Vertically-aligned graphene flakes on nanoporous templates: morphology, thickness, and defect level control by pre-treatment

Various morphologies of the vertically-aligned graphene flakes were fabricated on the nanoporous templates treated with metal ions in solutions, as well as coated with a thin gold layer and activated in the low-temperature Ar plasma. The thickness and level of structural defects in the graphene flakes could be effectively controlled by a proper selection of the pre-treatment method. We have also demonstrated that various combinations of the flake thickness and defect levels can be obtained, and the morphology and density of the graphene pattern can be effectively controlled. The result obtained could be of interest for various applications requiring fabrication of large graphene networks with controllable properties.

Inducing nonlocal reactions with a local probe

The scanning tunneling microscope (STM) has evolved continually since its invention, as scientists have expanded its use to encompass atomic-scale manipulation, momentum-resolved electronic characterization, localized chemical reactions (bond breaking and bond making) in adsorbed molecules, and even chain reactions at surfaces. This burgeoning field has recently expanded to include the use of the STM to inject hot electrons into substrate surface states; the injected electrons can travel laterally and induce changes in chemical structure in molecules located up to 100 nm from the STM tip. We describe several key demonstrations of this phenomenon, including one appearing in this issue of ACS Nano by Chen et al. Possible applications for this technique are also discussed, including characterizing the dispersion of molecule−substrate interface states and the controlled patterning of molecular overlayers.

Photoinduced DNA and Protein Cleavage Activity of Ferrocene-Conjugated Ternary Copper(II) Complexes

Ferrocene-conjugated ternary copper(II) complexes [Cu(L)(B)](ClO4)(2), where L is FcCH(2)N(CH2Py)(2) (Fc = (eta(5)-C5H4)Fe-II(eta(5)-C5H5)) and B is a phenanthroline base, viz., 2,2'-bipyridine (bpy, 1), 1, 10-phenanthroline (phen, 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 3), and dipyrido[3,2-a:2',3'-c]phenazine (dppz, 4), have been synthesized and characterized by various spectroscopic and analytical techniques. The bpy complex 1, as its hexafluorophosphate salt, has been structurally characterized by X-ray crystallography. The molecular structure shows the copper(II) center having an essentially square-pyramidal coordination geometry in which L with a pendant ferrocenyl (Fc) moiety and bpy show respective tridentate and bidentate modes of binding to the metal center. The complexes are redox active, showing a reversible cyclic voltammetric response of the Fc(+)-Fc couple near 0.5 V vs SCE and a quasi-reversible Cu(II)-Cu(I) couple near 0.0 V. Complexes 2-4 show binding affinity to calf thymus (CT) DNA, giving binding constant (K-b) values in the range of 4.2 x 10(4) to 2.5 x 10(5) M-1. Thermal denaturation and viscometric titration data suggest groove binding and/or a partial intercalative mode of binding of the complexes to CT DNA. The complexes show good binding propensity to the bovine serum albumin (BSA) protein, giving K-BSA values of similar to 10(4) M-1 for the bpy and phen complexes and similar to 10(5) M-1 for the dpq and dppz complexes. Complexes 2-4 exhibit efficient chemical nuclease activity in the presence of 3-mercapto-propionic acid (MPA) as a reducing agent or hydrogen peroxide (H2O2) as an oxidizing agent. Mechanistic studies reveal formation of hydroxyl radicals as the reactive species. The dpq and dppz complexes are active in cleaving supercoiled (SC) pUC19 DNA on photoexposure to visible light of different wavelengths including red light using an argon-krypton mixed gas ion laser. Mechanistic investigations using various inhibitors reveal the fort-nation of hydroxyl radicals in the DNA photocleavage reactions. The dppz complex 4, which shows efficient photoioduced BSA cleavage activity, is a potent multifunctional model nuclease and protease in the chemistry of photodynamic therapy (PDT) of cancer.

Hydrogen and fluorine in crystal engineering: systematics from crystallographic studies of hydrogen bonded tartrate-amine complexes and fluoro-substituted coumarins, styrylcoumarins and butadienes

Three aspects of crystal engineering in molecular crystals are presented to emphasize the role of intermolecular interactions and factors influencing crystal packing. Hydrogen bonded tartrate-amine complexes have been analyzed with the propensity for formation of multidirectional hydrogen bonding as a key design element in the generation of materials for second harmonic generation (SHG). The invariance of the framework in DBT and its possible implications on SHG is outlined. The role of Fluorine in orienting molecules of coumarins, styrylcoumarins and butadienes for photodimerization is described with particular emphasis on its steering capability. Usage of coumarin as an design element for the generation of polymorphs of substituted styrylcoumarins is examined with specific examples.

A Touch of Red : Archaeological and Ethnographic Approaches to Interpreting Finnish Rock Paintings

Approximately 125 prehistoric rock paintings have been found in the modern territory of Finland. The paintings were done with red ochre and are almost without exception located on steep lakeshore cliffs associated with ancient water routes. Most of the sites are found in the central and eastern parts of the country, especially on the shores of Lakes Päijänne and Saimaa. Using shore displacement chronology, the art has been dated to ca. 5000 – 1500 BC. It was thus created mainly during the Stone Age and can be associated with the so-called ‘Comb Ware’ cultures of the Subneolithic period. The range of motifs is rather limited, consisting mainly of schematic depictions of stick-figure humans, elks, boats, handprints and geometric signs. Few paintings include any evidence of narrative scenes, making their interpretation a rather difficult task. In Finnish archaeological literature, the paintings have traditionally been associated with ’sympathetic’ hunting magic, or the belief that the ritual shooting of the painted animals would increase hunting luck. Some writers have also suggested totemistic and shamanistic readings of the art. This dissertation is a critical review of the interpretations offered of Finnish rock art and an exploration of the potentials of archaeological and ethnographic research in increasing our knowledge of its meaning. Methods used include ’formal’ approaches such as archaeological excavation, landscape analysis and the application of neuropsychological research to the study of rock art, as well as ethnographically ’informed’ approaches that make use of Saami and Baltic Finnish ethnohistorical sources in interpretation. In conclusion, it is argued that although North European hunter-gatherer rock art is often thought to lie beyond the reach of ‘informed’ knowledge, the exceptional continuity of prehistoric settlement in Finland validates the informed approach in the interpretation of Finnish rock paintings. The art can be confidently associated with shamanism of the kind still practiced by the Saami of Northern Fennoscandia in the historical period. Evidence of similar shamanistic practices, concepts and cosmology are also found in traditional Finnish-Karelian epic poetry. Previous readings of the art based on ‘hunting magic’ and totemism are rejected. Most of the paintings appear to depict experiences of falling into a trance, of shamanic metamorphosis and trance journeys, and of ‘spirit helper’ beings comparable to those employed by the Saami shaman (noaidi). As demonstrated by the results of an excavation at the rock painting of Valkeisaari, the painted cliffs themselves find a close parallel in the Saami cult of the 'sieidi', or sacred cliffs and boulders worshipped as expressing a supernatural power. Like the Saami, the prehistoric inhabitants of the Finnish Lake Region seem to have believed that certain cliffs were ’alive’ and inhabited by the spirit helpers of the shaman. The rock paintings can thus be associated with shamanic vision quests, and the making of ‘art’ with an effort to socialize the other members of the community, especially the ritual specialists, with trance visions. However, the paintings were not merely to be looked at. The red ochre handprints pressed on images of elks, as well as the fact that many paintings appear ’smeared’, indicate that they were also to be touched – perhaps in order to tap into the supernatural potency inherent in the cliff and in the paintings of spirit animals.

Changes in Beer Labels and their Meaning : A Holistic Approach to the Semiosic Process

The purpose of this study is to find a framework for a holistic approach to, and form a conceptual toolbox for, investigating changes in signs and in their interpretation. Charles S. Peirce s theory of signs in a communicative perspective is taken as a basis for the framework. The concern directing the study is the problem of a missing framework in analysing signs of visual artefacts from a holistic perspective as well as that of the missing conceptual tools. To discover the possibility of such a holistic approach to semiosic processes and to form a conceptual toolbox the following issues are discussed: i) how the many Objects with two aspects involved in Peirce s definition of sign-action, promote multiple semiosis arising from the same sign by the same Interpretant depending on the domination of the Objects; ii) in which way can the relation of the individual and society or group be made more apparent in the construction of the self since this construction is intertwined with the process of meaning-creation and interpretation; iii) how to account for the fundamental role of emotions in semiosis, and the relation of emotions with the often neglected topic of embodiment; iv) how to take into account the dynamic, mediating and processual nature of sign-action in analysing and understanding the changes in signs and in the interpretation of signs. An interdisciplinary approach is chosen for this dissertation. Concepts that developed within social psychology, developmental psychology, neurosciences and semiotics, are discussed. The common aspect of the approaches is that they in one way or another concentrate on mediation provided by signs in explaining human activity and cognition. The holistic approach and conceptual toolbox found are employed in a case study. This consists of an analysis of beer brands including a comparison of brands from two different cultures. It becomes clear that different theories and approaches have mutual affinities and do complement each other. In addition, the affinities in different disciplines somewhat provide credence to the various views. From the combined approach described, it becomes apparent that by the semiosic process, the emerging semiotic self intertwined with the Umwelt, including emotions, can be described. Seeing the interpretation and meaning-making through semiosis allows for the analysis of groups, taking into account the embodied and emotional component. It is concluded that emotions have a crucial role in all human activity, including so-called reflective thinking, and that emotions and embodiment should be consciously taken into account in analysing signs, the interpretation, and in changes of signs and interpretations from both the social and individual level. The analysis of the beer labels expresses well the intertwined nature of the relationship between signs, individual consumers and society. Many direct influences from society on the label design are found, and also some indirect attitude changes that become apparent from magazines, company reports, etc. In addition, the analysis brings up the issues of the unifying tendency of the visual artefacts of different cultures, but also demonstrates that the visual artefacts are able to hold the local signs and meanings, and sometimes are able to represent the local meanings although the signs have changed in the unifying process.

Why are students choosing STEM and when do they make their choice?

BACKGROUND OR CONTEXT The higher education sector plays an important role in encouraging students into the STEM pipeline through fostering partnerships with schools, building on universities long tradition in engagement and outreach to secondary schools. Numerous activities focus on integrated STEM learning experiences aimed at developing conceptual scientific and mathematical knowledge with opportunities for students to show and develop skills in working with each other and actively engaging in discussion, decision making and collaborative problem solving. (NAS, 2013; AIG, 2015; OCS, 2014). This highlights the importance of the development and delivery of engaging integrated STEM activities connected to the curriculum to inspire the next generation of scientists and engineers and generally preparing students for post-secondary success. The broad research objective is to gain insight into which engagement activities and to what level they influence secondary school students’ selection of STEM-related career choices at universities. PURPOSE OR GOAL To evaluate and determine the effectiveness of STEM engagement activities impacting student decision making in choosing a STEM-related degree choice at university. APPROACH A survey was conducted with first-year domestic students studying STEM-related fieldswithin the Science and Engineering Faculty at Queensland University of Technology. Of the domestic students commencing in 2015, 29% responded to the survey. The survey was conducted using Survey Monkey and included a variety of questions ranging from academic performance at school to inspiration for choosing a STEM degree. Responses were analysed on a range of factors to evaluate the influence on students’ decisions to study STEM and whether STEM high school engagement activities impacted these decisions. To achieve this the timing of decision making for students choice in study area, degree, and university is compared with the timing of STEM engagement activities. DISCUSSION Statistical analysis using SPSS was carried out on survey data looking at reasons for choosing STEM degrees in terms of gender, academic performance and major influencers in their decision making. It was found that students choose their university courses based on what subjects they enjoyed and exceled at in school. These results found a high correlation between enjoyment of a school subject and their interest in pursuing this subject at university and beyond. Survey results indicated students are heavily influenced by their subject teachers and parents in their choice of STEM-related disciplines. In terms of career choice and when students make their decision, 60% have decided on a broad area of study by year 10, whilst only 15% had decided on a specific course and 10% had decided on which university. The timing of secondary STEM engagement activities is seen as a critical influence on choosing STEM disciplines or selection of senior school subjects with 80% deciding on specific degree between year 11 and 12 and 73% making a decision on which university in year 12. RECOMMENDATIONS/IMPLICATIONS/CONCLUSION Although the data does not support that STEM engagement activities increase the likelihood of STEM-related degree choice, the evidence suggests the students who have participated in STEM activities associate their experiences with their choice to pursue a STEM-related course. It is important for universities to continue to provide quality engaging and inspirational learning experiences in STEM, to identify and build on students’ early interest and engagement, increase STEM knowledge and awareness, engage them in interdisciplinary project-based STEM practices, and provide them with real-world application experiences to sustain their interest.

Adsorption Of Methanol On The Surfaces Of Copper-Alloys - Ups And Eels Studies

Methanol adsorbs molecularly on the surfaces of Cu–Pd alloys at low temperatures and transforms to CH3O or CO on warming, depending upon the alloy composition. On oxygen presorbed Cu–Pd alloy surfaces, adsorption of methanol gives rise to H2O and H2CO. CH3OH adsorbed molecularly on the surfaces of Cu–Au alloys and CH3O is formed only at relatively high temperatures.

Characterisation of sweetpotato from Papua New Guinea and Australia: Physicochemical, pasting and gelatinisation properties.

The physicochemical and functional properties of flours from 25 Papua New Guinean and Australian sweetpotato cultivars were evaluated. The cultivars (white-, orange-, cream-, and purple-fleshed, and with dry matter, from 15 to 28 g/100 g), were obovate, oblong, elliptic, curved, irregular in shape, and essentially thin-cortexed (1-2 mm). Flour yield was less than 90 g/100 g solids, while starch, protein, amylose, water absorption and solubility indices, as well as total sugars, varied significantly (p < 0.05). Potassium, sodium, calcium, and phosphorus were the major minerals measured, and there were differences in the pasting properties, which showed four classes of shear-thinning and shear-thickening behaviours. Differential scanning calorimetry showed single-stage gelatinisation behaviour, with cultivar-dependent temperatures (61-84 degrees C) and enthalpies (12-27 J/g dry starch). Oval-, round- and angular-shaped granules were observed with a scanning electron microscope, while X-ray diffraction revealed an A-type diffraction pattern in the cultivars, with about 30% crystallinity. This study shows a wide range of sweetpotato properties, reported for the first time.

Hybrid Materials Combining Photoactive 2,3-Didecyloxy Anthracene Physical Gels and Gold Nanoparticles

Organic/inorganic hybrid gels have been developed in order to control the three-dimensional structure of photoactive nanofibers and metallic nanoparticles (NPs). These materials are prepared by simultaneous self-assembly of the 2,3-didecyloxyanthracene (DDOA) gelator and of thiol-capped gold nanoparticles (AuNPs). TEM and fluorescence measurements show that alkane-thiol capped AuNPs are homogeneously dispersed and tightly attached to the thermoreversible fibrillar network formed by the organogelator in n-butanol or n-decanol. Rheology and thermal stability measurements reveal moreover that the mechanical and thermal stabilities of the DDOA organogels are not significantly altered and that they remain strong, viscoelastic materials. The hybrid materials display a variable absorbance in the visible range because of the AuNPs, whereas the strong luminescence of the DDOA nanofibers is efficiently quenched by micromolar amounts of AuNPs. Besides, we obtained hybrid aerogels using supercritical CO2. These arc very low-density porous materials showing fibrillar networks oil which fluorinated gold NPs arc dispersed. These hybrid materials are of high interest because of their tunable optical properties and are under investigation for efficient light scattering.

Controlling plant and fruit diseases in strawberry fields

Grey mould, powdery mildew and stem-end rot are major diseases affecting the strawberry industry. Some of the chemicals used are ineffective under wet weather, have limits to the number of applications allowed in a season or may become ineffective in the long-term because of the development of resistance in the fungi. We will assess the effectiveness of the chemicals currently used by the strawberry industry and whether the fruit rot fungi are resistant to these fungicides. We will screen other chemicals that are used to control these diseases in related crops. We will also evaluate new chemicals in collaboration with the crop protectant industry. We will also undertake similar work to control nematodes in strawberry fields.

High-level coordination and strategy in the 2007 equine influenza outbreak response.

The equine influenza (EI) outbreak presented many challenges that required high-level coordination and decision making, as well as the development of new approaches for satisfactory and consistent resolution. This paper outlines the elements of the national coordination arrangements, preparatory arrangements in place prior to the outbreak that facilitated national coordination, and some of the issues faced and resolved in the response.

Measuring route passenger load diversity for capacity and quality of service assessment

This paper develops theory that quantifies transit route passenger-relative load factor and distinguishes it from occupancy load factor. The ratio between these measures is defined as the load diversity coefficient, which as a single measure characterizes the diversity of passenger load factor between route segments according to the origin-destination profile. The relationship between load diversity coefficient and route coefficient of variation in occupancy load factor is quantified. Two tables are provided that enhance passenger capacity and quality of service (QoS) assessment regarding onboard passenger load. The first expresses the transit operator’s perspective of load diversity and the passengers’ perspective of load factor relative to the operator’s, across six service levels corresponding to ranges of coefficient of variation in occupancy load factor. The second interprets the relationships between passenger average travel time and each of passenger-relative load factor and occupancy load factor. The application of this methodology is illustrated using a case study of a premium radial bus route in Brisbane, Australia. The methodology can assist in benchmarking and decision making regarding route and schedule design. Future research will apply value of time to QoS measurement, reflecting perceived passenger comfort through crowding and average time spent aboard. This would also assist in transit service quality econometric modeling.

Agroforestry systems for sustainable livelihoods and improved land management in the East Usambara Mountains, Tanzania

Forest destruction for agriculture continues to be a major threat to the rich biological diversity in the East Usambara Mountains in the north-eastern corner of Tanzania. The highest ratio of endemic plant and animal species found on 100 km2 anywhere in the world is depending on the remaining natural forests. Forests are vitally important for the local population in many different ways, and nationally they are an important source of water and hydroelectricity. The soils, of low fertility and mostly acidic Ferrasols, mainly have the nutrients in the topsoil. After clear-cutting, the soils soon become poor when the topsoil is eroded. High-value cardamom is nowadays unsustainably cultivated in the natural forests of the East Usambaras. The general aim was to study the possibilities to develop new profitable and sustainable agroforestry systems for the benefit of the local people that could contribute to relieving the pressure on the remaining natural forests in the East Usambara Mountains. Results from a spice crop agroforestry trial, established in cooperation with a local farmer, showed a clear advantage of intercropping cardamom (Elettaria cardamomum) and black pepper (Piper nigrum) with trees, especially with Grevillea robusta. The nitrogen fixing tree species Gliricidia sepium also improved the nitrogen and organic matter content of the soil over levels found in the natural forest. With improved agroforestry methods for spice production the households generated as much as13 times the net income obtained with traditional forest cultivation practices. There are thus sustainable and profitable ways to cultivate spices as cash crops in well-managed homegardens. However, the farmers need stable markets, access to credit and comprehensive extension services. The soil fertility depletion should be reversed with organic manure application and an enabling policy environment for the smallholder-farming sector. Strong farmers organisations and equal rights to resources and decision-making are needed. Organic spices have an increasing demand, and their export would be profitable for these farmers. What is, however, most needed for a change is a political will of a government that understands the importance of agricultural and forestry development for poverty reduction.