Ultrafast excited state dynamics controlling photochemical isomerization of N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium coordinated to a {Re-1(CO)(3)(2,2 '-bipyridine)} chromophore

Two Multifunctional photoactive complexes [Re(Cl)(CO)(3)-(MeDpe(+))(2)](2+) and [Re(MeDpe(+))(CO)(3)(bpy)](2+) (MeDpe(+) = N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium, bpy = 2,2'-bipyridine) were synthesized. characterized. and their redox and photonic properties were investigated by cyclic voltammetry: ultraviolet-visible-infrared (UV/Vis/IR) spectroelectrochemistry, stationary UV/Vis and resonance Raman spectroscopy; photolysis; picosecond time-resolved absorption spectroscopy in the visible and infrared regions: and time-resolved resonance Raman spectroscopy. The first reduction step of either complex Occurs at about -1.1 V versus Fc/Fc(+) and is localized at MeDpe(+). Reduction alone does not induce a trans -> cis isomerization of MeDpe(+). [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) is photostable, while [Re(MeDpe(+))(CO)(3)(bpy)](2+) and free MeDpe(+) isomerize under near-UV irradiation. The lowest excited state of [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) has been identified as the Re(Cl)(CO)(3) -> MeDpe(+) (MLCT)-M-3 (MLCT = metal-to-ligand charge transfer), decaying directly to the ground state with lifetimes of approximate to 42 (73%) and approximate to 430ps (27%). Optical excitation of [Re(MeDpe(+))(CO)(3)(bpy)](2+) leads to population of Re(CO)(3) -> MeDpe(+) and Re(CO)(3) -> bpy (MLCT)-M-3 states, from which a MeDpe(+) localized intraligand 3 pi pi* excited state ((IL)-I-3) is populated with lifetimes of approximate to 0.6 and approximate to 10 ps, respectively. The 3IL state undergoes a approximate to 21 ps internal rotation, which eventually produces the cis isomer on a much longer timescale. The different excited-state behavior of the two complexes and the absence of thermodynamically favorable interligand electron transfer in excited [Re(MeDpe(+))(CO)(3)(bpy)](2+) reflect the fine energetic balance between excited states of different orbital origin, which can be tuned by subtle Structural variations. The complex [Re(MeDpe+)(CO)(3)(bpy)](2+) emerges as a prototypical, multifunctional species with complementary redox and photonic behavior.

Factors controlling the distribution of ozone in the West African lower troposphere during the AMMA (African Monsoon Multidisciplinary Analysis) wet season campaign

Ozone and its precursors were measured on board the Facility for Airborne Atmospheric Measurements (FAAM) BAe 146 Atmospheric Research Aircraft during the monsoon season 2006 as part of the African Monsoon Multidisciplinary Analysis (AMMA) campaign. One of the main features observed in the west African boundary layer is the increase of the ozone mixing ratios from 25 ppbv over the forested area (south of 12 degrees N) up to 40 ppbv over the Sahelian area. We employ a two-dimensional ( latitudinal versus vertical) meteorological model coupled with an O-3-NOx-VOC chemistry scheme to simulate the distribution of trace gases over West Africa during the monsoon season and to analyse the processes involved in the establishment of such a gradient. Including an additional source of NO over the Sahelian region to account for NO emitted by soils we simulate a mean NOx concentration of 0.7 ppbv at 16 degrees N versus 0.3 ppbv over the vegetated region further south in reasonable agreement with the observations. As a consequence, ozone is photochemically produced with a rate of 0.25 ppbv h(-1) over the vegetated region whilst it reaches up to 0.75 ppbv h(-1) at 16 degrees N. We find that the modelled gradient is due to a combination of enhanced deposition to vegetation, which decreases the ozone levels by up to 11 pbbv, and the aforementioned enhanced photochemical production north of 12 degrees N. The peroxy radicals required for this enhanced production in the north come from the oxidation of background CO and CH4 as well as from VOCs. Sensitivity studies reveal that both the background CH4 and partially oxidised VOCs, produced from the oxidation of isoprene emitted from the vegetation in the south, contribute around 5-6 ppbv to the ozone gradient. These results suggest that the northward transport of trace gases by the monsoon flux, especially during nighttime, can have a significant, though secondary, role in determining the ozone gradient in the boundary layer. Convection, anthropogenic emissions and NO produced from lightning do not contribute to the establishment of the discussed ozone gradient.

Exploring context-awareness in the construction logistics services delivery

Managing a construction project supply chain effectively and efficiently is extremely difficult due to involvement of numerous sectors that are supported by ineffective communication system. An efficient construction supply chain system ensures the delivery of materials and other services to construction site while minimising costs and rewarding all sectors based on value added to the supply chain. The advancement of information, communication and wireless technologies is driving construction companies to deploy supply chain management strategies to seek better outputs. As part of the emerging wireless technologies, contextaware computing capability represents the next generation of ICT to the construction services. Conceptually, context-awareness could be integrated with Web Services in order to ensure the delivery of pertinent information to construction site and enhance construction supply chain collaboration. An initial study has indicated that this integrated system has the potential of serving and improving the construction services delivery through access to context-specific data, information and services on as-needed basis.

Intelligent wireless web services: context-aware computing in construction-logistics supply chain

The construction industry has incurred a considerable amount of waste as a result of poor logistics supply chain network management. Therefore, managing logistics in the construction industry is critical. An effective logistic system ensures delivery of the right products and services to the right players at the right time while minimising costs and rewarding all sectors based on value added to the supply chain. This paper reports on an on-going research study on the concept of context-aware services delivery in the construction project supply chain logistics. As part of the emerging wireless technologies, an Intelligent Wireless Web (IWW) using context-aware computing capability represents the next generation ICT application to construction-logistics management. This intelligent system has the potential of serving and improving the construction logistics through access to context-specific data, information and services. Existing mobile communication deployments in the construction industry rely on static modes of information delivery and do not take into account the worker’s changing context and dynamic project conditions. The major problems in these applications are lack of context-specificity in the distribution of information, services and other project resources, and lack of cohesion with the existing desktop based ICT infrastructure. The research works focus on identifying the context dimension such as user context, environmental context and project context, selection of technologies to capture context-parameters such wireless sensors and RFID, selection of supporting technologies such as wireless communication, Semantic Web, Web Services, agents, etc. The process of integration of Context-Aware Computing and Web-Services to facilitate the creation of intelligent collaboration environment for managing construction logistics will take into account all the necessary critical parameters such as storage, transportation, distribution, assembly, etc. within off and on-site project.

Controlling steering and judging heading: retinal flow, visual direction, and extraretinal information

The contribution of retinal flow (RF), extraretinal (ER), and egocentric visual direction (VD) information in locomotor control was explored. First, the recovery of heading from RF was examined when ER information was manipulated; results confirmed that ER signals affect heading judgments. Then the task was translated to steering curved paths, and the availability and veracity of VD were manipulated with either degraded or systematically biased RE Large steering errors resulted from selective manipulation of RF and VD, providing strong evidence for the combination of RF, ER, and VD. The relative weighting applied to RF and VD was estimated. A point-attractor model is proposed that combines redundant sources of information for robust locomotor control with flexible trajectory planning through active gaze.

A technique for evaluation of interactive evolutionary systems

Very large scale scheduling and planning tasks cannot be effectively addressed by fully automated schedule optimisation systems, since many key factors which govern 'fitness' in such cases are unformalisable. This raises the question of an interactive (or collaborative) approach, where fitness is assigned by the expert user. Though well-researched in the domains of interactively evolved art and music, this method is as yet rarely used in logistics. This paper concerns a difficulty shared by all interactive evolutionary systems (IESs), but especially those used for logistics or design problems. The difficulty is that objective evaluation of IESs is severely hampered by the need for expert humans in the loop. This makes it effectively impossible to, for example, determine with statistical confidence any ranking among a decent number of configurations for the parameters and strategy choices. We make headway into this difficulty with an Automated Tester (AT) for such systems. The AT replaces the human in experiments, and has parameters controlling its decision-making accuracy (modelling human error) and a built-in notion of a target solution which may typically be at odds with the solution which is optimal in terms of formalisable fitness. Using the AT, plausible evaluations of alternative designs for the IES can be done, allowing for (and examining the effects of) different levels of user error. We describe such an AT for evaluating an IES for very large scale planning.

High signal to noise ratio THz spectroscopy with ASOPS and signal processing schemes for mapping and controlling molecular and bulk relaxation processes

Asynchronous Optical Sampling has the potential to improve signal to noise ratio in THz transient sperctrometry. The design of an inexpensive control scheme for synchronising two femtosecond pulse frequency comb generators at an offset frequency of 20 kHz is discussed. The suitability of a range of signal processing schemes adopted from the Systems Identification and Control Theory community for further processing recorded THz transients in the time and frequency domain are outlined. Finally, possibilities for femtosecond pulse shaping using genetic algorithms are mentioned.

The influence of organic acids in relation to acid deposition in controlling the acidity of soil and stream waters on a seasonal basis

Much uncertainty still exists regarding the relative importance of organic acids in relation to acid deposition in controlling the acidity of soil and surface waters. This paper contributes to this debate by presenting analysis of seasonal variations in atmospheric deposition, soil solution and stream water chemistry for two UK headwater catchments with contrasting soils. Acid neutralising capacity (ANC), dissolved organic carbon (DOC) concentrations and the Na:Cl ratio of soil and stream waters displayed strong seasonal patterns with little seasonal variation observed in soil water pH. These patterns, plus the strong relationships between ANC, Cl and DOC, suggest that cation exchange and seasonal changes in the production of DOC and seasalt deposition are driving a shift in the proportion of acidity attributable to strong acid anions, from atmospheric deposition, during winter to predominantly organic acids in summer.

Modelling sediment supply and transport in the River Lugg: strategies for controlling sediment loads

The River Lugg has particular problems with high sediment loads that have resulted in detrimental impacts on ecology and fisheries. A new dynamic, process-based model of hydrology and sediments (INCA- SED) has been developed and applied to the River Lugg system using an extensive data set from 1995–2008. The model simulates sediment sources and sinks throughout the catchment and gives a good representation of the sediment response at 22 reaches along the River Lugg. A key question considered in using the model is the management of sediment sources so that concentrations and bed loads can be reduced in the river system. Altogether, five sediment management scenarios were selected for testing on the River Lugg, including land use change, contour tillage, hedging and buffer strips. Running the model with parameters altered to simulate these five scenarios produced some interesting results. All scenarios achieved some reduction in sediment levels, with the 40% land use change achieving the best result with a 19% reduction. The other scenarios also achieved significant reductions of between 7% and 9%. Buffer strips produce the best result at close to 9%. The results suggest that if hedge introduction, contour tillage and buffer strips were all applied, sediment reductions would total 24%, considerably improving the current sediment situation. We present a novel cost-effectiveness analysis of our results where we use percentage of land removed from production as our cost function. Given the minimal loss of land associated with contour tillage, hedges and buffer strips, we suggest that these management practices are the most cost-effective combination to reduce sediment loads.

Processes controlling DOC in pore water during simulated drought cycles in six different UK peats

The effect of episodic drought on dissolved organic carbon (DOC) dynamics in peatlands has been the subject of considerable debate, as decomposition and DOC production is thought to increase under aerobic conditions, yet decreased DOC concentrations have been observed during drought periods. Decreased DOC solubility due to drought-induced acidification driven by sulphur (S) redox reactions has been proposed as a causal mechanism; however evidence is based on a limited number of studies carried out at a few sites. To test this hypothesis on a range of different peats, we carried out controlled drought simulation experiments on peat cores collected from six sites across Great Britain. Our data show a concurrent increase in sulphate (SO4) and a decrease in DOC across all sites during simulated water table draw-down, although the magnitude of the relationship between SO4 and DOC differed between sites. Instead, we found a consistent relationship across all sites between DOC decrease and acidification measured by the pore water acid neutralising capacity (ANC). ANC provided a more consistent measure of drought-induced acidification than SO4 alone because it accounts for differences in base cation and acid anions concentrations between sites. Rewetting resulted in rapid DOC increases without a concurrent increase in soil respiration, suggesting DOC changes were primarily controlled by soil acidity not soil biota. These results highlight the need for an integrated analysis of hydrologically driven chemical and biological processes in peatlands to improve our understanding and ability to predict the interaction between atmospheric pollution and changing climatic conditions from plot to regional and global scales.