Ethnic diversity and its impact on community social cohesion and neighborly exchange

Putnam's “constrict theory” suggests that ethnic diversity creates challenges for developing and sustaining social capital in urban settings. He argues that diversity decreases social cohesion and reduces social interactions among community residents. While Putnam's thesis is the subject of much debate in North America, the United Kingdom, and Europe, there is a limited focus on how ethnic diversity impacts upon social cohesion and neighborly exchange behaviors in Australia. Employing multilevel modeling and utilizing administrative and survey data from 4,000 residents living in 148 Brisbane suburbs, we assess whether ethnic diversity lowers social cohesion and increases “hunkering.” Our findings indicate that social cohesion and neighborly exchange are attenuated in ethnically diverse suburbs. However, diversity is less consequential for neighborly exchange among immigrants when compared to the general population. Our results provide at least partial support for Putnam's thesis.

Formation of the heterocumulene anion SCCCN- by a cyano migration from the radical anion of 1,2-dicyanoethylenedithiolate

The anionic heterocumulene SCCCN- was generated in the gas phase by collisional activation of the radical anion of 1,2-dicyanoethylenedithiolate. The mechanism of this reaction, as well as the structures of neutral and anionic products, was investigated by hybrid density functional theory (DFT) calculations. Dissociation to form SCCCN- and SCN is proposed to occur by a radical directed cyano migration reaction, with calculations suggesting this is the lowest energy fragmentation pathway available to the precursor anion. In contrast, the even-electron protonated 1,2-dicyanoethylenedithiolate anion fragmented by loss of HCN.

Energy Transformed : Building Capacity in the Engineering Profession in Australia

Global pressures of burgeoning population growth and consumption are threatening efforts to reduce negative environmental pressures associated with development such as atmospheric, land and water pollution. For example, the world’s population is now growing at over 70 million per year or 1 billion per decade (Brown, 2007), increasing from 3.5 billion in 1970, to 5 billion in 1990, to 7 billion by 2010 (United Nations, 2002). In 1990 only 13 percent of the global population lived in cities, while in 2007 more than half did. More than 60 percent of the global population lives within 100 kilometers of the coastline (World Resources Institute, 2005) and nearly all of the population growth hereon is forecast to happen in developing countries (Postel, 1999). Future levels of stress on the global environment are therefore likely to increase if current trends are used for forecasting, which is particularly challenging as scientists are already observing significant signs of degradation and failure in environmental systems. For example, the Intergovernmental Panel on Climate Change Fourth Assessment Report (IPCC, 2007) provided an nequivocal link between climate change and current human activities, in particular: the burning of fossil fuels; deforestation and land clearing; the use of synthetic greenhouse gases; and decomposition of wastes from landfill. The UK Stern Review concluded that within our lifetime there is between a 77 to 99 percent chance (depending on the climate model used) of the global average temperature rising by more than 2 degrees Celsius (Stern, 2006), with a likely greenhouse gas concentration in the atmosphere of 550 parts per million (ppm) or more by around 2100.

Pilot plant studies of ion exchange for desalination of coal seam gas produced water

This paper reports a study of ion exchange (IX) as an alternative CSG water treatment to the widely used reverse osmosis (RO) desalination process. An IX pilot plant facility has been constructed and operated using both synthetic and real CSG water samples. Application of appropriate synthetic resin technology has proved the effectiveness of IX processes.

Electron capture of tetracyanoethylene oxide in the gas phase. Rearrangement of the parent radical anion to form [(NC)(3)C](-). A joint experimental and ab initio study

Capture of an electron by tetracyanoethylene oxide can initiate a number of decomposition pathways. One of these decompositions yields [(NC)3C]− as the ionic product. Ab initio calculations (at the B3LYP/6-31+G∗ level of theory) indicate that the formation of [(NC)3C]− is initiated by capture of an electron into the LUMO of tetracyanoethylene oxide to yield the anion radical [(NC)2C–O–C(CN)2]−· that undergoes internal nucleophilic substitution to form intermediate [(NC)3C–OCCN]−·. This intermediate dissociates to form [(NC)3C]− (m/z 90) as the ionic product. The radical (NC)3C· has an electron affinity of 4.0 eV (385 kJ mol−1). Ab initio calculations show that [(NC)3C]− is trigonal planar with the negative charge mainly on the nitrogens. A pictorial representation of this structure is the resonance structure formed from three degenerate contributing structures (NC)2–CCN−. The other product of the reaction is nominally (NCCO)·, but there is no definitive experimental evidence to indicate whether this radical survives intact, or decomposes to NC· and CO. The overall process [(NC)2C–O–C(CN)2]−· → [(NC)3C]− + (NCCO)· is calculated to be endothermic by 21 kJ mol−1 with an overall barrier of 268 kJ mol−1.

Continuous after-the-fact leakage-resilient key exchange

Security models for two-party authenticated key exchange (AKE) protocols have developed over time to provide security even when the adversary learns certain secret keys. In this work, we advance the modelling of AKE protocols by considering more granular, continuous leakage of long-term secrets of protocol participants: the adversary can adaptively request arbitrary leakage of long-term secrets even after the test session is activated, with limits on the amount of leakage per query but no bounds on the total leakage. We present a security model supporting continuous leakage even when the adversary learns certain ephemeral secrets or session keys, and give a generic construction of a two-pass leakage-resilient key exchange protocol that is secure in the model; our protocol achieves continuous, after-the-fact leakage resilience with not much more cost than a previous protocol with only bounded, non-after-the-fact leakage.

Expanding Emergency Department capacity : a multisite study

Objectives: To i) identify predictors of admission, and ii) describe outcomes for patients who arrived via ambulance to three Australian public Emergency Departments (EDs), before and after the opening of 41 additional ED beds within the area. Methods: A retrospective, comparative, cohort study using deterministically linked health data collected between 3 September 2006 and 2 September 2008. Data included ambulance offload delay, time to see doctor, ED length of stay (ED LOS), admission requirement, access block, hospital length of stay and in-hospital mortality. Logistic regression analysis was undertaken to identify predictors of hospital admission. Results: One third of all 286,037 ED presentations were via ambulance (n= 79,196) and 40.3% required admission. After increasing emergency capacity, the only outcome measure to improve was in-hospital mortality. Ambulance offload delay, time to see doctor, ED length of stay (ED LOS), admission requirement, access block, hospital length of stay did not improve. Strong predictors of admission before and after increased capacity included: age over 65 years, Australian Triage Scale (ATS) category 1-3, diagnoses of circulatory or respiratory conditions and ED LOS > 4 hours. With additional capacity the odds ratios for these predictors increased for age >65 and ED LOS > 4 hours and decreased for triage category and ED diagnoses. Conclusions: Expanding ED capacity from 81 to 122 beds within a health service area impacted favourably on mortality outcomes but not on time-related service outcomes such as ambulance offload time, time to see doctor and ED LOS. To improve all service outcomes, when altering (increasing/decreasing) ED bed numbers, the whole healthcare system needs to be considered.

Optimising employee engagement with internal communication : a social exchange perspective

Drawing on principles of social exchange this thesis employs mediated regression to investigate the relationship between internal communication and employee engagement in the Australian workforce. Findings suggest organisations and supervisors should focus internal communication efforts toward building greater perceptions of support and stronger identification among employees in order to foster optimal engagement. This research contributes to public relations and management scholarship through understanding how perceived support and identification act as mediating mechanisms in the relationship between internal communication and employee engagement at the organisational and supervisory level.

Impacts of vessel capacity reduction programmes on efficiency in fisheries : the case of Australia’s multispecies northern prawn fishery

Capacity reduction programmes, in the form of buybacks or decommissioning, have had relatively widespread application in fisheries in the US, Europe and Australia. A common criticism of such programmes is that they remove the least efficient vessels first, resulting in an increase in average efficiency of the remaining fleet, which tends to increase the effective fishing power of the remaining fleet. In this paper, the effects of a buyback programme on average technical efficiency in Australia’s Northern Prawn Fishery are examined using a multi-output production function approach with an explicit inefficiency model. As expected, the results indicate that average efficiency of the remaining vessels was generally greater than that of the removed vessels. Further, there was some evidence of an increase in average scale efficiency in the fleet as the remaining vessels were closer, on average, to the optimal scale. Key factors affecting technical efficiency included company structure and the number of vessels fishing. In regard to fleet size, our model suggests positive externalities associated with more boats fishing at any point in time (due to information sharing and reduced search costs), but also negative externalities due to crowding, with the latter effect dominating the former. Hence, the buyback resulted in a net increase in the individual efficiency of the remaining vessels due to reduced crowding, as well as raising average efficiency through removal of less efficient vessels.

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.

Formation of neutral C7H2 isomers from pour isomeric C7H2 radical anion precursors in the gas phase

Consideration of theoretical calculations \[E3LYP/aug-cc-pVDZ//B3LYP/6-31G(d)\] of the structures of ten C7H2 neutral isomers and the nine corresponding C7H2 radical anions have led us to synthesize four stable C7H2 radical anions in the ion source of our ZAB 2HF mass spectrometer, and to convert these to C7H2 neutrals. The four radical anion isomers prepared were (i) \[(HC equivalent to C)(2)C=C=C\](-.) \[from the reaction between (HC equivalent to C)(3)COCH3 and HO- \], (ii) \[HC=C=C=C=C=C=CH\](-.) \[from the reaction between HC equivalent to C-C equivalent to C-CD(OH)-C equivalent to CH and HO-\], (iii) \[C=C=C=C=C=C=CH2\](-.) \[from the reaction between DC equivalent to C-C equivalent to C-C equivalent to C-CH2OCH2CH3 and HO-\], and (iv) \[C equivalent to C-CH2-C equivalent to C-C equivalent to C\](-.) \[from the bis desilylation reaction of (CH3)(3)Si-C equivalent to C-CH2-C equivalent to C-C equivalent to C-Si (CH3)(3)With SF6-.\]. The four anions were further characterized by their collisional activation (negative ion) and charge reversal (CR, positive ion) mass spectra. The anions were converted into their corresponding neutrals by charge stripping, and the correspondence between the charge reversal (CR) and neutralization reionization (-NR+) mass spectra of each anion is taken as evidence that within the time frame of the -NR+ experiment (some 10(-6) s), each neutral is stable and undergoes no major rearrangement or interconversion to a more stable isomer. Theory and experiment are in accord for these systems.

Formation of neutral C7H2 isomers from four isomeric C7H2 radical anion precursors in the gas phase

Consideration of theoretical calculations [B3LYP/aug-cc-pVDZ//B3LYP/6-31G(d)] of the structures of ten C7H2 neutral isomers and the nine corresponding C7H2 radical anions have led us to synthesize four stable C7H2 radical anions in the ion source of our ZAB 2HF mass spectrometer, and to convert these to C7H2 neutrals. The four radical anion isomers prepared were (i) [(HC≡C)2C=C=C]-̇ [from the reaction between (HC≡C)3COCH3 and HO- ], (ii) [HC=C=C=C=C=C=CH]-̇ [from the reaction between HC≡C-C≡C- CD(OH)-C≡CH and HO-], (iii) [C=C=C=C=C=C=CH2]-̇ [from the reaction between DC≡C-C≡C- C≡C-CH2OCH2CH3 and HO-], and (iv) [C≡C-CH2-C≡C-C≡C]-̇ [from the bis desilylation reaction of (CH3)3Si-C≡C-CH2-C≡C-C≡C-Si (CH3)3 with SF6 -̇]. The four anions were further characterized by their collisional activation (negative ion) and charge reversal (CR, positive ion) mass spectra. The anions were converted into their corresponding neutrals by charge stripping, and the correspondence between the charge reversal (CR) and neutralization reionization (-NR+) mass spectra of each anion is taken as evidence that within the time frame of the -NR+ experiment (some 10-6 s), each neutral is stable and undergoes no major rearrangement or interconversion to a more stable isomer. Theory and experiment are in accord for these systems.

Investigation of the gas phase reactivity of the 1-adamantyl radical using a distonic radical anion approach

The gas phase reactions of the bridgehead 3-carboxylato-1-adamantyl radical anion were observed with a series of neutral reagents using a modified electrospray ionisation linear ion trap mass spectrometer. This distonic radical anion was observed to undergo processes suggestive of radical reactivity including radical-radical combination reactions, substitution reactions and addition to carbon-carbon double bonds. The rate constants for reactions of the 3-carboxylato-1-adamantyl radical anion with the following reagents were measured ( in units 10(-12) cm(3) molecule(-1) s(-1)): O-18(2) ( 85 +/- 4), NO ( 38.4 +/- 0.4), I-2 ( 50 +/- 50), Br-2 ( 8 +/- 2), CH3SSCH3 ( 12 +/- 2), styrene ( 1.20 +/- 0.03), CHCl3 ( H abstraction 0.41 +/- 0.06, Cl abstraction 0.65 +/- 0.1), CDCl3 ( D abstraction 0.035 +/- 0.01, Cl abstraction 0.723 +/- 0.005), allyl bromide (Br abstraction 0.53 +/- 0.04, allylation 0.25 +/- 0.01). Collision rates were calculated and reaction efficiencies are also reported. This study represents the first quantitative measurement of the gas phase reactivity of a bridgehead radical and suggests that distonic radical anions are good models for the study of their elusive uncharged analogues.