Reaction of Aromatic Peroxyl Radicals with Alkynes: A Mass Spectrometric and Computational Study Using the Distonic Radical Ion Approach

The reaction of the aromatic distonic peroxyl radical cations N-methyl pyridinium-4-peroxyl (PyrOO center dot+) and 4-(N,N,N-trimethyl ammonium)-phenyl peroxyl (AnOO center dot+), with symmetrical dialkyl alkynes 10?ac was studied in the gas phase by mass spectrometry. PyrOO center dot+ and AnOO center dot+ were produced through reaction of the respective distonic aryl radical cations Pyr center dot+ and An center dot+ with oxygen, O2. For the reaction of Pyr center dot+ with O2 an absolute rate coefficient of k1=7.1X10-12 cm3 molecule-1 s-1 and a collision efficiency of 1.2?% was determined at 298 K. The strongly electrophilic PyrOO center dot+ reacts with 3-hexyne and 4-octyne with absolute rate coefficients of khexyne=1.5X10-10 cm3 molecule-1 s-1 and koctyne=2.8X10-10 cm3 molecule-1 s-1, respectively, at 298 K. The reaction of both PyrOO center dot+ and AnOO center dot+ proceeds by radical addition to the alkyne, whereas propargylic hydrogen abstraction was observed as a very minor pathway only in the reactions involving PyrOO center dot+. A major reaction pathway of the vinyl radicals 11 formed upon PyrOO center dot+ addition to the alkynes involves gamma-fragmentation of the peroxy O?O bond and formation of PyrO center dot+. The PyrO center dot+ is rapidly trapped by intermolecular hydrogen abstraction, presumably from a propargylic methylene group in the alkyne. The reaction of the less electrophilic AnOO center dot+ with alkynes is considerably slower and resulted in formation of AnO center dot+ as the only charged product. These findings suggest that electrophilic aromatic peroxyl radicals act as oxygen atom donors, which can be used to generate alpha-oxo carbenes 13 (or isomeric species) from alkynes in a single step. Besides gamma-fragmentation, a number of competing unimolecular dissociative reactions also occur in vinyl radicals 11. The potential energy diagrams of these reactions were explored with density functional theory and ab initio methods, which enabled identification of the chemical structures of the most important products.

Collision warning dissemination in vehicles strings : an empirical measurement

Inter-Vehicular Communications (IVC) are considered a promising technological approach for enhancing transportation safety and improving highway efficiency. Previous theoretical work has demonstrated the benefits of IVC in vehicles strings. Simulations of partially IVC-equipped vehicles strings showed that only a small equipment ratio is sufficient to drastically reduce the number of head on collisions. However, these results are based on the assumptions that IVC exhibit lossless and instantaneous messages transmission. This paper presents the research design of an empirical measurement of a vehicles string, with the goal of highlighting the constraints introduced by the actual characteristics of communication devices. A warning message diffusion system based on IEEE 802.11 wireless technology was developed for an emergency breaking scenario. Preliminary results are presented as well, showing the latencies introduced by using 802.11a and discussing early findings and experimental limitations

Efficient safety message dissemination for cooperative collision warning via context modelling

A Cooperative Collision Warning System (CCWS) is an active safety techno- logy for road vehicles that can potentially reduce traffic accidents. It provides a driver with situational awareness and early warnings of any possible colli- sions through an on-board unit. CCWS is still under active research, and one of the important technical problems is safety message dissemination. Safety messages are disseminated in a high-speed mobile environment using wireless communication technology such as Dedicated Short Range Communication (DSRC). The wireless communication in CCWS has a limited bandwidth and can become unreliable when used inefficiently, particularly given the dynamic nature of road traffic conditions. Unreliable communication may significantly reduce the performance of CCWS in preventing collisions. There are two types of safety messages: Routine Safety Messages (RSMs) and Event Safety Messages (ESMs). An RSM contains the up-to-date state of a vehicle, and it must be disseminated repeatedly to its neighbouring vehicles. An ESM is a warning message that must be sent to all the endangered vehi- cles. Existing RSM and ESM dissemination schemes are inefficient, unscalable, and unable to give priority to vehicles in the most danger. Thus, this study investigates more efficient and scalable RSM and ESM dissemination schemes that can make use of the context information generated from a particular traffic scenario. Therefore, this study tackles three technical research prob- lems, vehicular traffic scenario modelling and context information generation, context-aware RSM dissemination, and context-aware ESM dissemination. The most relevant context information in CCWS is the information about possible collisions among vehicles given a current vehicular traffic situation. To generate the context information, this study investigates techniques to model interactions among multiple vehicles based on their up-to-date motion state obtained via RSM. To date, there is no existing model that can represent interactions among multiple vehicles in a speciffic region and at a particular time. The major outcome from the first problem is a new interaction graph model that can be used to easily identify the endangered vehicles and their danger severity. By identifying the endangered vehicles, RSM and ESM dis- semination can be optimised while improving safety at the same time. The new model enables the development of context-aware RSM and ESM dissemination schemes. To disseminate RSM efficiently, this study investigates a context-aware dis- semination scheme that can optimise the RSM dissemination rate to improve safety in various vehicle densities. The major outcome from the second problem is a context-aware RSM dissemination protocol. The context-aware protocol can adaptively adjust the dissemination rate based on an estimated channel load and danger severity of vehicle interactions given by the interaction graph model. Unlike existing RSM dissemination schemes, the proposed adaptive scheme can reduce channel congestion and improve safety by prioritising ve- hicles that are most likely to crash with other vehicles. The proposed RSM protocol has been implemented and evaluated by simulation. The simulation results have shown that the proposed RSM protocol outperforms existing pro- tocols in terms of efficiency, scalability and safety. To disseminate ESM efficiently, this study investigates a context-aware ESM dissemination scheme that can reduce unnecessary transmissions and deliver ESMs to endangered vehicles as fast as possible. The major outcome from the third problem is a context-aware ESM dissemination protocol that uses a multicast routing strategy. Existing ESM protocols use broadcast rout- ing, which is not efficient because ESMs may be sent to a large number of ve- hicles in the area. Using multicast routing improves efficiency because ESMs are sent only to the endangered vehicles. The endangered vehicles can be identified using the interaction graph model. The proposed ESM protocol has been implemented and evaluated by simulation. The simulation results have shown that the proposed ESM protocol can prevent potential accidents from occurring better than existing ESM protocols. The context model and the RSM and ESM dissemination protocols can be implemented in any CCWS development to improve the communication and safety performance of CCWS. In effect, the outcomes contribute to the realisation of CCWS that will ultimately improve road safety and save lives.

Intelligent collision avoidance, control and guidance

This paper reviews a variety of advanced signal processing algorithms that have been developed at the University of Southampton as part of the Prometheus (Programme for European traffic flow with highest efficiency and unprecedented safety) programme to achieve an intelligent driver warning system (IDWS). The IDWS includes the detection of road edges, lanes, obstacles and their tracking and identification, estimates of time to collision, and behavioural modelling of drivers for a variety of scenarios. The underlying algorithms are briefly discussed in support of the IDWS.

On the efficiency of impingers with fritted nozzle tip for collection of ultrafine particles

The aim of this study was to determine the collection efficiency of ultrafine particles into an impinger fitted with a fritted nozzle tip as a means to increase contact surface area between the aerosol and the liquid. The influence of liquid sampling volume, frit porosity and the nature of the sampling liquid was explored and it was shown that all impact on the collection efficiency of particles smaller than 220 nm. Obtained values for overall collection efficiency were substantially higher (~30–95%) than have been previously reported, mainly due to the high deposition of particles in the fritted nozzle tip, especially in case of finer porosity frits and smaller particles. Values for the capture efficiency of the solvent alone ranged from 20 to 45%, depending on the type and the volume of solvent. Additionally, our results show that airstream dispersion into bubbles improves particle trapping by the liquid and that there is a difference in collection efficiencies based on the nature and volume of the solvent used.

Final report : tasks 1 and 4: eco-efficiency assessment of building refurbishment

The main objective was to compare the environmental impacts of a building undergoing refurbishment both before and after the refurbishment and to assist in the design of the refurbishment with what is learned.

Re-life of buildings - decision support tools for maximising project efficiency

This paper describes the process adopted in developing an integrated decision support framework for planning of office building refurbishment projects, with specific emphasize on optimising rentable floor space, structural strengthening, residual life and sustainability. Expert opinion on the issues to be considered in a tool is being captured through the DELPHI process, which is currently ongoing. The methodology for development of the integrated tool will be validated through decisions taken during a case study project: refurbishment of CH1 building of Melbourne City Council, which will be followed through to completion by the research team. Current status of the CH1 planning will be presented in the context of the research project.

Test architecture for prototyping automated dynamic airspace control

The automation of various aspects of air traffic management has many wide-reaching benefits including: reducing the workload for Air Traffic Controllers; increasing the flexibility of operations (both civil and military) within the airspace system through facilitating automated dynamic changes to en-route flight plans; ensuring safe aircraft separation for a complex mix of airspace users within a highly complex and dynamic airspace management system architecture. These benefits accumulate to increase the efficiency and flexibility of airspace use(1). Such functions are critical for the anticipated increase in volume of manned and unmanned aircraft traffic. One significant challenge facing the advancement of airspace automation lies in convincing air traffic regulatory authorities that the level of safety achievable through the use of automation concepts is comparable to, or exceeds, the accepted safety performance of the current system.

Sustainable construction for the future - the role of government in energy efficiency and sustainability in buildings

This paper will summarise the findings from a study that explored the link between dwelling design, or type, and energy efficiencies in sub-tropical climates. An increasing number of government and private sector development companies are initiating projects that aim to deliver enhanced environmental outcomes at both sub-divisional and dwelling levels. The study used AccuRate, a new thermal modelling tool developed by CSIRO that responds to the need to improve ventilation modelling. The study found that dwellings developed in conjunction with the Departments of Housing and Public Works have set the benchmark. It provides a snapshot of the energy efficiency of a range of dwelling types found in recent subdivisions. However, the trend toward increasing urban densities may reduce the likelihood that cooling breezes will be available to cool dwellings. The findings are relevant to regulators, designers and industry in all states interested in reducing the energy used to cool dwellings in summer.

Integrating eco-efficiency assessment of commercial buildings into the design process : LCADesign

The ability to assess a commercial building for its impact on the environment at the earliest stage of design is a goal which is achievable by integrating several approaches into a single procedure directly from the 3D CAD representation. Such an approach enables building design professionals to make informed decisions on the environmental impact of building and its alternatives during the design development stage instead of at the post-design stage where options become limited. The indicators of interest are those which relate to consumption of resources and energy, contributions to pollution of air, water and soil, and impacts on the health and wellbeing of people in the built environment as a result of constructing and operating buildings. 3D object-oriented CAD files contain a wealth of building information which can be interrogated for details required for analysis of the performance of a design. The quantities of all components in the building can be automatically obtained from the 3D CAD objects and their constituent materials identified to calculate a complete list of the amounts of all building products such as concrete, steel, timber, plastic etc. When this information is combined with a life cycle inventory database, key internationally recognised environmental indicators can be estimated. Such a fully integrated tool known as LCADesign has been created for automated ecoefficiency assessment of commercial buildings direct from 3D CAD. This paper outlines the key features of LCADesign and its application to environmental assessment of commercial buildings.

LCADesign : an integrated approach to automatic eco-efficiency assessment of commercial buildings

Buildings consume resources and energy, contribute to pollution of our air, water and soil, impact the health and well-being of populations and constitute an important part of the built environment in which we live. The ability to assess their design with a view to reducing that impact automatically from their 3D CAD representations enables building design professionals to make informed decisions on the environmental impact of building structures. Contemporary 3D object-oriented CAD files contain a wealth of building information. LCADesign has been designed as a fully integrated approach for automated eco-efficiency assessment of commercial buildings direct from 3D CAD. LCADesign accesses the 3D CAD detail through Industry Foundation Classes (IFCs) - the international standard file format for defining architectural and constructional CAD graphic data as 3D real-world objects - to permit construction professionals to interrogate these intelligent drawing objects for analysis of the performance of a design. The automated take-off provides quantities of all building components whose specific production processes, logistics and raw material inputs, where necessary, are identified to calculate a complete list of quantities for all products such as concrete, steel, timber, plastic etc and combines this information with the life cycle inventory database, to estimate key internationally recognised environmental indicators such as CML, EPS and Eco-indicator 99. This paper outlines the key modules of LCADesign and their role in delivering an automated eco-efficiency assessment for commercial buildings.

Multi-vehicles interaction graph model for cooperative collision warning system

Cooperative collision warning system for road vehicles, enabled by recent advances in positioning systems and wireless communication technologies, can potentially reduce traffic accident significantly. To improve the system, we propose a graph model to represent interactions between multiple road vehicles in a specific region and at a specific time. Given a list of vehicles in vicinity, we can generate the interaction graph using several rules that consider vehicle's properties such as position, speed, heading, etc. Safety applications can use the model to improve emergency warning accuracy and optimize wireless channel usage. The model allows us to develop some congestion control strategies for an efficient multi-hop broadcast protocol.