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(-)

Oxidation of 4-substituted TEMPO derivatives reveals modifications at the 1-and 4-positions

Potenital pathways for the deactivation of hindered amine light stabilisers (HALS) have been investigated by observing reactions of model compounds-based on 4-substituted derivatives of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)-with hydroxyl radicals. In these reactions, dilute aqueous suspensions of photocatalytic nanoparticulate titanium dioxide were irradiated with UV light in the presence of water-soluble TEMPO derivatives. Electron spin resonance (ESR) and electrospray ionisation mass-spectrometry (ESI-MS) data were acquired to provide complementary structural elucidation of the odd-and even-electron products of these reactions and both techniques show evidence for the formation of 4-oxo-TEMPO (TEMPONE). TEMPONE formation from the 4-substituted TEMPO compounds is proposed to be initiated by hydrogen abstraction at the 4-position by hydroxyl radical. High-level ab initio calculations reveal a thermodynamic preference for abstraction of this hydrogen but computed activation barriers indicate that, although viable, it is less favoured than hydrogen abstraction from elsewhere on the TEMPO scaffold. If a radical is formed at the 4-position however, calculations elucidate two reaction pathways leading to TEMPONE following combination with either a second hydroxyl radical or dioxygen. An alternate mechanism for conversion of TEMPOL to TEMPONE via an alkoxyl radical intermediate is also considered and found to be competitive with the other pathways. ESI-MS analysis also shows an increased abundance of analogous 4-substituted piperidines during the course of irradiation, suggesting competitive modification at the 1-position to produce a secondary amine. This modification is confirmed by characteristic fragmentation patterns of the ionised piperidines obtained by tandem mass spectrometry. The conclusions describe how reaction at the 4-position could be responsible for the gradual depletion of HALS in pigmented surface coatings and secondly, that modification at nitrogen to form the corresponding secondary amine species may play a greater role in the stabilisation mechanisms of HALS than previously considered.

MCF7/LCC2: A 4-hydroxytamoxifen resistant human breast cancer variant that retains sensitivity to the steroidal antiestrogen ICI 182,780

The development of resistance to the antiestrogen tamoxifen occurs in a high percentage of initially responsive patients. We have developed a new model in which to investigate acquired resistance to triphenylethylenes. A stepwise in vitro selection of the hormone-independent human breast cancer variant MCF-7/LCC1 against 4-hydroxytamoxifen produced a stable resistant population designated MCF7/LCC2. MCF7/LCC2 cells retain levels of estrogen receptor expression comparable to the parental MCF7/LCC1 and MCF-7 cells. Progesterone receptor expression remains estrogen inducible in MCF7/LCC2 cells, although to levels significantly lower than observed in MCF-7 and MCF7/LCC1 cells. MCF7/ LCC2 cells form tumors in ovariectomized nude mice without estrogen supplementation, and these tumors are tamoxifen resistant but can be tstrogen stimulated. Significantly, MCF7/LCC2 cells have retained sensitivity to the steroidal antiestrogen ICI 182,780. These data suggest that some breast cancer patients who acquire resistance to tamoxifen may not develop cross-resistance to treatment with steroidal antiestrogens.

A collagen prolyl 4-hydroxylase inhibitor reduces adhesions after tendon injury

Collagen synthesis inhibition potentially can reduce adhesion formation after tendon injury but also may affect cutaneous wound healing. We hypothesized that a novel orally administered collagen synthesis inhibitor (CPHI-I) would substantially reduce flexor tendon adhesions after injury, without any clinically important effect on cutaneous wound healing. The experiments were performed in a rat model with an in-continuity crush injury model in the rat hindfoot flexor tendon to provoke adhesion formation. Assays of dermal collagen production and the rate of healing of an excised wound were performed to assess cutaneous wound healing. Animals in the treatment groups received CPHI-I for 1, 2, or 6 weeks and were assessed at either 2 or 6 weeks. The work of flexion in the injured digit was reduced in the CPHI-I-treated animals compared with control animals, (0.188 J versus 0.0307 J at 2 weeks, and 0.0231 J versus 0.0331 J at 6 weeks) The cutaneous wound healing rate was similar in all animals, but dermal collagen synthesis was reduced in the treated animals. The CPHI-I seems to reduce tendon adhesion, and although collagen synthesis was reduced in cutaneous wounds, CPHI-I did not retard wound healing.

Outback institutions : an application of the Institutional Analysis and Development (IAD) framework to four case studies in Australia’s Outback -- Part 4 : Incentives for community participation and land use decisions in Etheridge Shire, Queensland

Natural resource management planning in the Northern Gulf region of Queensland is concerned with ‘how [natural assets] and community aspirations can be protected and enhanced to provide the Northern Gulf community with the economic, social and environmental means to meet the continuing growth of the region in an ecological and economically sustainable way’ (McDonald & Dawson 2004). In the Etheridge Shire, located in the tropical savanna of the Northern Gulf region, two of the activities that influence the balance between economic growth and long-term sustainable development are: 1. the land-use decisions people in the Shire make with regards to their own enterprises. 2. their decisions to engage in civically-minded activities aimed at improving conditions in the region. Land-use decision and engagement in community development activities were chosen for detailed analysis because they are activities for which policies can be devised to improve economic and sustainable development outcomes. Changing the formal and informal rules that guide and govern these two different kinds of decisions that people can make in the Etheridge Shire – the decision to improve one’s own situation and the decision to improve the situation for others in the community – may expand the set of available options for people in the Shire to achieve their goals and aspirations. Identifying appropriate and effective changes in rules requires, first, an understanding of the ‘action arena’, in this case comprised of a diversity of ‘participants’ from both within and outside the Etheridge Shire, and secondly knowledge of ‘action situations’ (land-use decisions and engagement in community development activities) in which stakeholders are involved and/or have a stake. These discussions are presented in sections 4.1.1.1 and 4.1.1.2.

Duty in the time of epidemics : what China and Zimbabwe teach us

In November 2002, a man with ‘atypical pneumonia’ treated in Foshan hospital, Guangdong Province, in the People's Republic of China, was the first known case of Severe Acute Respiratory Syndrome (SARS). However, it was not until April 2003 that the Chinese government admitted to the full scale of ‘atypical pneumonia’ cases infected with SARS, two months after the disease had rapidly spread across the world with initial infections in Hong Kong and Vietnam sourced to Guangdong. In 2008, Zimbabwe experienced one of the biggest outbreaks of cholera ever recorded. By February 2009, the disease had spread across all of Zimbabwe's 10 provinces and to neighbouring countries—Botswana, South Africa, Zambia and Mozambique—causing thousands of infections amongst their populations. This article seeks to examine what duties the Chinese and Zimbabwe states had to protect their citizens and the international community from these outbreaks. The article refers to the findings of the International Law Commission's study into the role of states and international organisations in protecting persons in the event of a disaster to consider whether there is an international duty to protect persons from epidemics. The article concludes that both cases reveal a growing concept of protection that entails an international duty to assist individuals when an affected state proves unwilling or unable to assist its own population in the event of a disease outbreak.

Supine to standing Cobb Angle change in idiopathic scoliosis: The effect of endplate preselection

Introduction Standing radiographs are the ‘gold standard’ for clinical assessment of adolescent idiopathic scoliosis (AIS), with the Cobb Angle used to measure the severity and progression of the scoliotic curve. Supine imaging modalities can provide valuable 3D information on scoliotic anatomy, however, due to changes in gravitational loading direction, the geometry of the spine alters between the supine and standing position which in turn affects the Cobb Angle measurement. Previous studies have consistently reported a 7-10° [1-3] Cobb Angle increase from supine to standing, however, none have reported the effect of endplate pre-selection and which (if any) curve parameters affect the supine to standing Cobb Angle difference. Methods Female AIS patients with right-sided thoracic major curves were included in the retrospective study. Clinically measured Cobb Angles from existing standing coronal radiographs and fulcrum bending radiographs [4] were compared to existing low-dose supine CT scans taken within 3 months of the reference radiograph. Reformatted coronal CT images were used to measure Cobb Angle variability with and without endplate pre-selection (end-plates selected on the radiographs used on the CT images). Inter and intra-observer measurement variability was assessed. Multi-linear regression was used to investigate whether there was a relationship between supine to standing Cobb Angle change and patient characteristics (SPSS, v.21, IBM, USA). Results Fifty-two patients were included, with mean age of 14.6 (SD 1.8) years; all curves were Lenke Type 1 with mean Cobb Angle on supine CT of 42° (SD 6.4°) and 52° (SD 6.7°) on standing radiographs. The mean fulcrum bending Cobb Angle for the group was 22.6° (SD 7.5°). The 10° increase from supine to standing is consistent with existing literature. Pre-selecting vertebral endplates was found to increase the Cobb Angle difference by a mean 2° (range 0-9°). Multi-linear regression revealed a statistically significant relationship between supine to standing Cobb Angle change with: fulcrum flexibility (p=0.001), age (p=0.027) and standing Cobb Angle (p<0.001). In patients with high fulcrum flexibility scores, the supine to standing Cobb Angle change was as great as 20°.The 95% confidence intervals for intra-observer and inter-observer measurement variability were 3.1° and 3.6°, respectively. Conclusion There is a statistically significant relationship between supine to standing Cobb Angle change and fulcrum flexibility. Therefore, this difference can be considered a measure of spinal flexibility. Pre-selecting vertebral endplates causes only minor changes.

Thoracoscopic scoliosis surgery – a cheaper option? A cost analysis of 189 consecutive cases

INTRODUCTION: Increasing health care costs, limited resources and increased demand makes cost effective and cost-efficient delivery of Adolescent Idiopathic Scoliosis (AIS) management paramount. Rising implant costs in deformity correction surgery have prompted analysis of whether high implant densities are justified. The objective of this study was to analyse the costs of thoracoscopic scoliosis surgery, comparing initial learning curve costs with those of the established technique and to the costs involved in posterior instrumented fusion from the literature. METHODS: 189 consecutive cases from April 2000 to July 2011 were assessed with a minimum of 2 years follow-up. Information was gathered from a prospective database covering perioperative factors, clinical and radiological outcomes, complications and patient reported outcomes. The patients were divided into three groups to allow comparison; 1. A learning curve cohort, 2. An intermediate cohort and 3. A third cohort of patients, using our established technique. Hospital finance records and implant manufacturer figures were corrected to 2013 costs. A literature review of AIS management costs and implant density in similar curve types was performed. RESULTS: The mean pre-op Cobb angle was 53°(95%CI 0.4) and was corrected postop to mean 22.9°(CI 0.4). The overall complication rate was 20.6%, primarily in the first cohort, with a rate of 5.6% in the third cohort. The average total costs were $46,732, operating room costs of $10,301 (22.0%) and ICU costs of $4620 (9.8%). The mean number of screws placed was 7.1 (CI 0.04) with a single rod used for each case giving average implant costs of $14,004 (29.9%). Comparison of the three groups revealed higher implant costs as the technique evolved to that in use today, from $13,049 in Group 1 to $14577 in Group 3 (P<0.001). Conversely operating room costs reduced from $10,621 in Group 1 to $7573 (P<0.001) in Group 3. ICU stay was reduced from an average of 1.2 to 0 days. In-patient stay was significantly (P=0.006) lower in Groups 2 and 3 (5.4 days) than Group 1 (5.9 days) (i.e. a reduction in cost of approximately $6,140). CONCLUSIONS: The evolution of our thoracoscopic anterior scoliosis correction has resulted in an increase in the number of levels fused and reduction in complication rate. Implant costs have risen as a result, however, there has been a concurrent decrease in those costs generated by operating room use, ICU and in-patient stay with increasing experience. Literature review of equivalent curve types treated posteriorly shows similar perioperative factors but higher implant density, 69-83% compared to the 50% in this study. Thoracoscopic Scoliosis surgery presents a low density, reliable, efficient and effective option for selected curves. A cost analysis of Thoracoscopic Scoliosis Surgery using financial records and a prospectively collected database of all patients since 2000, demonstrating a clear cost advantage compared to equivalent posterior instrumentation and fusion.

Low-cost railway level crossings - breaking down the barriers

Level crossing risk continues to be a significant safety concern for the security of rail operations around the world. Over the last decade or so, a third of railway related fatalities occurred as a direct result of collisions between road and rail vehicles in Australia. Importantly, nearly half of these collisions occurred at railway level crossings with no active protection, such as flashing lights or boom barriers. Current practice is to upgrade level crossings that have no active protection. However, the total number of level crossings found across Australia exceed 23,500, and targeting the proportion of these that are considered high risk (e.g. public crossings with passive controls) would cost in excess of AU$3.25 billion based on equipment, installation and commissioning costs of warning devices that are currently type approved. Level crossing warning devices that are low-cost provide a potentially effective control for reducing risk; however, over the last decade, there have been significant barriers and legal issues in both Australia and the US that have foreshadowed their adoption. These devices are designed to have significantly lower lifecycle costs compared with traditional warning devices. They often make use of use of alternative technologies for train detection, wireless connectivity and solar energy supply. This paper describes the barriers that have been encountered for the adoption of these devices in Australia, including the challenges associated with: (1) determining requisite safety levels for such devices; (2) legal issues relating to duty of care obligations of railway operators; and (3) issues of Tort liability around the use of less than fail-safe equipment. This paper provides an overview of a comprehensive safety justification that was developed as part of a project funded by a collaborative rail research initiative established by the Australian government, and describes the conceptual framework and processes being used to justify its adoption. The paper provides a summary of key points from peer review and discusses prospective barriers that may need to be overcome for future adoption. A successful outcome from this process would result in the development of a guideline for decision-making, providing a precedence for adopting low-cost level crossing warning devices in other parts of the world. The framework described in this paper also provides relevance to the review and adoption of analogous technologies in rail and other safety critical industries.

Intervertebral staple grading system with micro-CT

Introduction Intervertebral stapling is a leading method of fusionless scoliosis treatment which attempts to control growth by applying pressure to the convex side of a scoliotic curve in accordance with the Hueter-Volkmann principle. In addition to that, staples have the potential to damage surrounding bone during insertion and subsequent loading. The aim of this study was to assess the extent of bony structural damage including epiphyseal injury as a result of intervertebral stapling using an in vitro bovine model. Materials and Methods Thoracic spines from 6-8 week old calves were dissected and divided into motion segments including levels T4-T11 (n=14). Each segment was potted in polymethylemethacrylate. An Instron Biaxial materials testing machine with a custom made jig was used for testing. The segments were tested in flexion/extension, lateral bending and axial rotation at 37⁰C and 100% humidity, using moment control to a maximum 1.75 Nm with a loading rate of 0.3 Nm per second for 10 cycles. The segments were initially tested uninstrumented with data collected from the tenth load cycle. Next an anterolateral 4-prong Shape Memory Alloy (SMA) staple (Medtronic Sofamor Danek, USA) was inserted into each segment. Biomechanical testing was repeated as before. The staples were cut in half with a diamond saw and carefully removed. Micro-CT scans were performed and sagittal, transverse and coronal reformatted images were produced using ImageJ (NIH, USA).The specimens were divided into 3 grades (0, 1 and 2) according to the number of epiphyses damaged by the staple prongs. Results: There were 9 (65%) segments with grade 1 staple insertions and 5 (35%) segments with grade 2 insertions. There were no grade 0 staples. Grade 2 spines had a higher stiffness level than grade 1 spines, in all axes of movement, by 28% (p=0.004). This was most noted in flexion/extension with an increase of 49% (p=0.042), followed by non-significant change in lateral bending 19% (p=0.129) and axial rotation 8% (p=0.456) stiffness. The cross sectional area of bone destruction from the prongs was only 0.4% larger in the grade 2 group compared to the grade 1 group (p=0.961). Conclusion Intervertebral staples cause epiphyseal damage. There is a difference in stiffness between grade 1 and grade 2 staple insertion segments in flexion/extension only. There is no difference in the cross section of bone destruction as a result of prong insertion and segment motion.

A high frequency, low voltage stackable full bridge module for modular multilevel cascade converter (MMCC) research

A new small full bridge module for MMCC research is presented. Each full bridge converter cell is a single small (65 × 30 mm) multilayer PCB with two low voltage high current (22 V, 40 A) integrated half bridge ICs and the necessary isolated control signals and auxiliary power supply (2500 V isolation). All devices are surface mount, minimising cell height (4 mm) and parasitic inductance. Each converter cell can be physically stacked with PCB connectors propagating the control signals and inter-cell power connections. Many cells can be trivially stacked to create a large multilevel converter leg with isolated auxiliary power and control signals. Any of the MMCC family members is then easily formed. With a change in placement of stacking connector, a parallel connection of bridges is also possible. Operation of a nine level parallel full bridge is demonstrated at 12 V and 384 kHz switching frequency delivering a 30 W 2 kHz sinewave into a resistive load. A number of new applications for this novel module aside from MMCC development are listed.

A Raman spectroscopic study of the arsenate mineral chenevixite Cu2Fe23+(AsO4)2(OH)4⋅H2O

We have studied the mineral chenevixite from Manto Cuba Mine, San Pedro de Cachiyuyo District, Inca de Oro, Chañaral Province, Atacama Region, Chile, using a combination of scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDX) and vibrational spectroscopy. Qualitative chemical analysis shows a homogeneous composition, with predominance of As, Fe, Al, Cu, Fe and Cu. Minor amounts of Si were also observed. Raman spectroscopy complimented with infrared spectroscopy has been used to assess the molecular structure of the arsenate minerals chenevixite. Characteristic Raman and infrared bands of the (AsO4)3− stretching and bending vibrations are identified and described. The observation of multiple bands in the (AsO4)3− bending region offers support for the loss of symmetry of the arsenate anion in the structure of chenevixite. Raman bands attributable to the OH stretching vibrations of water and hydroxyl units were analysed. Estimates of the hydrogen bond distances were made based upon the OH stretching wavenumbers.

Volatile properties of CNG and Diesel bus emissions produced during steady state and transient driving modes

An analysis of the emissions from 14 CNG and 5 Diesel buses was conducted during April & May, 2006. Studies were conducted at both steady state and transient driving modes on a vehicle dynamometer utilising a CVS dilution system. This article will focus on the volatile properties of particles from 4 CNG and 4 Diesel vehicles from within this group with a priority given to the previously un-investigated CNG emissions produced at transient loads. Particle number concentration data was collected by three CPC’s (TSI 3022, 3010 & 3782WCPC) having D50 cut-offs set to 5nm, 10nm & 20nm respectively. Size distribution data was collected using a TSI 3080 SMPS with a 3025 CPC during the steady state driving modes. During transient cycles mono-disperse “slices” of between 5nm & 25nm were measured. The volatility of these particles was determined by placing a thermodenuder before the 3022 and the SMPS and measuring the reduction in particle number concentration as the temperature in the thermodenuder was increased. This was then normalised against the total particle count given by the 3010 CPC to provide high resolution information on the reduction in particle concentration with respect to temperature.