Exploitation of the menshutkin reaction for the controlled assembly of halogen bonded architectures incorporating 1,2-diiodotetrafluorobenzene and 1,3,5-Triiodotrifluorobenzene

1,4-Diazabicyclo[2.2.2]octane (DABCO) forms well-defined co-crystals with 1,2-diiodotetrafluorobenzene (1,2-DITFB), [(1,2-DITFB)2DABCO], and 1,3,5-triiodotrifluorobenzene, [(1,3,5-TITFB)2DABCO]. Both systems exhibited lower-than-expected supramolecular connectivity, which inspired a search for polymorphs in alternative crystallization solvents. In dichloromethane solution, the Menshutkin reaction was found to occur, generating chloride anions and quaternary ammonium cations through the reaction between the solvent and DABCO. The controlled in situ production of chloride ions facilitated the crystallization of new halogen bonded networks, DABCO–CH2Cl[(1,2-DITFB)Cl] (zigzag X-bonded chains) and (DABCO–CH2Cl)3[(1,3,5-TITFB)2Cl3]·CHCl3 (2D pseudo-trigonal X-bonded nets displaying Borremean entanglement), propagating with charge-assisted C–I···Cl– halogen bonds. The method was found to be versatile, and substitution of DABCO with triethylamine (TEA) gave (TEA-CH2Cl)3[(1,2-DITFB)Cl3]·4(H2O) (mixed halogen bond hydrogen bond network with 2D supramolecular connectivity) and TEA-CH2Cl[(1,3,5-TITFB)Cl] (tightly packed planar trigonal nets). The co-crystals were typically produced in high yield and purity with relatively predictable supramolecular topology, particularly with respect to the connectivity of the iodobenzene molecules. The potential to use this synthetic methodology for crystal engineering of halogen bonded architectures is demonstrated and discussed.

Subprime agriculture, and Australia?

Today, Australian agriculture is not where we hoped it would be. Despite being highly productive and the nation's only 'strongly competitive industry', it is struggling across the country. There are successes, as there always will be, but the bulk of our food and fibre production is from enterprises with minimal profitability and unstable or unsound finances. A debt-deflation spiral and subprime mortgage crisis are now being fuelled by property fire sales while leading bankers proclaim no problem and governments dance at the edges. However, it is not just the bush that has problems. National economic conditions are deteriorating with per capita incomes falling and real interest rates still high. Well-informed policy strategies and effective responses are needed quickly if Australians are to avoid needless losses of capacity and wealth destruction in the cities and the bush.

Subtropical futures : Victoria Park re-imagined

Brisbane, the capital of Queensland, in South-East Queensland is situated on the Brisbane River, one of the largest rivers (and floodplains) on the east coast of Australia. The river defines the city and gives it its name. The river has been a natural place to accommodate some population growth for the city with high-density development that capitalises on the natural amenity, cycleways and a string of parks and the flatter land. The major floods of 2011 and the scare of 2013, has seen a more malevolent quality of the river and shift of thinking on its role within the city. The floods have made council, for the first time, acquire prime development sites near the river, with proposals for high density development and made them parks, at great cost. The pressure for population growth in Brisbane remains. 140,000 new dwellings are required by 2031. Brownfield sites are less plentiful and there is interest to rethink of some of the other strategic locations in the city away from the river on higher ground and steeper slopes. Some of these places are currently open spaces. Victoria Park Golf Course sits on a high ridge line and a very strategic part of the city just north of the city centre is one of the few remaining golf courses close to the centre of an Australian capital city. While it is a public course and a valuable community asset, it has been compromised by the recently completed northern busway with two bus stations constructed on its edges. It is bounded on the west and north-east by two major community facilities, the Queensland University of Technology (QUT) to the west and RBW Hospital at its northern end. In a city in need of urban consolidation, perhaps it is time to review the future of the golf course. This question has been investigated as a conjecture in the Master of Architecture program at the QUT. The project has been to re-imagine Victoria Park as a new city parkland and a place that makes an urban connection from the QUT to the hospital. This new urban precinct is be a medium to high-density transit oriented development that capitalises on the bus way stations and the proximity of the university and hospital. The precinct will frame/define/interact with the new major urban park for the city. A key question being addressed is how the design can embody and define principles of a subtropical urbanism. Students are identifying the appropriate street and block structure, density and built form to be accommodated on blocks that define and activate a rich sequence of streets and public spaces. The paper will present a critical overview of the project work that provides a lens to how future professionals may respond to these issue that will be the focus of their professional lives.

Hybrid chalcogenide nanoparticles : 2D-WS2 nanocrystals inside nested WS2 fullerenes

The MOCVD assisted formation of nested WS2 inorganic fullerenes (IF-WS2) was performed by enhancing surface diffusion with iodine, and fullerene growth was monitored by taking TEM snapshots of intermediate products. The internal structure of the core-shell nanoparticles was studied using scanning electron microscopy (SEM) after cross-cutting with a focused ion beam (FIB). Lamellar reaction intermediates were found occluded in the fullerene particles. In contrast to carbon fullerenes, layered metal chalcogenides prefer the formation of planar, plate-like structures where the dangling bonds at the edges are stabilized by excess S atoms. The effects of the reaction and annealing temperatures on the composition and morphology of the final product were investigated, and the strength of the WS2 shell was measured by intermittent contact-mode AFM. The encapsulated lamellar structures inside the hollow spheres may lead to enhanced tribological activities.

Effects of clear-fell harvest on bat home range.

We investigated effects of roost loss due to clear-fell harvest on bat home range. The study took place in plantation forest, inhabited by the New Zealand long-tailed bat (Chalinolobus tuberculatus), in which trees are harvested between the ages 26-32 years. We determined home ranges by radiotracking different bats in areas that had and had not been recently clear-fell harvested. Home ranges were smaller in areas that had been harvested. Adult male bats selected 20-25 year old stands within home ranges before and after harvest. Males selected edges with open unplanted areas when harvest had not occurred but no longer selected these at proportions greater than their availability post harvest, probably because they were then readily available. This is the first radiotracking study to demonstrate a change in home range size and selection concomitant with felling of large areas of plantation forest, and thus quantify negative effects of forestry operations on this speciose group. The use of smaller home ranges post-harvest may reflect smaller colony sizes and lower roost availability, both of which may increase isolation of colonies and vulnerability to local extinction.

Home range and habitat selection by a threatened bat in exotic plantation forest

Individuals' home ranges are constrained by resource distribution and density, population size, and energetic requirements. Consequently, home ranges and habitat selection may vary between individuals of different sex and reproductive conditions. Whilst home ranges of bats are well-studied in native habitats, they are often not well understood in modified landscapes, particularly exotic plantation forests. Although Chalinolobus tuberculatus (Vespertilionidae, Chiroptera) are present in plantation forests throughout New Zealand their home ranges have only been studied in native forest and forest-agricultural mosaic and no studies of habitat selection that included males had occurred in any habitat type. Therefore, we investigated C. tuberculatus home range and habitat selection within exotic plantation forest. Home range sizes did not differ between bats of different reproductive states. Bats selected home ranges with higher proportions of relatively old forest than was available. Males selected edges with open unplanted areas within their home ranges, which females avoided. We suggest males use these edges, highly profitable foraging areas with early evening peaks in invertebrate abundance, to maintain relatively low energetic demands. Females require longer periods of invertebrate activity to fulfil their needs so select older stands for foraging, where invertebrate activity is higher. These results highlight additional understanding gained when data are not pooled across sexes. Mitigation for harvest operations could include ensuring that areas suitable for foraging and roosting are located within a radius equal to the home range of this bat species.

Long-tailed bats' use of a Pinus radiata stand in Kinleith Forest : Recommendations for monitoring

Targeted monitoring of threatened species within plantations is becoming more important due to forest certification programmes’ requirement to consider protection of threatened species, and to increase knowledge of the distribution of species. To determine patterns of long-tailed bat (Chalinolobus tuberculatus) activity in different habitat structures, with the aim of improving the likelihood of detection by targeting monitoring, we monitored one stand of 26 year-old Pinus radiata over seven months between December 2007 and June 2008 in Kinleith Forest, an exotic plantation forest centred around Tokoroa, South Waikato, New Zealand. Activity was determined by acoustic recording equipment, which is able to detect and record bats’ echolocation calls. We monitored activity from sunset to sunrise along a road through the stand, along stand edges, and in the interior of the stand. Bats were recorded on 80% of the 35 nights monitored. All activity throughout the monitoring period was detected on the edge of the stand or along the road. No bats were detected within the interior of the stand. Bat activity was highest along the road through the stand (40.4% of all passes), followed by an edge with stream running alongside (35.2%), along the road within a skidsite (19.8%), and along an edge without a stream (4.6%). There was a significant positive relationship between bat pass rate (bat passes h-1) and the feeding buzz rate (feeding buzzes h-1) indicating that bat activity was associated with feeding and not just commuting. Bat feeding activity was also highest along the road through the stand (59.2% of feeding buzzes), followed by the road within the skidsite (30.6%), and along the stream-side edge (10.2%). No feeding buzzes were recorded in either the interior or along the edge without the stream. Differences in overall feeding activity were significant only between the road and edge and between edges with and without a stream. Bat activity was detected each month and always by the second night of monitoring, and in this stand was highest during April. We recommend targeted monitoring for long-tailed bats be focused on road-side and stand edge habitat, and along streams, and that monitoring take place for at least three nights to maximise probability of detection.

Echolocation calls and wing morphology of bats from the West Indies

Echolocation calls of 119 bats belonging to 12 species in three families from Antillean islands of Puerto Rico, Dominica, and St. Vincent were recorded by using time-expansion methods. Spectrograms of calls and descriptive statistics of five temporal and frequency variables measured from calls are presented. The echolocation calls of many of these species, particularly those in the family Phyllostomidae, have not been described previously. The wing morphology of each taxon is described and related to the structure of its echolocation calls and its foraging ecology. Of slow aerial-hawking insectivores, the Mormoopidae and Natalidae Mormoops blainvillii, Pteronotus davyi davyi, P. quadridens fuliginosus, and Natalus stramineus stramineus can forage with great manoeuvrability in background-cluttered space (close to vegetation), and are able to hover. Pteronotus parnellii portoricensis is able to fly and echolocate in highly-cluttered space (dense vegetation). Among frugivores, nectarivores and omnivores in the family Phyllostomidae, Brachyphylla cavernarum intermedia is adapted to foraging in the edges of vegetation in background-cluttered space, while Erophylla bombifrons bombifrons, Glossophaga longirostris rostrata, Artibeus jamaicensis jamaicensis, A. jamaicensis schwartzi and Stenoderma rufum darioi are adapted to foraging under canopies in highly-cluttered space and do not have speed or efficiency in commuting flight. In contrast, Monophyllus plethodon luciae, Sturnira lilium angeli and S. lilium paulsoni are adapted to fly in highly-cluttered space, but can also fly fast and efficiently in open areas.

The use of a Riesz fractional differential-based approach for texture enhancement in image processing

Texture enhancement is an important component of image processing that finds extensive application in science and engineering. The quality of medical images, quantified using the imaging texture, plays a significant role in the routine diagnosis performed by medical practitioners. Most image texture enhancement is performed using classical integral order differential mask operators. Recently, first order fractional differential operators were used to enhance images. Experimentation with these methods led to the conclusion that fractional differential operators not only maintain the low frequency contour features in the smooth areas of the image, but they also nonlinearly enhance edges and textures corresponding to high frequency image components. However, whilst these methods perform well in particular cases, they are not routinely useful across all applications. To this end, we apply the second order Riesz fractional differential operator to improve upon existing approaches of texture enhancement. Compared with the classical integral order differential mask operators and other first order fractional differential operators, we find that our new algorithms provide higher signal to noise values and superior image quality.

Edge-weighting of gene expression graphs

In recent years, considerable research efforts have been directed to micro-array technologies and their role in providing simultaneous information on expression profiles for thousands of genes. These data, when subjected to clustering and classification procedures, can assist in identifying patterns and providing insight on biological processes. To understand the properties of complex gene expression datasets, graphical representations can be used. Intuitively, the data can be represented in terms of a bipartite graph, with weighted edges corresponding to gene-sample node couples in the dataset. Biologically meaningful subgraphs can be sought, but performance can be influenced both by the search algorithm, and, by the graph-weighting scheme and both merit rigorous investigation. In this paper, we focus on edge-weighting schemes for bipartite graphical representation of gene expression. Two novel methods are presented: the first is based on empirical evidence; the second on a geometric distribution. The schemes are compared for several real datasets, assessing efficiency of performance based on four essential properties: robustness to noise and missing values, discrimination, parameter influence on scheme efficiency and reusability. Recommendations and limitations are briefly discussed. Keywords: Edge-weighting; weighted graphs; gene expression; bi-clustering

Optimisation algorithms for microarray biclustering

In providing simultaneous information on expression profiles for thousands of genes, microarray technologies have, in recent years, been largely used to investigate mechanisms of gene expression. Clustering and classification of such data can, indeed, highlight patterns and provide insight on biological processes. A common approach is to consider genes and samples of microarray datasets as nodes in a bipartite graphs, where edges are weighted e.g. based on the expression levels. In this paper, using a previously-evaluated weighting scheme, we focus on search algorithms and evaluate, in the context of biclustering, several variations of Genetic Algorithms. We also introduce a new heuristic “Propagate”, which consists in recursively evaluating neighbour solutions with one more or one less active conditions. The results obtained on three well-known datasets show that, for a given weighting scheme,optimal or near-optimal solutions can be identified.

Crystal structures and hydrogen bonding in the proton transfer salts of nicotine with 3,5-dinitrosalicylic acid and 5-sulfosalicylic acid

The structures of the 1:1 anhydrous salts of nicotine (NIC) with 3,5-dinitrosalicylic acid (DNSA) and 5-sulfosalicylic acid (5-SSA), namely (1R,2S)-1-methyl-2-(3-pyridyl)-1H-pyrrolidin-1-ium 2-carboxy-4,6-dinitrophenolate, C10H15N2+ C7H3N2O7-, (I) and (1R,2S)-1-methyl-2-(3-pyridyl)-1H-pyrrolidin-1-ium 3-carboxy-4-hydroxybenzenesulfonate, C10H15N2+ C7H5O6S-, (II) are reported. The asymmetric units of both (I) and (II) comprise two independent nicotinium cations (C and D) and either two DNSA or two 5-SSA anions (A and B), respectively. One of the DNSA anions shows a 25% rotational disorder in the benzene ring system. In the crystal of (I), inter-unit pyrrolidinium N-H...N(pyridine) hydrogen bonds generate zigzag NIC cation chains which extend along a while the DNSA anions are not involved in any formal inter-species hydrogen bonding but instead form pi--pi associated stacks which parallel the NIC chains along a [ring centroid separation, 3.857(2)A]. Weak C-H...O interactions between chain substructures give an overall three-dimensional structure. With (II), A and B anions form independent zigzag chains with C and D cations, respectively, through carboxylic acid O-H...N(pyridine) hydrogen bonds. These chains, which extend along b are pseudo-centrosymmetrically related and give pi--pi interactions between the benzene rings of anions A and B and the pyridine rings of the NIC cations C and D, respectively [ring centroid separations, 3.6422(19) and 3.7117(19)A]. Present also are weak intermolecular C-H...O hydrogen-bonding interactions between the chains, giving an overall three-dimensional structure.

Intelligent collision avoidance, control and guidance

This paper reviews a variety of advanced signal processing algorithms that have been developed at the University of Southampton as part of the Prometheus (Programme for European traffic flow with highest efficiency and unprecedented safety) programme to achieve an intelligent driver warning system (IDWS). The IDWS includes the detection of road edges, lanes, obstacles and their tracking and identification, estimates of time to collision, and behavioural modelling of drivers for a variety of scenarios. The underlying algorithms are briefly discussed in support of the IDWS.

Test-retest reliability of graph theory measures of structural brain connectivity

The human connectome has recently become a popular research topic in neuroscience, and many new algorithms have been applied to analyze brain networks. In particular, network topology measures from graph theory have been adapted to analyze network efficiency and 'small-world' properties. While there has been a surge in the number of papers examining connectivity through graph theory, questions remain about its test-retest reliability (TRT). In particular, the reproducibility of structural connectivity measures has not been assessed. We examined the TRT of global connectivity measures generated from graph theory analyses of 17 young adults who underwent two high-angular resolution diffusion (HARDI) scans approximately 3 months apart. Of the measures assessed, modularity had the highest TRT, and it was stable across a range of sparsities (a thresholding parameter used to define which network edges are retained). These reliability measures underline the need to develop network descriptors that are robust to acquisition parameters.

Text segmentation in unconstrained hand-drawings in whiteboard photos

In this paper we present a robust method to detect handwritten text from unconstrained drawings on normal whiteboards. Unlike printed text on documents, free form handwritten text has no pattern in terms of size, orientation and font and it is often mixed with other drawings such as lines and shapes. Unlike handwritings on paper, handwritings on a normal whiteboard cannot be scanned so the detection has to be based on photos. Our work traces straight edges on photos of the whiteboard and builds graph representation of connected components. We use geometric properties such as edge density, graph density, aspect ratio and neighborhood similarity to differentiate handwritten text from other drawings. The experiment results show that our method achieves satisfactory precision and recall. Furthermore, the method is robust and efficient enough to be deployed in a mobile device. This is an important enabler of business applications that support whiteboard-centric visual meetings in enterprise scenarios. © 2012 IEEE.