Hyperbranched polymer-gold nanoparticle assemblies : role of polymer architecture in hybrid assembly formation and SERS activity

Plasmonic gold nano-assemblies that self-assemble with the aid of linking molecules or polymers have the potential to yield controlled hierarchies of morphologies and consequently result in materials with tailored optical (e.g. localized surface plasmon resonances (LSPR)) and spectroscopic properties (e.g. surface enhanced Raman scattering (SERS)). Molecular linkers that are structurally well-defined are promising for forming hybrid nano-assemblies which are stable in aqueous solution and are increasingly finding application in nanomedicine. Despite much ongoing research in this field, the precise role of molecular linkers in governing the morphology and properties of the hybrid nano-assemblies remains unclear. Previously we have demonstrated that branched linkers, such as hyperbranched polymers, with specific anchoring end groups can be successfully employed to form assemblies of gold NPs demonstrating near-infrared SPRs and intense SERS scattering. We herein introduce a tailored polymer as a versatile molecular linker, capable of manipulating nano-assembly morphologies and hot-spot density. In addition, this report explores the role of the polymeric linker architecture, specifically the degree of branching of the tailored polymer in determining the formation, morphology and properties of the hybrid nano-assemblies. The degree of branching of the linker polymer, in addition to the concentration and number of anchoring groups, is observed to strongly influence the self-assembly process. The assembly morphology shifts primarily from 1D-like chains to 2D plates and finally to 3D-like globular structures, with increase in degree of branching. Insights have been gained into how the morphology influences the SERS performance of these nano-assemblies with respect to hot-spot density. These findings supplement the understanding of the morphology determining nano-assembly formation and pave the way for the possible application of these nano-assemblies as SERS bio-sensors for medical diagnostics.

On-the-fly web content integrity check boosts users' confidence

Web servers are accessible by anyone who can access the Internet. Although this universal accessibility is attractive for all kinds of Web-based applications, Web servers are exposed to attackers who may want to alter their contents. Alterations range from humorous additions or changes, which are typically easy to spot, to more sinister tampering, such as providing false or damaging information.

Lower partial moment and information entropy-based dynamic electricity purchasing strategy

In the electricity market environment, load-serving entities (LSEs) will inevitably face risks in purchasing electricity because there are a plethora of uncertainties involved. To maximize profits and minimize risks, LSEs need to develop an optimal strategy to reasonably allocate the purchased electricity amount in different electricity markets such as the spot market, bilateral contract market, and options market. Because risks originate from uncertainties, an approach is presented to address the risk evaluation problem by the combined use of the lower partial moment and information entropy (LPME). The lower partial moment is used to measure the amount and probability of the loss, whereas the information entropy is used to represent the uncertainty of the loss. Electricity purchasing is a repeated procedure; therefore, the model presented represents a dynamic strategy. Under the chance-constrained programming framework, the developed optimization model minimizes the risk of the electricity purchasing portfolio in different markets because the actual profit of the LSE concerned is not less than the specified target under a required confidence level. Then, the particle swarm optimization (PSO) algorithm is employed to solve the optimization model. Finally, a sample example is used to illustrate the basic features of the developed model and method.

Characterization of a DC-driven microplasma between a capillary tube and water surface

A microplasma generated between a stainless-steel capillary and water surface in ambient air with flowing argon as working gas appears as a bright spot at the tube orifice and expands to form a larger footprint on the water surface, and the dimensions of the bell-shaped microplasma are all below 1 mm. The electron density of the microplasma is estimated to be ranging from 5.32 × 109 cm−3 to 2.02 × 1014 cm−3 for the different operating conditions, which is desirable for generating abundant amounts of reactive species. A computational technique is adopted to fit the experimental emission from the N2 second positive system with simulation results. It is concluded that the vibrational temperature (more than 2000 K) is more than twice the gas temperature (more than 800 K), which indicates the non-equilibrium state of the microplasma. Both temperatures showed dependence on the discharge parameters (i.e., gas flow and discharge current). Such a plasma device could be arranged in arrays for applications utilizing plasmainduced liquid chemistry.

The use of penumbrae to define and analyse non-standard fields

Aim A new method of penumbral analysis is implemented which allows an unambiguous determination of field size and penumbra size and quality for small fields and other non-standard fields. Both source occlusion and lateral electronic disequilibrium will affect the size and shape of cross-axis profile penumbrae; each is examined in detail. Method A new method of penumbral analysis is implemented where the square of the derivative of the cross-axis profile is plotted. The resultant graph displays two peaks in the place of the two penumbrae. This allows a strong visualisation of the quality of a field penumbra, as well as a mathematically consistent method of determining field size (distance between the two peak’s maxima), and penumbra (full-widthtenth-maximum of peak). Cross-axis profiles were simulated in a water phantom at a depth of 5 cm using Monte Carlo modelling, for field sizes between 5 and 30 mm. The field size and penumbra size of each field was calculated using the method above, as well as traditional definitions set out in IEC976. The effect of source occlusion and lateral electronic disequilibrium on the penumbrae was isolated by repeating the simulations removing electron transport and using an electron spot size of 0 mm, respectively. Results All field sizes calculated using the traditional and proposed methods agreed within 0.2 mm. The penumbra size measured using the proposed method was systematically 1.8 mm larger than the traditional method at all field sizes. The size of the source had a larger effect on the size of the penumbra than did lateral electronic disequilibrium, particularly at very small field sizes. Conclusion Traditional methods of calculating field size and penumbra are proved to be mathematically adequate for small fields. However, the field size definition proposed in this study would be more robust amongst other nonstandard fields, such as flattening filter free. Source occlusion plays a bigger role than lateral electronic disequilibrium in small field penumbra size.

Did Brisbane grow smartly? Drivers of city growth 1991-2001 and lessons for current policies

Urban areas are growing unsustainably around the world; however, the growth patterns and their associated drivers vary between contexts. As a result, research has highlighted the need to adopt case study based approaches to stimulate the development of new theoretic understandings. Using land-cover data sets derived from Landsat images (30 m × 30 m), this research identifies both patterns and drivers of urban growth in a period (1991-2001) when a number of policy acts were enacted aimed at fostering smart growth in Brisbane, Australia. A linear multiple regression model was estimated using the proportion of lands that were converted from non-built-up (1991) to built-up usage (2001) within a suburb as a dependent variable to identify significant drivers of land-cover changes. In addition, the hot spot analysis was conducted to identify spatial biases of land-cover changes, if any. Results show that the built-up areas increased by 1.34% every year. About 19.56% of the non-built-up lands in 1991 were converted into built-up lands in 2001. This conversion pattern was significantly biased in the northernmost and southernmost suburbs in the city. This is due to the fact that, as evident from the regression analysis, these suburbs experienced a higher rate of population growth, and had the availability of habitable green field sites in relatively flat lands. The above findings suggest that the policy interventions undertaken between the periods were not as effective in promoting sustainable changes in the environment as they were aimed for.

Infringement notices: stimulus for prevention or trivialising offences?

In the OHS field increasing use is being made of administrative penalties to enforce OHS legislation. Infringement notices (also known as penalty notices or on-the-spot fines) are used in several Australian jurisdictions and there are plans to introduce them in others. Overseas jurisdictions with some form of OHS administrative penalty include the United States, some Canadian provinces, and the system recently enacted in New Zealand. This article reviews empirical evidence and legal arguments about the use of infringement notices for enforcing OHS legislation. Key factors influencing the impact of these notices are discussed, including the monetary amounts of penalties, the nature of offences, the criteria and processes for issuing notices, and other implementation issues. There is a need for further empirical studies to determine the characteristics of infringement notice schemes that are most effective in motivating preventive action.

Stories have the power to save us: A neurological framework for the imperative to tell stories

The evolutionary advantage of humans is in our unique ability to process stories – we have highly evolved ‘narrative organs.’ Through storytelling, vicarious knowledge, even guarded knowledge, is used to help our species to survive. We learn, regardless of whether the story being told is ‘truth’ or ‘fiction.’ This article discusses how humans place themselves in stories, as both observer and participant, to create a ‘neural balance’ or sweet spot that allows them to be immersed in a story without being entirely threatened by it – and how this involvement in story is the formation of empathy – an empathy that is integral to forging a future humanity. It is through empathy, we argue, that stories have the power to save us.

Excitation of bound plasmons along nanoscale stripe waveguides: A comparison of end and grating coupling techniques

In this paper we excite bound long range stripe plasmon modes with a highly focused laser beam. We demonstrate highly confined plasmons propagating along a 50 μm long silver stripe 750 nm wide and 30 nm thick. Two excitation techniques were studied: focusing the laser spot onto the waveguide end and focusing the laser spot onto a silver grating. By comparing the intensity of the out-coupling photons at the end of the stripe for both grating and end excitation we are able to show that gratings provide an increase of a factor of two in the output intensity and thus out-coupling of plasmons excited by this technique are easier to detect. Authors expect that the outcome of this paper will prove beneficial for the development of passive nano-optical devices based on stripe waveguides, by providing insight into the different excitation techniques available and the advantages of each technique.

A smooth transition logit model of the effects of deregulation in the electricity market

This paper introduces the smooth transition logit (STL) model that is designed to detect and model situations in which there is structural change in the behaviour underlying the latent index from which the binary dependent variable is constructed. The maximum likelihood estimators of the parameters of the model are derived along with their asymptotic properties, together with a Lagrange multiplier test of the null hypothesis of linearity in the underlying latent index. The development of the STL model is motivated by the desire to assess the impact of deregulation in the Queensland electricity market and ascertain whether increased competition has resulted in significant changes in the behaviour of the spot price of electricity, specifically with respect to the occurrence of periodic abnormally high prices. The model allows the timing of any change to be endogenously determined and also market participants' behaviour to change gradually over time. The main results provide clear evidence in support of a structural change in the nature of price events, and the endogenously determined timing of the change is consistent with the process of deregulation in Queensland.

A magnetic climbing robot for marine inspection services

Currently, the inspection of sea-going vessels is performed manually. Ship surveyors do a visual inspection; in some cases they also use cameras and non-destructive testing methods. Prior to a ship surveying process a lot of scaffolding has to be provided in order to make every spot accessible for the surveyor. In this work a robotic system is presented, which is able to access many areas of a cargo hold of a ship and perform visual inspection without any scaffolding. The paper also describes how the position of the acquired data is estimated with an optical 3D tracking unit and how critical points on the hull can be marked via a remote controlled marker device. Furthermore first results of onboard tests with the system are provided.

Performance-Based Quality Assurance/Quality Control (QA/QC) Acceptance Procedures for In-Place Soil Testing Phase 3

One of the objectives of this study was to evaluate soil testing equipment based on its capability of measuring in-place stiffness or modulus values. As design criteria transition from empirical to mechanistic-empirical, soil test methods and equipment that measure properties such as stiffness and modulus and how they relate to Florida materials are needed. Requirements for the selected equipment are that they be portable, cost effective, reliable, a ccurate, and repeatable. A second objective is that the selected equipment measures soil properties without the use of nuclear materials.The current device used to measure soil compaction is the nuclear density gauge (NDG). Equipment evaluated in this research included lightweight deflectometers (LWD) from different manufacturers, a dynamic cone penetrometer (DCP), a GeoGauge, a Clegg impact soil tester (CIST), a Briaud compaction device (BCD), and a seismic pavement analyzer (SPA). Evaluations were conducted over ranges of measured densities and moistures.Testing (Phases I and II) was conducted in a test box and test pits. Phase III testing was conducted on materials found on five construction projects located in the Jacksonville, Florida, area. Phase I analyses determined that the GeoGauge had the lowest overall coefficient of variance (COV). In ascending order of COV were the accelerometer-type LWD, the geophone-type LWD, the DCP, the BCD, and the SPA which had the highest overall COV. As a result, the BCD and the SPA were excluded from Phase II testing.In Phase II, measurements obtained from the selected equipment were compared to the modulus values obtained by the static plate load test (PLT), the resilient modulus (MR) from laboratory testing, and the NDG measurements. To minimize soil and moisture content variability, the single spot testing sequence was developed. At each location, test results obtained from the portable equipment under evaluation were compared to the values from adjacent NDG, PLT, and laboratory MR measurements. Correlations were developed through statistical analysis. Target values were developed for various soils for verification on similar soils that were field tested in Phase III. The single spot testing sequence also was employed in Phase III, field testing performed on A-3 and A-2-4 embankments, limerock-stabilized subgrade, limerock base, and graded aggregate base found on Florida Department of Transportation construction projects. The Phase II and Phase III results provided potential trend information for future research—specifically, data collection for in-depth statistical analysis for correlations with the laboratory MR for specific soil types under specific moisture conditions. With the collection of enough data, stronger relationships could be expected between measurements from the portable equipment and the MR values. Based on the statistical analyses and the experience gained from extensive use of the equipment, the combination of the DCP and the LWD was selected for in-place soil testing for compaction control acceptance. Test methods and developmental specifications were written for the DCP and the LWD. The developmental specifications include target values for the compaction control of embankment, subgrade, and base materials.

Decompression melting driving intraplate volcanism in Australia: Evidence from magnetotelluric sounding

A long-period magnetotelluric (MT) survey, with 39 sites covering an area of 270 by 150 km, has identified melt within the thinned lithosphere of Pleistocene-Holocene Newer Volcanics Province (NVP) in southeast Australia, which has been variously attributed to mantle plume activity or edge-driven mantle convection. Two-dimensional inversions from the MT array imaged a low-resistivity anomaly (10-30Ωm) beneath the NVP at ∼40-80 km depth, which is consistent with the presence of ∼1.5-4% partial melt in the lithosphere, but inconsistent with elevated iron content, metasomatism products or a hot spot. The conductive zone is located within thin juvenile oceanic mantle lithosphere, which was accreted onto thicker Proterozoic continental mantle lithosphere. We propose that the NVP owes its origin to decompression melting within the asthenosphere, promoted by lithospheric thickness variations in conjunction with rapid shear, where asthenospheric material is drawn by shear flow at a "step" at the base of the lithosphere.

Low δ18O zircons from the Bruneau-­Jarbidge eruptive center: A key to crustal anatexis along the track of the Yellowstone hotspot

The Bruneau-Jarbidge eruptive center (BJEC) in the central Snake River Plain, Idaho, USA consists of the Cougar Point Tuff (CPT), a series of ten, high-temperature (900-1000°C) voluminous ignimbrites produced over the explosive phase of volcanism (12.8-10.5 Ma) and more than a dozen equally high-temperature rhyolite lava flows produced during the effusive phase (10.5-8 Ma). Spot analyses by ion microprobe of oxygen isotope ratios in 210 zircons demonstrate that all of the eruptive units of the BJEC are characterized by zircon δ¹⁸O values ≤ 2.5‰, thus documenting the largest low δ¹⁸O silicic volcanic province known on Earth (>10⁴ km³). There is no evidence for voluminous normal δ¹⁸O magmatism at the BJEC that precedes generation of low δ¹⁸O magmas as there is at other volcanic centers that generate low δ¹⁸O magmas such as Heise and Yellowstone. At these younger volcanic centers of the hotspot track, such low δ¹⁸O magmas represent ~45 % and ~20% respectively of total eruptive volumes. Zircons in all BJEC tuffs and lavas studied (23 units) document strong δ¹⁸O depletion (median CPT δ¹⁸OZrc = 1.0‰, post-CPT lavas = 1.5‰) with the third member of the CPT recording an excursion to minimum δ¹⁸O values (δ¹⁸OZrc= -1.8‰) in a supereruption > 2‰ lower than other voluminous low δ¹⁸O rhyolites known worldwide (δ¹⁸OWR ≤0.9 vs. 3.4‰). Subsequent units of the CPT and lavas record a progressive recovery in δ¹⁸OZrc to ~2.5‰ over a ~ 4 m.y. interval (12 to 8 Ma). We present detailed evidence of unit-to-unit systematic patterns in O isotopic zoning in zircons (i.e. direction and magnitude of Δcore-rim), spectrum of δ¹⁸O in individual units, and zircon inheritance patterns established by re-analysis of spots for U-Th-Pb isotopes by LA-ICPMS and SHRIMP. In conjunction with mineral thermometry and magma compositions, these patterns are difficult to reconcile with the well-established model for "cannibalistic" low δ¹⁸O magma genesis at Heise and Yellowstone. We present an alternative model for the central Snake River Plain using the modeling results of Leeman et al. (2008) for ¹⁸O depletion as a function of depth in a mid-upper crustal protolith that was hydrothermally altered by infiltrating meteoric waters prior to the onset of silicic magmatism. The model proposes that BJEC silicic magmas were generated in response to the propagation of a melting front, driven by the incremental growth of a vast underlying mafic sill complex, over a ~5 m.y. interval through a crustal volume in which a vertically asymmetric δ¹⁸OWR gradient had previously developed that was sharply inflected from ~ -1 to 10‰ at mid-upper crustal depths. Within the context of the model, data from BJEC zircons are consistent with incremental melting and mixing events in roof zones of magma reservoirs that accompany surfaceward advance of the coupled mafic-silicic magmatic system.

Direct observations of pedestrian unsafe crossing at urban Australian level crossings

The number of pedestrian victims at Australian and foreign level crossings has remained stable over the past decade and it continues to be a significant problem. To examine the factors contributing to pedestrians’ unsafe crossing behaviours, direct observations were conducted at three black spot urban level crossings in Brisbane for a total of 45 h during morning and afternoon peak. In total, 129 pedestrians transgressed the active controls. More transgressions were observed at the crossings located in more populated suburbs in close proximity to large shopping centres and school zones, whereas the smallest number of transgressions were observed at the least populated locations. In addition to characteristics associated with the larger socio-economic area, the patterns of transgression could be associated with the properties of the existing safety equipment and the design of each level crossing (i.e. location of the platforms, number of rail tracks). Indeed, the largest number of crossed unoccupied but “at risk” rail tracks (where a train could have passed), was observed at the crossing with the least transgressions. Contrary to previous findings, younger adults were the most frequent transgressors. School children and elderly were most likely to transgress in groups. Potential directions for future research and more effective measures are discussed.