Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase : direct evidence for products and pathways in low temperature benzene oxidation

The phenylperoxyl radical has long been accepted as a critical intermediate in the oxidation of benzene and an archetype for arylperoxyl radicals in combustion and atmospheric chemistry. Despite being central to many contemporary mechanisms underpinning these chemistries, reports of the direct detection or isolation of phenylperoxyl radicals are rare and there is little experimental evidence connecting this intermediate with expected product channels. We have prepared and isolated two charge-tagged phenyl radical models in the gas phase [i.e., 4-(N,N,N-trimethylammonium) phenyl radical cation and 4-carboxylatophenyl radical anion] and observed their reactions with dioxygen by ion-trap mass spectrometry. Measured reaction rates show good agreement with prior reports for the neutral system (k(2)[(Me3N+)C6H4 center dot + O-2] = 2.8 x 10(-11) cm(3) molecule(-1) s(-1), Phi = 4.9%; k(2)[(-O2C)C6H4 center dot + O-2] = 5.4 x 10(-1)1 cm(3) molecule(-1) s(-1), Phi = 9.2%) and the resulting mass spectra provide unequivocal evidence for the formation of phenylperoxyl radicals. Collisional activation of isolated phenylperoxyl radicals reveals unimolecular decomposition by three pathways: (i) loss of dioxygen to reform the initial phenyl radical; (ii) loss of atomic oxygen yielding a phenoxyl radical; and (iii) ejection of the formyl radical to give cyclopentadienone. Stable isotope labeling confirms these assignments. Quantum chemical calculations for both charge-tagged and neutral phenylperoxyl radicals confirm that loss of formyl radical is accessible both thermodynamically and entropically and competitive with direct loss of both hydrogen atom and carbon dioxide.

The syntheses of C6CH2.– and the corresponding carbenoid cumulene C6CH2 in the gas phase

The ion (C6CH2)(.-) is formed in the gas phase by the process -C=C-C=C-C=CH2OEt --> (C6CH2)(.-) + EtO., and charge stripping of the product radical anion yields the carbenoid neutral C6CH2; this can be either a singlet (the ground state), which is best represented as the carbene :C=C=C=C=C=C=CH2, or a triplet; the adiabatic electron affinity and the dipole moment of the carbenoid neutral are calculated to be 2.82 eV and 7.33 D respectively.

State-of-the-art : track degradation at bridge transitions

Transition zones between bridge decks and rail tracks suffer early failure due to poor interaction between rail vehicles and sudden changes of stiffness. This has been an ongoing problem to rail industry and yet still no systematic studies appear to have been taken to maintain a gradually smoothening transmission of forces between the bridge and its approach. Differential settlement between the bridge deck and rail track in the transition zone is the fundamental issue, which negatively impacts the rail industry by causing passenger discomfort, early damage to infrastructure and vehicle components, speed reduction, and frequent maintenance cycles. Identification of mechanism of the track degradation and factors affecting is imperative to design any mitigation method for reducing track degradation rate at the bridge transition zone. Unfortunately this issue is still not well understood, after conducting a numbers of reviews to evaluate the key causes, and introducing a wide range of mitigation techniques. In this study, a comprehensive analysis of the available literature has been carried out to develop either a novel design framework or a mitigation technique for the bridge transition zone. This paper addresses three critical questions in relation to the track degradation at transition zone: (1) what are the causes of bridge transition track degradation?; (2) what are the available mitigation techniques in reducing the track degradation rate?; (3) what are the factors affecting on poor performance of the existing mitigation techniques?. It is found that the absence of soil-water response, dynamic loading response, and behaviour of geotechnical characteristics under long-term conditions in existing track transition design frameworks critically influence on the failures of existing mitigation techniques. This paper also evaluates some of the existing design frameworks to identify how each design framework addresses the track degradation at the bridge transition zone.

State-of-the-art of the Australian thin bed concrete structural masonry

With a view to minimising the spiraling labour costs, the concrete masonry industry is developing thin layer mortar technology (known as thin bed technology) collaboratively with Queensland University of Technology. Similar technologies are practiced in Europe mainly for clay brick masonry; in the UK thin layer mortared concrete masonry has been researched under commercial contract with limited information published. This paper presents numerous experimental data generated over the past three years. It is shown that this form of masonry requires special drymixed mortar containing a minimum of 2% polymer for improved workability and blocks with tighter height tolerance, both of which might increase the cost of these constituent materials. However, through semiskilled labour, tools to dispense and control the thickness of mortar and the associated increase in productivity, reduction to the overall costs of this form of construction can be achieved. Further the polymer mortar provides several advantages: (1) improved sustainability due to dry curing and (2) potential to construct mortar layers of 2mm thickness and (3) ability for mechanisation of mortar application and control of thickness without the need for skilled labour.

Potential interstellar molecules : Formation of neutral C6CO from C6CO- in the gas phase

Computations at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G* level of theory indicate that neutral C6CO is a stable species. The ground state of this neutral is the singlet cumulene oxide :C=C=C=C=C=C=C=O. The adiabatic electron affinity and dipole moment of singlet C6CO are 2.47 eV and 4.13 D, respectively, at this level of theory. The anion (C6CO)(-.) should be a possible precursor to this neutral. It has been formed by an unequivocal synthesis in the ion source of a mass spectrometer by the S(N)2(Si) reaction between (CH3)(3)Si-C=C-C=C-C=C-CO-CMe3 and F- to form C-=C-C=C-C=C-CO-CMe3 which loses Me3C in the source to form C6CO-.. Charge stripping of this anion by vertical Franck-Condon oxidation forms C6CO, characterised by the neutralisation-reionisation spectrum (-NR+) of C6CO-., which is stable during the timeframe of this experiment (10(-6) s), Copyright (C) 2000 John Wiley & Sons, Ltd.

State of Energy Efficiency Education in Australian Technical & Further Education (TAFE) : A Report to the Australian Government Skills for the Carbon Challenge Initiative, The Natural Edge Project (TNEP), Queensland University of Technology

The Australian Government’s Skills for the Carbon Challenge (SCC) initiative aims to accelerate industry and the education sectors response to climate change. As part of the SCC initiative, the Department of Industry, Innovation, Climate Change, Science, Research and Tertiary Education (DIICCSRTE) provided funding to investigate the state of energy efficiency education in engineering-related Australian Technical and Further Education (TAFE) Programs. The following document reports on the outcomes of a multi-stage consultation project that engaged with participants from over 80% of TAFE institutions across Australia with the aim of supporting and enhancing future critical skills development in this area. Specifically, this report presents the findings of a national survey, based on a series of TAFE educator focus groups, conducted in May 2013 aimed at understanding the experiences and insights of Australian TAFE educators teaching engineering-related courses. Responses were received from 224 TAFE Educators across 50 of the 61 TAFE institutions in Australia (82% response rate).

Time-domain hydroelastic analysis of a flexible marine structure using state-space models

This article deals with time-domain hydroelastic analysis of a marine structure. The convolution terms associated with fluid memory effects are replaced by an alternative state-space representation, the parameters of which are obtained by using realization theory. The mathematical model established is validated by comparison to experimental results of a very flexible barge. Two types of time-domain simulations are performed: dynamic response of the initially inert structure to incident regular waves and transient response of the structure after it is released from a displaced condition in still water. The accuracy and the efficiency of the simulations based on the state-space model representations are compared to those that integrate the convolutions.

On optimal control of constrained linear systems with imperfect state information and stochastic disturbances

We address the problem of finite horizon optimal control of discrete-time linear systems with input constraints and uncertainty. The uncertainty for the problem analysed is related to incomplete state information (output feedback) and stochastic disturbances. We analyse the complexities associated with finding optimal solutions. We also consider two suboptimal strategies that could be employed for larger optimization horizons.

In the shadow of the welfare state : the role of payday lending in poverty survival in Australia

A defining characteristic of contemporary welfare governance in many western countries has been a reduced role for governments in direct provision of welfare, including housing, education, health and income support. One of the unintended consequences of devolutionary trends in social welfare is the development of a ‘shadow welfare state’ (Fairbanks, 2009; Gottschalk, 2000), which is a term used to describe the complex partnerships between statebased social protection, voluntarism and marketised forms of welfare. Coupled with this development, conditional workfare schemes in countries such as the United States, Canada, the UK and Australia are pushing more people into informal and semi-formal means of poverty survival (Karger, 2005). These transformations are actively reshaping welfare subjectivities and the role of the state in urban governance. Like other countries such as the US, Canada and the UK, the fringe lending sector in Australia has experienced considerable growth over the last decade. Large numbers of people on low incomes in Australia are turning to non-mainstream financial services, such as payday lenders, for the provision of credit to make ends meet. In this paper, we argue that the use of fringe lenders by people on low incomes reveals important theoretical and practical insights into the relationship between the mixed economy of welfare and the mixed economy of credit in poverty survival.

Freedom to choose? Embryo selection, reproductive decision-making and the role of the state

Involving the biopsy of an eight-cell embryo, PGD has been hailed as a means of making reproductive decisions without having to face the heart-wrenching decision to abort an affected foetus. However, controversy around the kinds of traits for which testing can be done, and who has access to the technology, has led to questions about the way in which the technology is developing. Women who are allowed to access in vitro fertilisation (IVF) services can currently also access PGD in limited circumstances.

Ethylenedione : An intrinsically short-lived molecule

Ethylenedione C2O2 is one of the elusive small molecules which have remained undetected even after numerous attempts with different experimental techniques, This is surprising, since theoretical studies predicted the triplet state of C2O2 to be stable towards spin-allowed dissociation and hence long-lived. Here we report a comprehensive study of charged and neutral ethylenedione by means of charge reversal and neutralization -reionization mass spectrometry. These experimental results, in conjunction with theoretical calculations, suggest that neutral ethylenedione is intrinsically short-lived rather than being elusive, Both the singlet and triplet states of C2O2 are predicted to dissociate rapidly into two ground-state CO molecules, and for the triplet species, this dissociation involves facile curve-crossing to the singlet surface within a few nanoseconds.

Effective channel state information (CSI) feedback for MIMO systems in wireless broadband communications

This research has analysed both reciprocity and feedback mechanisms in multi-antenna wireless systems. It has presented the basis of an effective CSI feedback mechanism that efficiently provides the transmitter with the minimum information to allow the accurate knowledge of a rapidly changing channel. The simulations have been conducted using MATLAB to measure the improvement when the channel is estimated at the receiver in a 2 X 2 multi-antenna system and compared to the case of perfect channel knowledge at the receiver.

Competitive charge-remote and anion-induced fragmentations of the non-8-enoate anion. A charge-remote reaction which co-occurs with hydrogen scrambling

The non-8-enoate anion undergoes losses of the elements of C3H6, C4H8 and C6H12 on collisional activation, The mechanisms of these processes have been elucidated by a combination of product ion and labelling (H-2 and C-13) studies, together with a neutralisation reionisation mass spectrometric study. These studies allow the following conclusions to be made. (i) The loss of C3H6 involves cyclisation of the enolate anion of non-8-enoic acid to yield the cyclopentyl carboxylate anion and propene. (ii) The loss of 'C4H8' is a charge-remote process (one which proceeds remote from the charged centre) which yields the pent-4-enoate anion, butadiene and dihydrogen. This process co-occurs and competes with complex H scrambling. (iii) The major loss of 'C6H12' occurs primarily by a charge-remote process yielding the acrylate anion, hexa-1,5-diene and dihydrogen, but in this case no H scrambling accompanies the process. (iv) It is argued that the major reason why the two charge-remote processes occur in preference to anion-induced losses of but-l-ene and hex-l-ene from the respective 4- and 2-anions is that although these anions are formed, they have alternative and lower energy fragmentation pathways than those involving the losses of but-l-ene and hex-l-ene; viz. the transient 4-anion undergoes facile proton transfer to yield a more stable anion, whereas the 2-(enolate) anion undergoes preferential cyclisation followed by elimination of propene [see (i) above].

The loss of CO from the ortho, meta and para forms of deprotonated methyl benzoate in the gas phase

The ortho, meta and para anions of methyl benzoate may be made in the source of a mass spectrometer by the S(N)2(Si) reactions between HO- and methyl (o-, m-, and p-trimethylsilyl)benzoate respectively. All three anions lose CO upon collisional activation to form the ortho anion of anisole in the ratio ortho>>meta > para. The rearrangement process is charge directed through the ortho anion. Theoretical calculations at the B3LYP/6-311++G(d,p)//HF/6-31+G(d) level of theory indicate that the conversion of the meta and para anions to the ortho anion prior to loss of CO involve 1,2-H transfer(s), rather than carbon scrambling of the methoxycarbonylphenyl anion. There are two mechanisms which can account for this rearrangement, viz. (A) cyclisation of the ortho anion centre to the carbonyl group of the ester to give a cyclic carbonyl system in which the incipient methoxide anion substitutes at one of the two equivalent ring carbons of the three membered ring to yield an intermediate which loses CO to give the ortho anion of anisole, and (B) an elimination reaction to give an intermediate benzyne-methoxycarbonyl anion complex in which the MeOCO- species acts as a MeO- donor, which then adds to benzyne to yield the ortho anion of anisole. Calculations at the B3LYP/6-311++G(d,p)//HF/6-31+G(d) level of theory indicate that (i) the barrier in the first step (the rate determining step) of process A is 87 kJ mol(-1) less than that for the synchronous benzyne process B, and (ii) there are more low frequency vibrations in the transition state for benzyne process B than for the corresponding transition state for process A. Stepwise process A has the lower barrier for the rate determining step, and the lower Arrhenius factor: we cannot differentiate between these two mechanisms on available evidence.

Syntheses of NCN and NC3N from ionic precursors in the gas phase and an unusual rearrangement of neutral NC3N : A joint experimental and theoretical study

Neutral NCN is made in a mass spectrometer by charge stripping of NCN-., while neutral dicyanocarbene NCCCN can be formed by neutralization of either the corresponding anionic and cationic species, NCCCN-. and NCCCN+.. Theoretical calculations at the RCCSD(T)/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory indicate that the (3)Sigma (-)(g) State of NCCCN is 18 kcal mol(-1) more stable than the (1)A(1) state. While the majority of neutrals formed from either NCCCN-. or NCCCN+. correspond to NCCCN, a proportion of the neutral NCCCN molecules have sufficient excess energy to effect rearrangement, as evidenced by a loss of atomic carbon in the neutralization reionization (NR) spectra of either NCCCN+. and NCCCN-.. C-13 labeling studies indicate that loss of carbon occurs statistically following or accompanied by scrambling of all three carbon atoms. A theoretical study at the B3LYP/6-31+G(d)//B3LYP/6-31+G(d) level of theory indicates that C loss is a consequence of the rearrangement sequence NCCCN --> CNCCN --> CNCNC and that C scrambling occurs within singlet CNCCN via the intermediacy of a four-membered C-2v-symmetrical transition structure.