Poly-[μ-aqua-μ5-[(2,3,6-trichlorophenyl)acetato)-caesium]

In the structure of the title complex [Cs(C8H4Cl3O2)(H2O)]n, the Cs salt of the commercial herbicide fenac [(2,3,6-trichlorophenyl)acetic acid], the irregular eight-coordination about Cs+ comprises a bidentate chelate (O:Cl) interaction involving a carboxyl O-atom and an ortho-related ring substituted Cl atom which is also bridging, a triple-bridging carboxyl O-atom and a bridging water molecule. A two-dimensional sheet polymer is generated, lying parallel to (100), within which there are water O---H...O(carboxyl) hydrogen-bonding interactions.

Poly[μ-aqua-aqua-μ5-(4-nitrobenzoato)-caesium]

In the structure of the title complex [Cs(C7H4N2O2)(H2O)2]n, the Cs salt of 4-nitrobenzoic acid, the irregular CsO9 coordination sphere comprises three bridging nitro O-donors, a bidentate carboxyl (O,O')-chelate interaction, a triple-bridging water molecule and a monodentate water molecule. A three-dimensional framework polymer is generated, within which there are water O-H...Ocarboxyl and water O-H...O(water) hydrogen-bonding interactions.

Mechanisms of glycerol dehydration

Dehydration of neutral and protonated glycerol was investigated using quantum mechanical calculations (CBS-QB3). Calculations on neutral glycerol show that there is a high barrier for simple 1,2-dehydration, E-a = 70.9 kcal mol(-1), which is lowered to 65.2 kcal mol(-1) for pericyclic 1,3-dehydration. In contrast, the barriers for dehydration of protonated glycerol are much lower. Dehydration mechanisms involving hydride transfer, pinacol rearrangement, or substitution reactions have barriers between 20 and 25 kcal mol(-1). Loss of water from glycerol via substitution results in either oxirane or oxetane intermediates, which can interconvert over a low barrier. Subsequent decomposition of these intermediates proceeds via either a second dehydration step or loss of formaldehyde. The computed mechanisms for decomposition of protonated glycerol are supported by the gas-phase fragmentation of protonated glycerol observed using a triple-quadrupole mass spectrometer.

Conversion of linear to rhombic C-4 in the gas phase: A joint experimental and theoretical study

Charge reversal (CR) and neutralization reionization (NR) experiments carried out on a 4-sector mass spectrometer demonstrate that isotopically labeled, linear C-4 anion rearranges upon collisional oxidation. The cations and neutrals formed in these experiments exhibit differing degrees of isotopic scrambling in their fragmentation patterns, indicative of (at least) partial isomerization of both states. Theoretical studies, employing the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory, favor conversion to the rhombic C-4 isomer on both cationic and neutral potential-energy surfaces with the rhombic structures predicted to be slightly more stable than the linear forms in each case. The combination of experiment with theory indicates that the elusive rhombic C-4 is formed as a cation and as a neutral following charge stripping of linear C-4(-)

Generation of two isomers of C5H from the corresponding anions. A theoretically motivated mass spectrometric study

Molecular orbital calculations have predicted the stability of a range of connectivities for the radical C5H potential surface. The most energetically favorable of these include the linear C4CH geometry and two ring-chain structures HC2C3 and C2C3H The corresponding anions are also shown to be theoretically stable, and furthermore, a fourth isomer, C2CHC2, is predicted to be the most stable anion connectivity. These results have motivated experimental efforts. Methodologies for the generation of the non-ring-containing isomeric anions C4CH and C2CHC2 have been developed utilizing negative ion mass spectrometry. The absolute connectivities of the anions have been established using deuterium labeling, charge reversal, and neutralization reionization techniques. The success of the latter experiment confirms theoretical predictions of stability of the corresponding neutral species. This is the first reported observation of the neutral C2CHC2 species that calculations predict to be substantially less stable than the C4CH connectivity but still bound relative to isomerization processes.

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.

A mass spectrometry study of XCO+, X = Si, Ge : Is SiCO+ a main group carbonyl? Comments on the bonding in ground state SiCO and the Si,C,O (+) potential energy surface

The cation\[Si,C,O](+) has been generated by 1) the electron ionisation (EI) of tetramethoxysilane and 2) chemical ionisation (CI) of a mixture of silane and carbon monoxide. Collisional activation (CA) experiments performed for mass-selected \[Si,C,O](+), generated by using both methods, indicate that the structure is not inserted OSiC+; however, a definitive structural assignment as Si+-CO, Si+-OC or some cyclic variant is impossible based on these results alone. Neutralisation-reionisation (+NR+) experiments for EI-generated \[Si,C,O](+) reveal a small peak corresponding to SiC+, but no detectable SiO+ signal, and thus establishes the existence of the Si+-CO isomer. CCSD(T)//B3LYP calculations employing a triple-zeta basis set have been used to explore the doublet and quartet potential-energy surfaces of the cation, as well as some important neutral states The results suggest that both Si+-CO and Si+ - OC isomers are feasible; however, the global minimum is (2)Pi SiCO+. Isomeric (2)Pi SiOC+ is 12.1 kcal mol(-1) less stable than (2)Pi SiCO+, and all quartet isomers are much higher in energy. The corresponding neutrals Si-CO and Si-OC are also feasible, but the lowest energy Si - OC isomer ((3)A") is bound by only 1.5 kcal mol(-1). We attribute most, if nor all, of the recovery signal in the +NR' experiment to SiCO+ survivor ions. The nature of the bonding in the lowest energy isomers of Si+ -(CO,OC) is interpreted with the aid of natural bond order analyses, and the ground stale bonding of SiCO+ is discussed in relation to classical analogues such as metal carbonyls and ketenes.

Structural identification of hindered amine light stabilisers in coil coatings using electrospray ionisation tandem mass spectrometry

Hindered amine light stabilisers (HALS) are the most effective antioxidants currently available for polymer systems in post-production, in-service applications, yet the mechanism of their action is still not fully understood. Structural characterisation of HALS in polymer matrices, particularly the identification of structural modifications brought about by oxidative conditions, is critical to aid mechanistic understanding of the prophylactic effects of these molecules. In this work, electrospray ionisation tandem mass spectrometry (ESI-MS/MS) was applied to the analysis of a suite of commercially available 2,2,6,6-tetramethylpiperidine-based HALS. Fragmentation mechanisms for the \[M + H](+) ions are proposed, which provide a rationale for the product ions observed in the MS/MS and MS(3) mass spectra of N-H, N-CH(3), N-C(O)CH(3) and N-OR containing HALS (where R is an alkyl substituent). A common product ion at m/z 123 was identified for the group of antioxidants containing N-H, N-CH3 or N-C(0)CH3 functionality, and this product ion was employed in precursor ion scans on a triple quadrupole mass spectrometer to identify the HALS species present in a crude extract from of a polyester-based coil coating. Using MS/MS, two degradation products were unambiguously identified. This technique provides a simple and selective approach to monitoring HALS structures within complex matrices. Copyright (C) 2010 John Wiley & Sons, Ltd.

The Medics - "Foundations"

The Medics “Foundations” is a full-length album of popular music completed over a 13-month period and released in 2012, with work taking place in Byron Bay’s 301 studios and Brisbane’s Airlock studios. “Foundations” contributes to studies in the field of music production, as well as furthering research into the place of Indigenous youth culture within contemporary rock music. The music draws on elements of folk, post rock and hardcore to create a dynamic and cinematic sound, framed by lyrics that focus on spirituality, nature and a connection to the land. Artists such as At the Drive In and Mars Volta were referenced in the production of the record. Scholars such as Joe Bennett have argued that the relationship between songwriting practice and song product is an under-explored area in popular musicology, and, by using a practice-led research methodology, the production of “Foundations” extends these creative inquiries. “Foundations” was produced with the assistance of a competitive grant, the Cultural Minister’s Council Breakthrough initiative, which assists emerging Indigenous contemporary musicians. The album was well received and positively reviewed, resulting in the band signing a record deal with Warner Music and a publishing deal with Albert’s Music. It was album of the week on Triple J and several singles were placed on high rotation. A review on Themusic.com.au highlighted the production work: “Producer Yanto Browning has captured the impassioned live intent the band have built their reputation on and bottled it into 11 impeccable tracks, the album maintaining their onstage vigour while polishing it just enough to allow it to burn brightly through the speakers.” As a result of the record, The Medics were invited to play Splendour in the Grass, the national Big Day Out tour and a series of shows in South America.

Art of sleeping - "Like a Thief"

Research background Art of Sleeping’s “Like a Thief” is an EP of popular music produced at Airlock studios and released in 2012 by the record label Dew Process. “Like a Thief” contributes to studies in the field of music production, as well as furthering research into the role of of national radio play in the development of emerging musicians and artists. Using Australian bands such as Boy and Bear as a reference point, the EP showcases the vocal range of Caleb Hodges and investigates possibilities in extending the modes of musicality possible within the recording studio through use of multiple layering of processed keyboards and electric guitar. Scholars such as Ben Eltham and journalists such as Everett True have written about the importance of the support of Australia’s national youth broadcaster Triple J in the early stages of a band’s development. The approach of the production of the EP was conceived with this agenda in mind, and asked, what can we learn about the relationships between popular music production, distribution and consumption, and the role that national public radio has come to play in the Australian context? Research contribution This project has identified that certain avenues of the music industry continue to aligned with Triple J airplay, that these avenues play an important role in the level of success that artists are likely to achieve, and that targeted understanding of music production techniques and aesthetics may contribute to success in this regard. Research significance The EP’s two singles were both in the top 100 most frequently played tracks on Triple J in 2012, and the band were able to leverage this exposure in securing a record deal with Dew Process, along with being selected as part of the competitive peer review process for festival performances such as Splendour in the Grass. The work received positive peer reviews, with indieshuffle writing: “Brisbane's Art of Sleeping are a truly talented band. … the five-piece gained plenty of local attention earlier this year with their stunning single "Empty Hands.” This was the first single off their new EP, Like a Thief, which was produced by the renowned Yanto Browning (The Medics, The Jungle Giants) … The EP includes five tracks of incredible power and sentiment … Title track "Like a Thief” is … [a] standout, again a vast and expansive song which showcases the band's completeness”

Enhancing paramedics procedural skills using a cadaveric model

Background Paramedic education has evolved in recent times from vocational post-employment to tertiary pre-employment supplemented by clinical placement. Simulation is advocated as a means of transferring learned skills to clinical practice. Sole reliance of simulation learning using mannequin-based models may not be sufficient to prepare students for variance in human anatomy. In 2012, we trialled the use of fresh frozen human cadavers to supplement undergraduate paramedic procedural skill training. The purpose of this study is to evaluate whether cadaveric training is an effective adjunct to mannequin simulation and clinical placement. Methods A multi-method approach was adopted. The first step involved a Delphi methodology to formulate and validate the evaluation instrument. The instrument comprised of knowledge-based MCQs, Likert for self-evaluation of procedural skills and behaviours, and open answer. The second step involved a pre-post evaluation of the 2013 cadaveric training. Results One hundred and fourteen students attended the workshop and 96 evaluations were included in the analysis, representing a return rate of 84%. There was statistically significant improved anatomical knowledge after the workshop. Students' self-rated confidence in performing procedural skills on real patients improved significantly after the workshop: inserting laryngeal mask (MD 0.667), oropharyngeal (MD 0.198) and nasopharyngeal (MD 0.600) airways, performing Bag-Valve-Mask (MD 0.379), double (MD 0.344) and triple (MD 0.326,) airway manoeuvre, doing 12-lead electrocardiography (MD 0.729), using McGrath(R) laryngoscope (MD 0.726), using McGrath(R) forceps to remove foreign body (MD 0.632), attempting thoracocentesis (MD 1.240), and putting on a traction splint (MD 0.865). The students commented that the workshop provided context to their theoretical knowledge and that they gained an appreciation of the differences in normal tissue variation. Following engagement in/ completion of the workshop, students were more aware of their own clinical and non-clinical competencies. Conclusions The paramedic profession has evolved beyond patient transport with minimal intervention to providing comprehensive both emergency and non-emergency medical care. With limited availability of clinical placements for undergraduate paramedic training, there is an increasing demand on universities to provide suitable alternatives. Our findings suggested that cadaveric training using fresh frozen cadavers provides an effective adjunct to simulated learning and clinical placements.

'Not a Local Win': Rural Australian perceptions of the sustainable impacts of forest plantations

Australian forestry plantations have doubled in the past 15 years, with rural communities harbouring a diverse range of positive and negative of economic, environmental and social impacts – the so-called triple bottom line (TBL). Utilising two Australian rural communities in Eden/Gippsland and Tasmania as qualitative case studies, this research explores how 23 non-forestry affiliated rural residents perceived and experienced the TBL economic, environmental and social impacts of plantation forestry. Residents criticised the economic plantation forestry benefits because of lengthy periods of inactivity and limited local employment, explaining that their community was reliant on the industry yet the promised economic benefits had never fully materialised. There was a sense the industry ‘plant and walk away.’ Residents were concerned about the environment impact on water quality, water tables and fire hazards, although they praised plantation forestry for carbon sequestering, eradicating erosion and water run-off. Negative social impacts were described, specifically how the land-use change from farming to forestry had significantly reduced the local population, employment and need for services. Natural resource management and communication strategies are offered, derived from non-forestry affiliated rural resident perspectives on how best to ensure sustainable forest development in their community.

Women IN Sport or Women OR Sport - The search for work/sport/life balance.

The current ‘holy grail’ for our health and well-being centres around the search for, and establishment of, a work/life balance. For many individuals, this appears to be an ever-elusive goal – forever slipping from our grasp as we juggle the day-to-day battle for our attention and time from an array of sources. When we add the word ‘Women’ to this mix, often the number of sources related to these demands multiplies in alignment with the number of roles we fill. To take this to even another level, consider the addition of the words ‘Sport’ or ‘Elite Athlete’ to ‘Women’ and ‘Work/Life Balance’, and the search for the ‘holy grail’ becomes more literal! Many sportswomen at the elite level face significant challenges in balancing working to support themselves and/or their families, studying to lay the foundations of a post-sport career, (often) spending the equivalent of full-time hours training towards their sporting goals, and additionally investing in the things that are important for them outside of these two areas – the ‘Life’ component. Getting the work/life balance ‘balanced’ has been suggested to be a key component of investing in our health and well-being. The same is applicable to sportswomen, with the added suggestion that if the balance between work/sport/life is achieved, this can positively impact upon sporting performance itself. These ideas and observations will be explored via experience within the Australian elite sporting environment from a psychologist’s perspective, with questions and invitations for further discussion.

Experimental evidence for competitive N–O and O–C bond homolysis in gasphase alkoxyamines

The extensive use of alkoxyamines in controlled radical polymerisation and polymer stabilisation is based on rapid cycling between the alkoxyamine (R1R2NO–R3) and a stable nitroxyl radical (R1R2NO•) via homolysis of the labile O–C bond. Competing homolysis of the alkoxyamine N–O bond has been predicted to occur for some substituents leading to production of aminyl and alkoxyl radicals. This intrinsic competition between the O–C and N–O bond homolysis processes has to this point been difficult to probe experimentally. Herein we examine the effect of local molecular structure on the competition between N–O and O–C bond cleavage in the gas phase by variable energy tandem mass spectrometry in a triple quadrupole mass spectrometer. A suite of cyclic alkoxyamines with remote carboxylic acid moieties (HOOC–R1R2NO–R3) were synthesised and subjected to negative ion electrospray ionisation to yield [M – H]− anions where the charge is remote from the alkoxyamine moiety. Collision-induced dissociation of these anions yield product ions resulting, almost exclusively, from homolysis of O–C and/or N–O bonds. The relative efficacy of N–O and O–C bond homolysis was examined for alkoxyamines incorporating different R3 substituents by varying the potential difference applied to the collision cell, and comparing dissociation thresholds of each product ion channel. For most R3 substituents, product ions from homolysis of the O–C bond are observed and product ions resulting from cleavage of the N–O bond are minor or absent. A limited number of examples were encountered however, where N–O homolysis is a competitive dissociation pathway because the O–C bond is stabilised by adjacent heteroatom(s) (e.g., R3 = CH2F). The dissociation threshold energies were compared for different alkoxyamine substituents (R3) and the relative ordering of these experimentally determined energies is shown to correlate with the bond dissociation free energies, calculated by ab initio methods. Understanding the structure-dependent relationship between these rival processes will assist in the design and selection of alkoxyamine motifs that selectively promote the desirable O–C homolysis pathway.

The kite string tangle : blissed-out beats at the Brisbane Festival

Danny Harley has had a pretty big year with his one-man band project The Kite String Tangle. There have been festival appearances, both at home and abroad, a song in the top 20 of Triple J’s iconic Hottest 100 annual music poll and a sold-out tour to mark the release of his debut EP, which wrapped up this week with two shows in the Spiegeltent at the Brisbane Festival...