Switching radical stability by pH-induced orbital conversion

In most radicals the singly occupied molecular orbital (SOMO) is the highest-energy occupied molecular orbital (HOMO); however, in a small number of reported compounds this is not the case. In the present work we expand significantly the scope of this phenomenon, known as SOMO-HOMO energy-level conversion, by showing that it occurs in virtually any distonic radical anion that contains a sufficiently stabilized radical (aminoxyl, peroxyl, aminyl) non-pi-conjugated with a negative charge (carboxylate, phosphate, sulfate). Moreover, regular orbital order is restored on protonation of the anionic fragment, and hence the orbital configuration can be switched by pH. Most importantly, our theoretical and experimental results reveal a dramatically higher radical stability and proton acidity of such distonic radical anions. Changing radical stability by 3-4 orders of magnitude using pH-induced orbital conversion opens a variety of attractive industrial applications, including pH-switchable nitroxide-mediated polymerization, and it might be exploited in nature.

Residential balconies with road traffic noise : a combined source image and radiosity model

Several significant studies have been made in recent decades toward understanding road traffic noise and its effects on residential balconies. These previous studies have used a variety of techniques such as theoretical models, scale models and measurements on real balconies. The studies have considered either road traffic noise levels within the balcony space or inside an adjacent habitable room or both. Previous theoretical models have used, for example, simplified specular reflection calculations, boundary element methods (BEM), adaptations of CoRTN or the use of Sabine Theory. This paper presents an alternative theoretical model to predict the effects of road traffic noise spatially within the balcony space. The model includes a specular reflection component by calculating up to 10 orders of source images. To account for diffusion effects, a two compartment radiosity component is utilised. The first radiosity compartment is the urban street, represented as a street with building facades on either side. The second radiosity compartment is the balcony space. The model is designed to calculate the predicted road traffic noise levels within the balcony space and is capable of establishing the effect of changing street and balcony geometries. Screening attenuation algorithms are included to determine the effects of solid balcony parapets and balcony ceiling shields.

Carbon nanotube membranes with ultrahigh specific adsorption capacity for water desalination and purification

Development of technologies for water desalination and purification is critical to meet the global challenges of insufficient water supply and inadequate sanitation, especially for point-of-use applications. Conventional desalination methods are energy and operationally intensive, whereas adsorption-based techniques are simple and easy to use for point-of-use water purification, yet their capacity to remove salts is limited. Here we report that plasma-modified ultralong carbon nanotubes exhibit ultrahigh specific adsorption capacity for salt (exceeding 400% by weight) that is two orders of magnitude higher than that found in the current state-of-the-art activated carbon-based water treatment systems. We exploit this adsorption capacity in ultralong carbon nanotube-based membranes that can remove salt, as well as organic and metal contaminants. These ultralong carbon nanotube-based membranes may lead to next-generation rechargeable, point-of-use potable water purification appliances with superior desalination, disinfection and filtration properties. © 2013 Macmillan Publishers Limited.

Room-temperature, atmospheric plasma needle reduces adenovirus gene expression in HEK 293A host cells

Room-temperature, atmospheric-pressure plasma needle treatment is used to effectively minimize the adenovirus (AdV) infectivity as quantified by the dramatic reduction of its gene expression in HEK 293A primary human embryonic kidney cells studied by green fluorescent protein imaging. The AdV titer is reduced by two orders of magnitude within only 8 min of the plasma exposure. This effect is due to longer lifetimes and higher interaction efficacy of the plasma-generated reactive species in confined space exposed to the plasma rather than thermal effects commonly utilized in pathogen inactivation. This generic approach is promising for the next-generation anti-viral treatments and imunotherapies.

Plasma Nanoscience : from nature's mastery to deterministic plasma-aided nanofabrication

This paper introduces the plasma-nanoscience research area and shows the way from Nature's mastery in assembling nanosized dust grains in the Universe to deterministic plasma-aided nanofabrication. The concept of deterministic nanoassembly is explained, and the multidisciplinary approach to bridge the spatial gap of nine orders of magnitude between the sizes of plasma reactors and atomic building units is discussed. Ongoing numerical simulation and experimental efforts on highly controlled synthesis of carbon nanotip and semiconducting quantum-dot structures show potential benefits of using ionized-gas environments in nanofabrication. © 2007 IEEE.

SWCNT networks on nanoporous silica catalyst support : morphological and connectivity control for nanoelectronic, gas-sensing, and biosensing devices

Effective control of morphology and electrical connectivity of networks of single-walled carbon nanotubes (SWCNTs) by using rough, nanoporous silica supports of Fe catalyst nanoparticles in catalytic chemical vapor deposition is demonstrated experimentally. The very high quality of the nanotubes is evidenced by the G-to-D Raman peak ratios (>50) within the range of the highest known ratios. Transitions from separated nanotubes on smooth SiO2 surface to densely interconnected networks on the nanoporous SiO2 are accompanied by an almost two-order of magnitude increase of the nanotube density. These transitions herald the hardly detectable onset of the nanoscale connectivity and are confirmed by the microanalysis and electrical measurements. The achieved effective nanotube interconnection leads to the dramatic, almost three-orders of magnitude decrease of the SWCNT network resistivity compared to networks of similar density produced by wet chemistry-based assembly of preformed nanotubes. The growth model, supported by multiscale, multiphase modeling of SWCNT nucleation reveals multiple constructive roles of the porous catalyst support in facilitating the catalyst saturation and SWCNT nucleation, consistent with the observed higher density of longer nanotubes. The associated mechanisms are related to the unique surface conditions (roughness, wettability, and reduced catalyst coalescence) on the porous SiO2 and the increased carbon supply through the supporting porous structure. This approach is promising for the direct integration of SWCNT networks into Si-based nanodevice platforms and multiple applications ranging from nanoelectronics and energy conversion to bio- and environmental sensing.

Field-effect transistors based on self-organized molecular nanostripes

Charge transport properties in organic semiconductors depend strongly on molecular order. Here we demonstrate field-effect transistors where drain current flows through a precisely defined array of nanostripes made of crystalline and highly ordered molecules. The molecular stripes are fabricated across the channel of the transistor by a stamp-assisted deposition of the molecular semiconductors from a solution. As the solvent evaporates, the capillary forces drive the solution to form menisci under the stamp protrusions. The solute precipitates only in the regions where the solution is confined by the menisci once the critical concentration is reached and self-organizes into molecularly ordered stripes 100-200 nm wide and a few monolayers high. The charge mobility measured along the stripes is 2 orders of magnitude larger than the values measured for spin-coated thin films.

Accelerating taxonomic discovery through automated character extraction

This paper discusses the following key messages. Taxonomy is (and taxonomists are) more important than ever in times of global change. Taxonomic endeavour is not occurring fast enough: in 250 years since the creation of the Linnean Systema Naturae, only about 20% of Earth's species have been named. We need fundamental changes to the taxonomic process and paradigm to increase taxonomic productivity by orders of magnitude. Currently, taxonomic productivity is limited principally by the rate at which we capture and manage morphological information to enable species discovery. Many recent (and welcomed) initiatives in managing and delivering biodiversity information and accelerating the taxonomic process do not address this bottleneck. Development of computational image analysis and feature extraction methods is a crucial missing capacity needed to enable taxonomists to overcome the taxonomic impediment in a meaningful time frame. Copyright © 2009 Magnolia Press.

Parallel streaming signature EM-tree: A clustering algorithm for web scale applications

The proliferation of the web presents an unsolved problem of automatically analyzing billions of pages of natural language. We introduce a scalable algorithm that clusters hundreds of millions of web pages into hundreds of thousands of clusters. It does this on a single mid-range machine using efficient algorithms and compressed document representations. It is applied to two web-scale crawls covering tens of terabytes. ClueWeb09 and ClueWeb12 contain 500 and 733 million web pages and were clustered into 500,000 to 700,000 clusters. To the best of our knowledge, such fine grained clustering has not been previously demonstrated. Previous approaches clustered a sample that limits the maximum number of discoverable clusters. The proposed EM-tree algorithm uses the entire collection in clustering and produces several orders of magnitude more clusters than the existing algorithms. Fine grained clustering is necessary for meaningful clustering in massive collections where the number of distinct topics grows linearly with collection size. These fine-grained clusters show an improved cluster quality when assessed with two novel evaluations using ad hoc search relevance judgments and spam classifications for external validation. These evaluations solve the problem of assessing the quality of clusters where categorical labeling is unavailable and unfeasible.

Who are our repeating students? Profiling students persisting after failure

Research on attrition has focused on the economic significance of low graduation rates in terms of costs to students (fees that do not culminate in a credential) and impact on future income. For a student who fails a unit and repeats the unit multiple times, the financial impact is significant and lasting (Bexley, Daroesman, Arkoudis & James 2013). There are obvious advantages for the timely completion of a degree, both for the student and the institution. Advantages to students include fee minimisation, enhanced engagement opportunities, effectual pathway to employment and a sense of worth, morale and cohort-identity benefits. Work undertaken by the QUT Analytics Project in 2013 and 2014 explored student engagement patterns capturing a variety of data sources and specifically, the use of LMS amongst students in 804 undergraduate units in one semester. Units with high failure rates were given further attention and it was found that students who were repeating a unit were less likely to pass the unit than students attempting it for the first time. In this repeating cohort, academic and behavioural variables were consistently more significant in the modelling than were any demographic variables, indicating that a student’s performance at university is far more impacted by what they do once they arrive than it is by where they come from. The aim of this poster session is to examine the findings and commonalities of a number of case studies that articulated the engagement activities of repeating students (which included collating data from Individual Unit Reports, academic and peer advising programs and engagement with virtual learning resources). Understanding the profile of the repeating student cohort is therefore as important as considering the characteristics of successful students so that the institution might be better placed to target the repeating students and make proactive interventions as early as possible.

Seasonal and spatial variations in rare earth elements to identify inter-aquifer linkages and recharge processes in an Australian catchment

With the aim of elucidating the seasonal behaviour of rare earth elements (REEs), surface and groundwaters were collected under dry and wet conditions in different hydrological units of the Teviot Brook catchment (Southeast Queensland, Australia). Sampled waters showed a large degree of variability in both REE abundance and normalised patterns. Overall REE abundance ranged over nearly three orders of magnitude, and was consistently lower in the sedimentary bedrock aquifer (18ppt<∑REE<477ppt) than in the other hydrological systems studied. Abundance was greater in springs draining rhyolitic rocks (∑REE=300 and 2054ppt) than in springs draining basalt ranges (∑REE=25 and 83ppt), yet was highly variable in the shallow alluvial groundwater (16ppt<∑REE<5294ppt) and, to a lesser extent, in streamwater (85ppt<∑REE<2198ppt). Generally, waters that interacted with different rock types had different REE patterns. In order to obtain an unbiased characterisation of REE patterns, the ratios between light and middle REEs (R(M/L)) and the ratios between middle and heavy REEs (R(H/M)) were calculated for each sample. The sedimentary bedrock aquifer waters had highly evolved patterns depleted in light REEs and enriched in middle and heavy REEs (0.17of the sedimentary bedrock from upgradient to downgradient; typically they showed flat patterns in the upstream section of the alluvium (median R(M/L)=0.21 and median R(H/M)=-0.06) gradually evolving towards patterns depleted in light REEs and enriched in middle and heavy REEs downgradient (median R(M/L)=0.48 and median R(H/M)=0.38). To document the seasonal variations in REE patterns, the difference in ratios between dry and wet sampling campaigns was determined for each repeated sampling location. Contributions from the sedimentary bedrock water to the alluvium during the wet season were identified at two locations (increase from R(H/M)=0.03 and 0.35 to R(H/M)=0.62 and 0.89). The effect of recharge through fractured igneous rocks was also observed in two boreholes intercepting the sedimentary bedrock, where the freshly recharged waters likely contributed to the deeper groundwater flow during the wet season (decrease from R(M/L)=0.81 and 0.56 to R(M/L)=0.46 and 0.17). Results from this study suggest that REEs may be usefully applied as indicators of recharge processes and inter-aquifer mixing. They also underline the importance of conducting seasonal sampling campaigns to capture possible short-term variations in REE patterns and abundance, which is essential to enable a better understanding of hydrological and hydrochemical processes in complex geological settings

FreeS: A fast algorithm to discover frequent free subtrees using a novel canonical form

Web data can often be represented in free tree form; however, free tree mining methods seldom exist. In this paper, a computationally fast algorithm FreeS is presented to discover all frequently occurring free subtrees in a database of labelled free trees. FreeS is designed using an optimal canonical form, BOCF that can uniquely represent free trees even during the presence of isomorphism. To avoid enumeration of false positive candidates, it utilises the enumeration approach based on a tree-structure guided scheme. This paper presents lemmas that introduce conditions to conform the generation of free tree candidates during enumeration. Empirical study using both real and synthetic datasets shows that FreeS is scalable and significantly outperforms (i.e. few orders of magnitude faster than) the state-of-the-art frequent free tree mining algorithms, HybridTreeMiner and FreeTreeMiner.