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.

Reactions of the hydroperoxide anion with dimethyl methylphosphonate in an ion trap mass spectrometer : evidence for a gas phase alpha-effect

The gas phase degradation reactions of the chemical warfare agent (CWA) simulant, dimethyl methylphosphonate (DMMP), with the hydroperoxide anion (HOO(-)) were investigated using a modified quadrupole ion trap mass spectrometer. The HOO(-) anion reacts readily with neutral DMMP forming two significant product ions at m/z 109 and m/z 123. The major reaction pathways correspond to (i) the nucleophilic substitution at carbon to form \[CH(3)P(O)(OCH(3))O](-) (m/z 109) in a highly exothermic process and (ii) exothermic proton transfer. The branching ratios of the two reaction pathways, 89% and 11% respectively, indicate that the former reaction is significantly faster than the latter. This is in contrast to the trend for the methoxide anion with DMMP, where proton transfer dominates. The difference in the observed reactivities of the HOO(-) and CH(3)O(-) anions can be considered as evidence for an a-effect in the gas phase and is supported by electronic structure calculations at the B3LYP/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory that indicate the S(N)2(carbon) process has an activation energy 7.8 kJ mol(-1) lower for HOO(-) as compared to CH(3)O(-). A similar alpha-effect was calculated for nucleophilic addition-elimination at phosphorus, but this process an important step in the perhydrolysis degradation of CWAs in solution - was not observed to occur with DMMP in the gas phase. A theoretical investigation revealed that all processes are energetically accessible with negative activation energies. However, comparison of the relative Arrhenius pre-exponential factors indicate that substitution at phosphorus is not kinetically competitive with respect to the S(N)2(carbon) and deprotonation processes.

Generation of three isomers of C7H- in the gas phase. A joint experimental and theoretical study

Three anion isomers of formula C7H have been synthesised in the mass spectrometer by unequivocal routes. The structures of the isomers are \[HCCC(C-2)(2)](-), C6CH- and C2CHC4-. One of these, \[HCCC(C-2)(2)](-), is formed in sufficient yield to allow it to be charge stripped to the corresponding neutral radical.

The loss of carbon dioxide from activated perbenzoate anions in the gas phase : Unimolecular rearrangement via epoxidation of the benzene ring

The unimolecular reactivities of a range of perbenzoate anions (X-C6H5CO3-), including the perbenzoate anion itself (X=H), nitroperbenzoates (X=para-, meta-, ortho-NO2), and methoxyperbenzoates (X=para-, meta-OCH3) were investigated in the gas phase by electrospray ionization tandem mass spectrometry. The collision-induced dissociation mass spectra of these compounds reveal product ions consistent with a major loss of carbon dioxide requiring unimolecular rearrangement of the perbenzoate anion prior to fragmentation. Isotopic labeling of the perbenzoate anion supports rearrangement via an initial nucleophilic aromatic substitution at the ortho carbon of the benzene ring, while data from substituted perbenzoates indicate that nucleophilic attack at the ipso carbon can be induced in the presence of electron-withdrawing moieties at the ortho and para positions. Electronic structure calculations carried out at the B3LYP/6311++G(d,p) level of theory reveal two competing reaction pathways for decarboxylation of perbenzoate anions via initial nucleophilic substitution at the ortho and ipso positions, respectively. Somewhat surprisingly, however, the computational data indicate that the reaction proceeds in both instances via epoxidation of the benzene ring with decarboxylation resulting-at least initially-in the formation of oxepin or benzene oxide anions rather than the energetically favored phenoxide anion. As such, this novel rearrangement of perbenzoate anions provides an intriguing new pathway for epoxidation of the usually inert benzene ring.

Coal seam gas water : potential hazards and exposure pathways in Queensland

The extraction of coal seam gas (CSG) produces large volumes of potentially contaminated water. It has raised concerns about the environmental health impacts of the co-produced CSG water. In this paper, we review CSG water contaminants and their potential health effects in the context of exposure pathways in Queensland’s CSG basins. The hazardous substances associated with CSG water in Queensland include fluoride, boron, lead and benzene. The exposure pathways for CSG water are: (1) water used for municipal purposes, (2) recreational water activities in rivers, (3) occupational exposures, (4) water extracted from contaminated aquifers, and; (5) indirect exposure through the food chain. We recommend mapping of exposure pathways into communities in CSG regions to determine the potentially exposed populations in Queensland. Future efforts to monitor chemicals of concern and consolidate them into a central database will build the necessary capability to undertake a much needed environmental health impact assessment.

The importance of use and end-of-life phases to the life cycle greenhouse gas (GHG) emissions of concrete : a review

Global climate change is one of the most significant environmental impacts at the moment. One central issue for the building and construction industry to address global climate change is the development of credible carbon labelling schemes for building materials. Various carbon labelling schemes have been developed for concrete due to its high contribution to global greenhouse gas (GHG) emissions. However, as most carbon labelling schemes adopt cradle-to-gate as system boundary, the credibility of the eco-label information may not be satisfactory because recent studies show that the use and end-of-life phases can have a significant impact on the life cycle GHG emissions of concrete in terms of carbonation, maintenance and rehabilitation, other indirect emissions, and recycling activities. A comprehensive review on the life cycle assessment of concrete is presented to holistically examine the importance of use and end-of-life phases to the life cycle GHG quantification of concrete. The recent published ISO 14067: Carbon footprint of products – requirements and guidelines for quantification and communication also mandates the use of cradle-to-grave to provide publicly available eco-label information when the use and end-of-life phases of concrete can be appropriately simulated. With the support of Building Information Modelling (BIM) and other simulation technologies, the contribution of use and end-of-life phases to the life cycle GHG emissions of concrete should not be overlooked in future studies.

Resilience and opportunity : regions and the roll-out of Australia's greenhouse gas abatement programs. A manual for Queensland's NRM regions

Voluntary and compliance markets for forest carbon and other (emission avoidance and biosequestration) activities are growing internationally and across Australia. Queensland and its Natural Resource Management (NRM) regions have an opportunity to take a variety of actions to help guide these markets to secure multiple landscape benefits and to build landscape resilience in the face of climate change. As the national arrangements for offsets within Australia’s Clean Energy Package (CEP) and emissions trading environment emerge, Queensland’s regions can prepare themselves and their landholding communities to take advantage of these opportunities to deliver improved climate resilience in their regional landscapes.

Characterisations of ideal threshold schemes

We characterise ideal threshold schemes from different approaches. Since the characteristic properties are independent to particular descriptions of threshold schemes, all ideal threshold schemes can be examined by new points of view and new results on ideal threshold schemes can be discovered.

Ideal secret sharing schemes from permutations

The work presents a new method for the design of ideal secret sharing. The method uses regular mappings that are well suited for construction of perfect secret sharing. The restriction of regular mappings to permutations gives a convenient tool for investigation of the relation between permutations and ideal secret sharing generated by them.

Ideal threshold schemes from MDS codes

We observe that MDS codes have interesting properties that can be used to construct ideal threshold schemes. These schemes permit the combiner to detect cheating, identify cheaters and recover the correct secret. The construction is later generalised so the resulting secret sharing is resistant against the Tompa-Woll cheating.

Ideal threshold schemes from orthogonal arrays

The work investigates the design of ideal threshold secret sharing in the context of cheating prevention. We showed that each orthogonal array is exactly a defining matrix of an ideal threshold scheme. To prevent cheating, defining matrices should be nonlinear so both the cheaters and honest participants have the same chance of guessing of the valid secret. The last part of the work shows how to construct nonlinear secret sharing based on orthogonal arrays.

An ideal and robust threshold RSA

We present a novel implementation of the threshold RSA. Our solution is conceptually simple, and leads to an easy design of the system. The signing key is shared in additive form, which is desirable for collaboratively performing cryptographic transformations, and its size, at all times, is logn, where n is the RSA modulus. That is, the system is ideal.

Plasma-produced phase-pure cuprous oxide nanowires for methane gas sensing

Phase-selective synthesis of copper oxide nanowires is warranted by several applications, yet it remains challenging because of the narrow windows of the suitable temperature and precursor gas composition in thermal processes. Here, we report on the room-temperature synthesis of small-diameter, large-area, uniform, and phase-pure Cu2O nanowires by exposing copper films to a custom-designed low-pressure, thermally non-equilibrium, high-density (typically, the electron number density is in the range of 10 11-1013cm-3) inductively coupled plasmas. The mechanism of the plasma-enabled phase selectivity is proposed. The gas sensors based on the synthesized Cu2O nanowires feature fast response and recovery for the low-temperature (∼140°C) detection of methane gas in comparison with polycrystalline Cu2O thin film-based gas sensors. Specifically, at a methane concentration of 4%, the response and the recovery times of the Cu2O nanowire-based gas sensors are 125 and 147s, respectively. The Cu2O nanowire-based gas sensors have a potential for applications in the environmental monitoring, chemical industry, mining industry, and several other emerging areas.

Effect of atmospheric gas plasmas on cancer cell signaling

Cancer is one of the most life-threatening diseases with many forms still regarded as incurable. The conventional cancer treatments have unwanted side effects such as the death of normal cells. A therapy that can accurately target and effectively kill tumor cells could address the inadequacies of the available therapies. Atmospheric gas plasmas (AGP) that are able to specifically kill cancerous cells offer a promising alternative approach compared to conventional therapies. AGP have been shown to exploit tumor-specific genetic defects and a recent trial in mice has confirmed its antitumor effects. The mechanism by which the AGP act on tumor cells but not normal cells is not fully understood. A review of the current literature suggests that reactive oxygen species (ROS) generated by AGP induce death of cancer cells by impairing the function of intracellular regulatory factors. The majority of cancer cells are defective in tumor suppressors that interfere normal cell growth pathways. It appears that pro-oncogene or tumor suppressor-dependent regulation of antioxidant/or ROS signaling pathways may be involved in AGP-induced cancer cell death. The toxic effects of ROS are mitigated by normal cells by adjustment of their metabolic pathways. On the other hand, tumor cells are mostly defective in several regulatory signaling pathways which lead to the loss of metabolic balance within the cells and consequently, the regulation of cell growth. This review article evaluates the impact of AGP on the activation of cellular signaling and its importance for exploring mechanisms for safe and efficient anticancer therapies.

Atmospheric gas plasma–induced ROS production activates TNF-ASK1 pathway for the induction of melanoma cancer cell apoptosis

Atmospheric gas plasmas (AGPs) are able to selectively induce apoptosis in cancer cells, offering a promising alternative to conventional therapies that have unwanted side effects such as drug resistance and toxicity. However, the mechanism of AGP-induced cancer cell death is unknown. In this study, AGP is shown to up-regulate intracellular reactive oxygen species (ROS) levels and induce apoptosis in melanoma but not normal melanocyte cells. By screening genes involved in apoptosis, we identify tumor necrosis factor (TNF)-family members as the most differentially expressed cellular genes upon AGP treatment of melanoma cells. TNF receptor 1 (TNFR1) antagonist-neutralizing antibody specifically inhibits AGP-induced apoptosis signal, regulating apoptosis signal-regulating kinase 1 (ASK1) activity and subsequent ASK1-dependent apoptosis. Treatment of cells with intracellular ROS scavenger N-acetyl-l-cysteine also inhibits AGP-induced activation of ASK1, as well as apoptosis. Moreover, depletion of intracellular ASK1 reduces the level of AGP-induced oxidative stress and apoptosis. The evidence for TNF-signaling dependence of ASK1-mediated apoptosis suggests possible mechanisms for AGP activation and regulation of apoptosis-signaling pathways in tumor cells.