomous, albeit unconscious, self-will. As such, sleepwalking subjectivity is a gift to paternalism; a mastery it does not have to produce. In conclusion, it is this undetermined quality, rather than a simple lack of agency, that characterizes the maid in the novel, and which continues to exclude domestic servants from critical narrative.

Highly contrasting effects of different climate forcing agents on terrestrial ecosystem services

Many atmospheric constituents besides carbon dioxide (CO2) contribute to global warming, and it is common to compare their influence on climate in terms of radiative forcing, which measures their impact on the planetary energy budget. A number of recent studies have shown that many radiatively active constituents also have important impacts on the physiological functioning of ecosystems, and thus the ‘ecosystem services’ that humankind relies upon. CO2 increases have most probably increased river runoff and had generally positive impacts on plant growth where nutrients are non-limiting, whereas increases in near-surface ozone (O3) are very detrimental to plant productivity. Atmospheric aerosols increase the fraction of surface diffuse light, which is beneficial for plant growth. To illustrate these differences, we present the impact on net primary productivity and runoff of higher CO2, higher near-surface O3, and lower sulphate aerosols, and for equivalent changes in radiative forcing.We compare this with the impact of climate change alone, arising, for example, from a physiologically inactive gas such as methane (CH4). For equivalent levels of change in radiative forcing, we show that the combined climate and physiological impacts of these individual agents vary markedly and in some cases actually differ in sign. This study highlights the need to develop more informative metrics of the impact of changing atmospheric constituents that go beyond simple radiative forcing.

Controlling market power of vertically integrated firms in electricity networks: demand response of aggregator agents

This article reports the results of an experiment that examined how demand aggregators can discipline vertically-integrated firms - generator and distributor-retailer holdings-, which have a high share in wholesale electricity market with uniform price double auction (UPDA). We initially develop a treatment where holding members redistribute the profit based on the imposition of supra-competitive prices, in equal proportions (50%-50%). Subsequently, we introduce a vertical disintegration (unbundling) treatment with holding-s information sharing, where profits are distributed according to market outcomes. Finally, a third treatment is performed to introduce two active demand aggregators, with flexible interruptible loads in real time. We found that the introduction of responsive demand aggregators neutralizes the power market and increases market efficiency, even beyond what is achieved through vertical disintegration.

Activities related with electricity consumption in the Spanish residential sector: variations between days of the week, Autonomous Communities and size of towns

Nowadays the electricity consumption in the residential sector attracts policy and research efforts, in order to propose saving strategies and to attain a better balance between production and consumption, by integrating renewable energy production and proposing suitable demand side management methods. To achieve these objectives it is essential to have real information about household electricity demand profiles in dwellings, highly correlated, among other aspects, with the active occupancy of the homes and to the personal activities carried out in homes by their occupants. Due to the limited information related to these aspects, in this paper, behavioral factors of the Spanish household residents, related to the electricity consumption, have been determined and analyzed, based on data from the Spanish Time Use Surveys, differentiating among the Autonomous Communities and the size of municipalities, or the type of days, weekdays or weekends. Activities involving a larger number of houses are those related to Personal Care, Food Preparation and Washing Dishes. The activity of greater realization at homes is Watching TV, which together with Using PC, results in a high energy demand in an aggregate level. Results obtained enable identify prospective targets for load control and for efficiency energy reduction recommendations to residential consumers.

Heuristic based evolution for the coordination of autonomous vehicles in the absence of speed lanes

The current state of the art in the planning and coordination of autonomous vehicles is based upon the presence of speed lanes. In a traffic scenario where there is a large diversity between vehicles the removal of speed lanes can generate a significantly higher traffic bandwidth. Vehicle navigation in such unorganized traffic is considered. An evolutionary based trajectory planning technique has the advantages of making driving efficient and safe, however it also has to surpass the hurdle of computational cost. In this paper, we propose a real time genetic algorithm with Bezier curves for trajectory planning. The main contribution is the integration of vehicle following and overtaking behaviour for general traffic as heuristics for the coordination between vehicles. The resultant coordination strategy is fast and near-optimal. As the vehicles move, uncertainties may arise which are constantly adapted to, and may even lead to either the cancellation of an overtaking procedure or the initiation of one. Higher level planning is performed by Dijkstra's algorithm which indicates the route to be followed by the vehicle in a road network. Re-planning is carried out when a road blockage or obstacle is detected. Experimental results confirm the success of the algorithm subject to optimal high and low-level planning, re-planning and overtaking.

Dynamic distributed lanes: motion planning for multiple autonomous vehicles

Unorganized traffic is a generalized form of travel wherein vehicles do not adhere to any predefined lanes and can travel in-between lanes. Such travel is visible in a number of countries e.g. India, wherein it enables a higher traffic bandwidth, more overtaking and more efficient travel. These advantages are visible when the vehicles vary considerably in size and speed, in the absence of which the predefined lanes are near-optimal. Motion planning for multiple autonomous vehicles in unorganized traffic deals with deciding on the manner in which every vehicle travels, ensuring no collision either with each other or with static obstacles. In this paper the notion of predefined lanes is generalized to model unorganized travel for the purpose of planning vehicles travel. A uniform cost search is used for finding the optimal motion strategy of a vehicle, amidst the known travel plans of the other vehicles. The aim is to maximize the separation between the vehicles and static obstacles. The search is responsible for defining an optimal lane distribution among vehicles in the planning scenario. Clothoid curves are used for maintaining a lane or changing lanes. Experiments are performed by simulation over a set of challenging scenarios with a complex grid of obstacles. Additionally behaviours of overtaking, waiting for a vehicle to cross and following another vehicle are exhibited.

A study of anticipatory non-autonomous systems

Rhythms are manifested ubiquitously in dynamical biological processes. These fundamental processes which are necessary for the survival of living organisms include metabolism, breathing, heart beat, and, above all, the circadian rhythm coupled to the diurnal cycle. Thus, in mathematical biology, biological processes are often represented as linear or nonlinear oscillators. In the framework of nonlinear and dissipative systems (ie. the flow of energy, substances, or sensory information), they generate stable internal oscillations as a response to environmental input and, in turn, utilise such output as a means of coupling with the environment.