The active site behaviour of electrochemically synthesised gold nanomaterials

Even though gold is the noblest of metals, a weak chemisorber and is regarded as being quite inert, it demonstrates significant electrocatalytic activity in its nanostructured form. It is demonstrated here that nanostructured and even evaporated thin films of gold are covered with active sites which are responsible for such activity. The identification of these sites is demonstrated with conventional electrochemical techniques such as cyclic voltammetry as well as a large amplitude Fourier transformed alternating current (FT-ac) method under acidic and alkaline conditions. The latter technique is beneficial in determining if an electrode process is either Faradaic or capacitive in nature. The observed behaviour is analogous to that observed for activated gold electrodes whose surfaces have been severely disrupted by cathodic polarisation in the hydrogen evolution region. It is shown that significant electrochemical oxidation responses occur at discrete potential values well below that for the formation of the compact monolayer oxide of bulk gold and are attributed to the facile oxidation of surface active sites. Several electrocatalytic reactions are explored in which the onset potential is determined by the presence of such sites on the surface. Significantly, the facile oxidation of active sites is used to drive the electroless deposition of metals such as platinum, palladium and silver from their aqueous salts on the surface of gold nanostructures. The resultant surface decoration of gold with secondary metal nanoparticles not only indicates regions on the surface which are rich in active sites but also provides a method to form interesting bimetallic surfaces.

Decoration of active sites to create bimetallic surfaces and its implication for electrochemical processes

The creation of electrocatalysts based on noble metals has received a significant amount of research interest due to their extensive use as fuel cell catalysts and electrochemical sensors. There have been many attempts to improve the activity of these metals through creating nanostructures, as well as post-synthesis treatments based on chemical, electrochemical, sonochemical and thermal approaches. In many instances these methods result in a material with active surface states, which can be considered to be adatoms or clusters of atoms on the surface that have a low lattice co-ordination number making them more prone to electrochemical oxidation at a wide range of potentials that are significantly less positive than those of their bulk metal counterparts. This phenomenon has been termed pre-monolayer oxidation and has been reported to occur on a range of metallic surfaces. In this work we present findings on the presence of active sites on Pd that has been: evaporated as a thin film; electrodeposited as nanostructures; as well as commercially available Pd nanoparticles supported on carbon. Significantly, advantage is taken of the low oxidation potential of these active sites whereby bimetallic surfaces are created by the spontaneous deposition of Ag from AgNO3 to generate Pd/Ag surfaces. Interestingly this approach does not increase the surface area of the original metal but has significant implications for its further use as an electrode material. It results in the inhibition or promotion of electrocatalytic activity which is highly dependent on the reaction of interest. As a general approach the decoration of active catalytic materials with less active metals for a particular reaction also opens up the possibility of investigating the role of the initially present active sites on the surface and identifying the degree to which they are responsible for electrocatalytic activity.

Reliability of spatiotemporal and kinetic gait parameters determined by a new instrumented treadmill system

Background Despite the emerging use of treadmills integrated with pressure platforms as outcome tools in both clinical and research settings, published evidence regarding the measurement properties of these new systems is limited. This study evaluated the within– and between–day repeatability of spatial, temporal and vertical ground reaction forces measured by a treadmill system instrumented with a capacitance–based pressure platform. Methods Thirty three healthy adults (mean age, 21.5 ± 2.8 years; height, 168.4 ± 9.9 cm; and mass, 67.8 ± 18.6 kg), walked barefoot on a treadmill system (FDM–THM–S, Zebris Medical GmbH) on three separate occasions. For each testing session, participants set their preferred pace but were blinded to treadmill speed. Spatial (foot rotation, step width, stride and step length), temporal (stride and step times, duration of stance, swing and single and double support) and peak vertical ground reaction force variables were collected over a 30–second capture period, equating to an average of 52 ± 5 steps of steady–state walking. Testing was repeated one week following the initial trial and again, for a third time, 20 minutes later. Repeated measures ANOVAs within a generalized linear modelling framework were used to assess between–session differences in gait parameters. Agreement between gait parameters measured within the same day (session 2 and 3) and between days (session 1 and 2; 1 and 3) were evaluated using the 95% repeatability coefficient. Results There were statistically significant differences in the majority (14/16) of temporal, spatial and kinetic gait parameters over the three test sessions (P < .01). The minimum change that could be detected with 95% confidence ranged between 3% and 17% for temporal parameters, 14% and 33% for spatial parameters, and 4% and 20% for kinetic parameters between days. Within–day repeatability was similar to that observed between days. Temporal and kinetic gait parameters were typically more consistent than spatial parameters. The 95% repeatability coefficient for vertical force peaks ranged between ± 53 and ± 63 N. Conclusions The limits of agreement in spatial parameters and ground reaction forces for the treadmill system encompass previously reported changes with neuromuscular pathology and footwear interventions. These findings provide clinicians and researchers with an indication of the repeatability and sensitivity of the Zebris treadmill system to detect changes in common spatiotemporal gait parameters and vertical ground reaction forces.

Effect of defects on fracture strength of graphene sheets

With a hexagonal monolayer network of carbon atoms, graphene has demonstrated exceptional electrical 22 and mechanical properties. In this work, the fracture of graphene sheets with Stone–Wales type defects and vacancies were investigated using molecular dynamics simulations at different temperatures. The initiation of defects via bond rotation was also investigated. The results indicate that the defects and vacancies can cause significant strength loss in graphene. The fracture strength of graphene is also affected by temperature and loading directions. The simulation results were compared with the prediction from the quantized fracture mechanics.

Hydraulic instability onset detection in Kaplan turbines by monitoring shaft vibrations

Design of hydraulic turbines has often to deal with hydraulic instability. It is well-known that Francis and Kaplan types present hydraulic instability in their design power range. Even if modern CFD tools may help to define these dangerous operating conditions and optimize runner design, hydraulic instabilities may fortuitously arise during the turbine life and should be timely detected in order to assure a long-lasting operating life. In a previous paper, the authors have considered the phenomenon of helical vortex rope, which happens at low flow rates when a swirling flow, in the draft tube conical inlet, occupies a large portion of the inlet. In this condition, a strong helical vortex rope appears. The vortex rope causes mechanical effects on the runner, on the whole turbine and on the draft tube, which may eventually produce severe damages on the turbine unit and whose most evident symptoms are vibrations. The authors have already shown that vibration analysis is suitable for detecting vortex rope onset, thanks to an experimental test campaign performed during the commissioning of a 23 MW Kaplan hydraulic turbine unit. In this paper, the authors propose a sophisticated data driven approach to detect vortex rope onset at different power load, based on the analysis of the vibration signals in the order domain and introducing the so-called "residual order spectrogram", i.e. an order-rotation representation of the vibration signal. Some experimental test runs are presented and the possibility to detect instability onset, especially in real-time, is discussed.

Influence of different nitrogen rates and DMPP nitrification inhibitor on annual N2O emissions from a subtropical wheat–maize cropping system

Global cereal production will need to increase by 50% to 70% to feed a world population of about 9 billion by 2050. This intensification is forecast to occur mostly in subtropical regions, where warm and humid conditions can promote high N2O losses from cropped soils. To secure high crop production without exacerbating N2O emissions, new nitrogen (N) fertiliser management strategies are necessary. This one-year study evaluated the efficacy of a nitrification inhibitor (3,4-dimethylpyrazole phosphate—DMPP) and different N fertiliser rates to reduce N2O emissions in a wheat–maize rotation in subtropical Australia. Annual N2O emissions were monitored using a fully automated greenhouse gas measuring system. Four treatments were fertilized with different rates of urea, including a control (40 kg-N ha−1 year−1), a conventional N fertiliser rate adjusted on estimated residual soil N (120 kg-N ha−1 year−1), a conventional N fertiliser rate (240 kg-N ha−1 year−1) and a conventional N fertiliser rate (240 kg-N ha−1 year−1) with nitrification inhibitor (DMPP) applied at top dressing. The maize season was by far the main contributor to annual N2O emissions due to the high soil moisture and temperature conditions, as well as the elevated N rates applied. Annual N2O emissions in the four treatments amounted to 0.49, 0.84, 2.02 and 0.74 kg N2O–N ha−1 year−1, respectively, and corresponded to emission factors of 0.29%, 0.39%, 0.69% and 0.16% of total N applied. Halving the annual conventional N fertiliser rate in the adjusted N treatment led to N2O emissions comparable to the DMPP treatment but extensively penalised maize yield. The application of DMPP produced a significant reduction in N2O emissions only in the maize season. The use of DMPP with urea at the conventional N rate reduced annual N2O emissions by more than 60% but did not affect crop yields. The results of this study indicate that: (i) future strategies aimed at securing subtropical cereal production without increasing N2O emissions should focus on the fertilisation of the summer crop; (ii) adjusting conventional N fertiliser rates on estimated residual soil N is an effective practice to reduce N2O emissions but can lead to substantial yield losses if the residual soil N is not assessed correctly; (iii) the application of DMPP is a feasible strategy to reduce annual N2O emissions from sub-tropical wheat–maize rotations. However, at the N rates tested in this study DMPP urea did not increase crop yields, making it impossible to recoup extra costs associated with this fertiliser. The findings of this study will support farmers and policy makers to define effective fertilisation strategies to reduce N2O emissions from subtropical cereal cropping systems while maintaining high crop productivity. More research is needed to assess the use of DMPP urea in terms of reducing conventional N fertiliser rates and subsequently enable a decrease of fertilisation costs and a further abatement of fertiliser-induced N2O emissions.

A biomechanical analysis of anterior instrumentation used in the surgical correction of adolescent idiopathic scoliosis

Scoliosis is a deformity of the spine which affects children and adolescents, and remains a challenge to treat. This study measured the forces used during surgery to correct scoliosis and studied changes to spinal mechanics from the implantation of metal rods used to hold the spine straight. The results of this study will help surgeons and engineers understand how to straighten the spine more efficiently to provide patients with better outcomes.

A biomechanical analysis of growing rods used in the management of early onset scoliosis (EOS)

The use of dual growing rods is a fusionless surgical approach to the treatment of early onset scoliosis (EOS) which aims to harness potential growth in order to correct spinal deformity. This study compared through in-vitro experiments the biomechanical response of two different rod designs under axial rotation loading. The study showed that a new design of telescoping growing rod preserved the rotational flexibility of the spine in comparison with rigid rods indicating them to be a more physiological way to improve the spinal deformity.

Poly[mu5-{hydrogen bis[(E)-cinnamato]}-caesium

In the structure of the title polymeric complex [Cs2(C9H7O2)(C9H8O2)]n, the Cs salt-adduct of trans-cinnamic acid, the Cs+ ions of the two individual irregular CsO8 coordination polyhedra lie on a twofold rotation axis and are linked by four bridging carboxyl O-donors from the two cinnamate ligand species. These two ligand components are inter-linked through a delocalized H atom within a short O...H...O hydrogen bond. Structure extension gives a two-dimensional coordination polymer which lies parallel to (001). The crystal was determined from a crystal twinned by non-merohedry, with a twin component ratio of approximately 1:1.

Neck movement and muscle activity characteristics in female office workers with neck pain

Study Design Cross-sectional study. Objective To explore aspects of cervical musculoskeletal function in female office workers with neck pain. Summary of Background Data Evidence of physical characteristics that differentiate computer workers with and without neck pain is sparse. Patients with chronic neck pain demonstrate reduced motion and altered patterns of muscle control in the cervical flexor and upper trapezius (UT) muscles during specific tasks. Understanding cervical musculoskeletal function in office workers will better direct intervention and prevention strategies. Methods Measures included neck range of motion; superficial neck flexor muscle activity during a clinical test, the craniocerivcal flexion test; and a motor task, a unilateral muscle coordination task, to assess the activity of both the anterior and posterior neck muscles. Office workers with and without neck pain were formed into 3 groups based on their scores on the Neck Disability Index. Nonworking women without neck pain formed the control group. Surface electromyographic activity was recorded bilaterally from the sternocleidomastoid, anterior scalene (AS), cervical extensor (CE) and UT muscles. Results Workers with neck pain had reduced rotation range and increased activity of the superficial cervical flexors during the craniocervical flexion test. During the coordination task, workers with pain demonstrated greater activity in the CE muscles bilaterally. On completion of the task, the UT and dominant CE and AS muscles demonstrated an inability to relax in workers with pain. In general, there was a linear relationship between the workers’ self-reported levels of pain and disability and the movement and muscle changes. Conclusion These results are consistent with those found in other cervical musculoskeletal disorders and may represent an altered muscle recruitment strategy to stabilize the head and neck. An exercise program including motor reeducation may assist in the management of neck pain in office workers.

Photoelectron spectroscopic study of the oxyallyl diradical

The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O center dot-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (B-3(2) and B-3(1)) of OXA and the ground doublet state ((2)A(2)) of the radical anion using density, functional theory (DFT). Spectral simulations have been carried out for the triplet statics based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the B-3(2) state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the B-3(2) feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the B-3(2) state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ((1)A(1)) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the (1)A(1) state and its vibrational progression of the CO stretching mode. The A, state is the lowest electronic state of,OXA, and the electron affinity (EA) of OXA is 1.940 +/- 0.010 eV. The B-3(2) state is the first excited state with an electronic term energy of 55 +/- 2 meV. The widths of the vibronic peaks of the (X) over tilde (1)A(1) state are much broader than those of the (a) over tilde B-3(2) state, implying that the (1)A(1) state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the (1)A(1) state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cydopropanone. The simulation of (b) over tilde B-3(1) OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the B-3(1) state is 0.883 +/- 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O center dot- reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to the (X) over tilde (3)A '' state of AC. The ground ((2)A '') and first excited ((2)A') states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

Modeling nitrous oxide emissions from irrigated agriculture : testing DayCent with high-frequency measurements

A unique high temporal frequency dataset from an irrigated cotton-wheat rotation was used to test the agroecosystem model DayCent to simulate daily N2O emissions from sub-tropical vertisols under different irrigation intensities. DayCent was able to simulate the effect of different irrigation intensities on N2O fluxes and yield, although it tended to overestimate seasonal fluxes during the cotton season. DayCent accurately predicted soil moisture dynamics and the timing and magnitude of high fluxes associated with fertilizer additions and irrigation events. At the daily scale we found a good correlation of predicted vs. measured N2O fluxes (r2 = 0.52), confirming that DayCent can be used to test agricultural practices for mitigating N2O emission from irrigated cropping systems. A 25 year scenario analysis indicated that N2O losses from irrigated cotton-wheat rotations on black vertisols in Australia can be substantially reduced by an optimized fertilizer and irrigation management system (i.e. frequent irrigation, avoidance of excessive fertiliser application), while sustaining maximum yield potentials.

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.

Short-term changes in axial length during simulations of typical far, intermediate and near tasks

Purpose: To investigate the changes in axial length with the combined effect of accommodation and angle of gaze (convergence and downward gaze) over 5 minutes in groups of myopes and emmetropes. Methods: A total of 31 subjects (nine emmetropes, 10 low myopes, and 12 moderate to high myopes) aged from 18 to 31 years were recruited. To measure ocular biometrics in inferonasal gaze with accommodation, an optical biometer (Lenstar LS900) was inclined on a tilt and height adjustable stage, with the subject’s chinrest mounted on a rotary stage to induce various levels of convergence by rotation of the subject’s head in primary or downward gaze. Initially, the subjects performed a distance viewing task in primary gaze for 10 minutes to provide a ‘wash-out’ period for prior visual tasks, and then the subject’s axial length and ocular biometrics were measured in nine different combinations of gaze/accommodation over 5 minutes. These nine sessions for all gaze measurements (i.e. three levels of accommodation 9 three levels of convergence) were completed across 3 days of testing (one accommodation condition on each day).The nine combinations of gaze/accommodation were based on those required to view the centre, right and left edges of a distant TV at 6 m in primary gaze, an intermediate task (i.e. computer at 50 cm in 10° downward gaze) and a near task (i.e. reading A4 page at 20 cm in 20° downward gaze). Subjects were wearing a custom built three-axes head tracker throughout the experiment that monitored subjects’ relative head movements (roll, pitch and yaw) during measurements. Results: A significant increase in axial length occurred with the combined effect of accommodation, convergence and downward gaze (repeated measures ANOVA, p < 0.001), with the greatest axial elongation during the near task in downward gaze with convergence (i.e. downward 20°/inward 33°, with 5 D accommodation) (mean change 33 ± 13 lm, after 5 minutes task) followed by the intermediate task (i.e. downward 10°/inward 25°, with 2 D accommodation) (mean change 14 ± 11 lm, after 5 minutes task).Changes in axial length for the distance task (i.e. primary gaze/9° convergence, with 0.16 D accommodation) were not statistically significant (mean change 4 ± 8 lm, after 5 minutes task, p > 0.05). Moderate to high myopes had a greater change in the axial length (mean change 40 ± 11 lm after 5 minutes of near task) than that of emmetropes (mean change 29 ± 15 lm after 5 minutes of near task) and low myopes (mean change 29 ± 16 lm after 5 minutes of near task) associated with time (p = 0.02) and accommodation by time (p = 0.03). Conclusions: The combination of accommodation, convergence and downward angle has a significant short term effect on axial length over time. The near task in downward gaze with convergence caused a greater change in axial length than the intermediate and distant visual tasks. The greater axial elongation measured in the infero-nasal direction with accommodation is most likely associated with a combination of biomechanical factors such as, extraocular muscle forces and ciliary muscle contraction.

Qualitative spatial reasoning about directions in a corridor containing a single turn

An experiment was conducted to investigate the process of reasoning about directions in an egocentric space. Each participant walked through a corridor containing an angular turn ranging in size from 0° to 90°, in 15° increments. A direction was given to participants at the entrance of the corridor and they were asked to answer this direction at the end of this corridor. Considering the fact that participants had to reason the direction in the featureless corridor, two hypotheses were proposed: (i) reasoning about directions falls into qualitative reasoning by using a small number of coarse angular categories (four 90° categories or eight 45° categories: 90° categories consist of front, back, left, right; 45° categories consist of 90° categories and the four intermediates) that reference axes generate; (ii) reasoning about directions would be done by recalling the rotation angle from the traveling direction to the direction that participants tried to answer. In addition, the configuration of reference axes that participants employed was examined. Both hypotheses were supported, and the data designated that reference axes consisted of eight directions: a pair of orthogonal axes and diagonals.