Copper(II) Complexes of l-Arginine as Netropsin Mimics Showing DNA Cleavage Activity in Red Light

Copper(II) complexes [Cu(L-arg)(2)](NO3)(2) (1) and [Cu(L-arg)(B)Cl]Cl (2-5), where B is a heterocyclic base, namely, 2,2'-bipyridine (bpy, 2), 1,10-phenanthroline (phen, 3), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 4), and dipyrido[3,2-a:2',3'-c)phenazine (dppz, 5), are prepared and their DNA binding and photoinduced DNA cleavage activity studied. Ternary complex 3, structurally characterized using X-ray crystallography, shows a square-pyramidal (4 + 1) coordination geometry in which the N,O-donor L-arginine and N,N-donor 1,10-phenanthroline form the basal plane with one chloride at the elongated axial site. The complex has a pendant cationic guanidinium moiety. The one-electron paramagnetic complexes display a metal-centered d-d band in the range of 590-690 nm in aqueous DMF They show quasireversible cyclic voltammetric response due to the Cu(II)/Cu(I) couple in the range of -0.1 to -0.3 V versus a saturated calomel electrode in a DMF-Tris HCl buffer (pH 7.2). The DNA binding propensity of the complexes is studied using various techniques. Copper(II) bis-arginate 1 mimics the minor groove binder netropsin by showing preferential binding to the AT-rich sequence of double-strand (ds) DNA. DNA binding study using calf thymus DNA gives an order: 5 (L-arg-dppz) >= 1 (biS-L-arg) > 4 (L-arg-dpq) > 3 (L-arg-phen) >> 2 (L-arg-bpy). Molecular docking calculations reveal that the complexes bind through extensive hydrogen bonding and electrostatic interactions with ds-DNA. The complexes cleave supercoiled pUC19 DNA in the presence of 3-mercaptopropionic acid as a reducing agent forming hydroxyl ((OH)-O-center dot) radicals. The complexes show oxidative photoinduced DNA cleavage activity in UV-A light of 365 nm and red light of 647.1 nm (Ar-Kr mixed-gas-ion laser) in a metal-assisted photoexcitation process forming singlet oxygen (O-1(2)) species in a type-II pathway. All of the complexes, barring complex 2, show efficient DNA photocleavage activity. Complexes 4 and 5 exhibit significant double-strand breaks of DNA in red light of 647.1 nm due to the presence of two photosensitizers, namely, L-arginine and dpq or dppz in the molecules.

Photoinduced DNA and Protein Cleavage Activity of Ferrocene-Appended L-Methionine Reduced Schiff Base Copper(II) Complexes of Phenanthroline Bases

Ferrocene-appended ternary copper(H) complexes of phenanthroline bases having CuN3OS coordination with an axial Cu-S bond derived from L-methionine reduced Schiff base shows red light induced oxidative DNA cleavage activity following a hydroxyl radical pathway. The dipyridophenazine complex, in addition, displays photoinduced oxidative cleavage of bovine serum albumin protein in UV-A light.

XANES and EXAFS of copper compounds: Studies of copper carboxylates with metal-metal bonds and of the complex formed byPseudomonas aeruginosa

X-ray absorpion near edge structure (xanes) of copper compounds with copper in 1+, 2+ and 3+ states has been studied. Extended x-ray absorption fine structure (exafs) has been employed to determine bond distances and coordination numbers in several model copper compounds. Employing bothxanes andexafs, the structure of the copper complex formed by the micro-organismPseudomonas aeruginosa has been shown to be square-planar with the Cu-O distance close to that in cupric glucuronates and cupric acetylacetonate.exafs has been shown to be useful for studying metal-metal bonds in copper carboxylates.

Crystal structures of 1,4-diaza bicyclo[2.2.2.]octane and N,N-dimethyl formamide adducts of copper acetate

The crystal structures of copper acetate adducts with 1,4-diaza bicyclo [2.2.2.]octane and N,N-dimethyl formamide are shown to be dimeric with Cu---Cu distances of 2.633 Å and 2.616 Å respectively.

The nature of non-equilibrium solidification of undercooled Agsingle bondCu alloys in contact with primary copper dendrites

Liquids of silver-copper alloys with near eutectic compositions embedded in a copper matrix were undercooled. The structural and microstructural investigations of these alloys solidified from undercooled temperature indicated the absence of both the eutectic reaction and diffusionless transformation below the equal free energy curve (T0). Instead the liquid maintained local equilibrium with the copper dendrites continuously until it intersected the extended solidus of the silver rich solid solution.

Changing Lived Worlds of Contemporary Amazonian Native Young People : Manchineri Youths in the Reserve and the City, Brazil-Acre

This thesis discusses the contemporary construction of the lived worlds of indigenous Amazonian youths. Today’s native peoples are considerably affected by the processes of globalization and urbanization, which have led to new ways of relating to their cultural traditions. This work presents a case study of Manchineri youngsters aged between 14 and 24 years old living in Acre state in Brazilian Amazonia. The Arawak-speaking Manchineri number some 1,000 people; their legally demarcated reserve is situated next to the River Yaco. The research is based on ethnographic material collected in the Mamoadate reserve and in the state capital, Rio Branco. By comparing the youth in different physical and social environments (the reserve and the city), my attempt has been to search for the most typical elements maintained, altered and created in the current lived worlds of Manchineri youths. Fieldwork methods included interviews, participant observation, photographs, video recordings, and drawings. The material was analyzed within the multidisciplinary framework of the social and cultural construction of knowledge. The study applies the concepts of social field, symbolic capital, and habitus as they have been used by Pierre Bourdieu; perspective as developed recently in Amazonian ethnology; the sacred as a cultural category as understood in the study of religion; and individual and person as concepts central to anthropology and sociology. Additionally, the study can be contextualized within youth studies, Latin American studies, and urban studies. The results of the study show that the everyday lives of young Amazonian native people are formed by a complex mixture of ‘modernity’ and ‘tradition’, fragmentation, and transitions between different conceptual frameworks. Part II discusses the ethnographic material in depth and shows that indigenous adolescents act from a variety of social perspectives: the native youth’s own ethnic group, divided into sub-groups, especially into urban residents and those living in the reserve; ancestors, super-human agents and spirits; other indigenous groups and non-natives. Consequently, besides the traditional initiation ritual, we find various contemporary rites of passage to adulthood: state-education, learning traditional practices, shamanism, matrimony, and transitions between the reserve and urban areas. According to these results, new social roles, political organization, responsibilities, and in general the desire to be respected, require both ‘modern’ and ‘traditional’ abilities. In Part III, the study shows that the current power relations constituted by new social contacts, ethnic recognition, and cooperation with different institutions have resulted in the formation of new social fields: youth cultures, the ethnic group, shamanic practices, the ethnopolitical movement, and indigenous students. The capacity of young Amazonian Indians to act in contemporary social fields produces them as full persons. The study also argues that the elements of the lived worlds can be divided into these social fields. When focusing on these fields, it became evident that these comprise the strategies adopted by young Indians to break through social and cultural barriers.

Copper-doped mesoporous silica nanospheres, a promising immunomodulatory agent for inducing osteogenesis

The application of mesoporous silica nanospheres (MSNs) loaded with drugs/growth factors to induce osteogenic differentiation of stem cells has been trialed by a number of researchers recently. However, limitations such as high cost, complex fabrication and unintended side effects from supraphysiological concentrations of the drugs/growth factors represent major obstacles to any potential clinical application in the near term. In this study we reported an in situ one-pot synthesis strategy of MSNs doped with hypoxia-inducing copper ions and systematically evaluated the nanospheres by in vitro biological assessments. The Cu-containing mesoporous silica nanospheres (Cu-MSNs) had uniform spherical morphology (∼100 nm), ordered mesoporous channels (∼2 nm) and homogeneous Cu distribution. Cu-MSNs demonstrated sustained release of both silicon (Si) and Cu ions and controlled degradability. The Cu-MSNs were phagocytized by immune cells and appeared to modulate a favorable immune environment by initiating proper pro-inflammatory cytokines, inducing osteogenic/angiogenic factors and suppressing osteoclastogenic factors by the immune cells. The immune microenvironment induced by the Cu-MSNs led to robust osteogenic differentiation of bone mesenchymal stem cells (BMSCs) via the activation of Oncostation M (OSM) pathway. These results suggest that the novel Cu-MSNs could be used as an immunomodulatory agent with osteostimulatory capacity for bone regeneration/therapy application. Statement of significance In order to stimulate both osteogenesis and angiogenesis of stem cells for further bone regeneration, a new kind of hypoxia-inducing copper doped mesoporous silica nanospheres (Cu-MSNs) were prepared via one-pot synthesis. Biological assessments under immune environment which better reflect the in vivo response revealed that the nanospheres possessed osteostimulatory capacity and had potential as immunomodulatory agent for bone regeneration/therapy application. The strategy of introducing controllable amount of therapeutic ions instead of loading expensive drugs/growth factors in mesoporous silica nanosphere provides new options for bioactive nanomaterial functionalization.

Extent of dense native woodland and exotic weed infestation in the extensive grazing lands of the Upper Herbert and Upper Burdekin River Catchments of far north Queensland: results of a producer survey

The Mt Garnet Landcare Group commissioned a survey of landholders within the Upper Herbert and Upper Burdekin River Catchments to assess the density of native woodlands and to gauge the extent of exotic weed infestation. Twenty-four of 49 landholders responded, representing an area of nearly 500 000 ha or 47% of the total area. Dense native woodland covers 24% (>117 000 ha) of the area surveyed, while a further 30% (140 000 ha) supports moderately dense stands. The dense stands are largely confined to the highly fertile alluvial soils (26% dense woodland) and the lower fertility sandy-surfaced soils (33% or >96 000 ha). Moderate and dense infestations of exotic weeds, principally Lantana camara, occur on 54% (20 000 ha) of alluvial soils and on 13% of sandy-surfaced soils (39 000 ha), where praxelis (Praxelis clematidia) is the major weed. Basaltic soils have low levels of both dense woodland and exotic weed infestation. Some implications of the results are discussed.

Assessment of prey overlap between a native (Polistes humilis) and an introduced (Vespula germanica) social wasp using morphology and phylogenetic analyses of 16S rDNA

In newly invaded communities, interspecific competition is thought to play an important role in determining the success of the invader and its impact on the native community. In southern Australia, the native Polistes humilis was the predominant social wasp prior to the arrival of the exotic Vespula germanica (Hymenoptera: Vespidae). Both species forage for similar resources (water, pulp, carbohydrate and protein prey), and concerns have arisen about potential competition between them. The aim of this study was to identify the protein foods that these wasps feed on. As many prey items are masticated by these wasps to the degree that they cannot be identified using conventional means, morphological identification was complemented by sequencing fragments of the mitochondrial 16S rRNA gene. GenBank searches using blast and phylogenetic analyses were used to identify prey items to at least order level. The results were used to construct complete prey inventories for the two species. These indicate that while P. humilis is restricted to feeding on lepidopteran larvae, V. germanica collects a variety of prey of invertebrate and vertebrate origin. Calculated values of prey overlap between the two species are used to discuss the implications of V. germanica impacting on P. humilis. Results obtained are compared to those gained by solely 'conventional' methods, and the advantages of using DNA-based taxonomy in ecological studies are emphasized.

Influence of nitrogen based supplements on live weight, fertility and mortality of heifers grazing dry season native pasture

Supplements containing urea or biuret were fed in the dry season to yearling and two year old pregnant heifers grazing native spear grass pastures in north Queensland. Liveweight change and survival during the dry season and fertility in the following year were measured. In the first experiment during a relatively favourable dry season, supplementation significantly (P<0.01) reduced liveweight loss in yearling heifers (5 vs. 32 kg). In the following year during a drought, supplement significantly (P<.01) reduced liveweight loss in yearling heifers (32 vs. 41 kg) and significantly (P <0.01) reduced mortalities (23.5% vs. 5.2%) in pregnant and lactating heifers. The supplement had no significant effect on subsequent fertility in either experiment. 14th Biennial Conference.

Field evaluation of a plant activator, captan, chlorothalonil, copper hydroxide, iprodione, mancozeb and strobilurins for the control of citrus brown spot of mandarin

Brown spot (caused by Alternaria alternata) is a major disease of citrus in subtropical areas of Australia. A number of chemicals, the strobilurins azoxystrobin, trifloxystrobin, pyraclostrobin and methoxycrylate, a plant activator (acibenzolar), copper hydroxide, mancozeb, captan, iprodione and chlorothalonil/pyrimthanil were tested in the field for its control. Over three seasons, trees in a commercial orchard received 16, 14 and 7 fungicide sprays, respectively, commencing at flowering in the first season, and petal fall in the later seasons. In all experiments, the strobilurins used alone, or incorporated with copper and mancozeb, were as effective as, or better than the industry standard of copper and mancozeb alone. The only exception was trifloxystrobin, which when used alone was less effective than the industry standard. Acibenzolar used alone was ineffective. Applying a mixture of azoxystrobin and acibenzolar was found to reduce the incidence of brown spot compared with applying azoxystrobin alone but, in either case, disease levels were not found to be significantly different to the industry standard. Captan, iprodione and chlorothalonil/pyrimthanil were as effective as the industry standard. The incidence and severity of rind damage were significantly lowest in the azoxystrobin, methoxycrylate, iprodione and chlorothalonil/pyrimthanil treatments. Medium and high rates of trifloxystrobin (0.07 g/L, 0 .15 g/L) and pyraclostrobin (0.8 g/L, 1.2 g/L) applied alone were the only treatments found to be IPM-incompatible as shown by the elevated level of scale infection on fruit.

The risk of pollen-mediated gene flow from exotic Corymbia plantations into native Corymbia populations in Australia

Sectors of the forest plantation industry in Australia are set to expand in the near future using species or hybrids of the spotted gums (Corymbia, Section Politaria). Plantations of these taxa have already been introduced across temperate and subtropical Australia, representing locally exotic introductions from native stands in Queensland and New South Wales. A literature review was undertaken to provide insights into the potential for pollen-mediated gene flow from these plantations into native populations. Three factors suggest that such gene flow is likely; (1) interspecific hybridisation within the genus has frequently been recorded, including between distantly related species from different sections, (2) apparent high levels of vertebrate pollinator activity may result in plantation pollen being moved over hundreds of kilometres, (3) much of the plantation estate is being established among closely related taxa and therefore few barriers to gene flow are expected. Across Australia, 20 of the 100 native Corymbia taxa were found to have regional level co-occurrence with plantations. These were located most notably within regions of north-east New South Wales and south-east Queensland, however, co-occurrence was also found in south-west Western Australia and eastern Victoria. The native species found to have co-occurrence were then assessed for the presence of reproductive barriers at each step in the process of gene flow that may reduce the number of species at risk even further. The available data suggest three risk categories exist for Corymbia. The highest risk was for gene flow from plantations of spotted gums to native populations of spotted gums. This was based on the expected limited existence of pre- and post-zygotic barriers, substantial long-distance pollen dispersal and an apparent broad period of flowering in Corymbia citriodora subsp. variegata plantations. The following risk category focussed on gene flow from Corymbia torelliana × C. c. variegata hybrid plantations into native C. c. variegata, as the barriers associated with the production and establishment of F1 hybrids have been circumvented. For the lowest risk category, Corymbia plantations may present a risk to other non-spotted gum species, however, further investigation of the particular cross-combinations is required. A list of research directions is provided to better quantify these risks. Empirical data will need to be combined within a risk assessment framework that will not only estimate the likelihood of exotic gene flow, but also consider the conservation status/value of the native populations. In addition, the potential impacts of pollen flow from plantations will need to be weighed up against their various economic and environmental benefits.

Quambalaria species associated with plantation and native eucalypts in Australia

This study aimed to determine which species of Quambalaria are associated with shoot blight symptoms on Corymbia spp. An additional aim was to determine the presence and impact of quambalaria shoot blight on Eucalyptus species used in plantation development in subtropical and tropical regions of eastern Australia. Surveys identified three Quambalaria spp. -Q. pitereka, Q. eucalypti and Q. cyanescens - from native and plantation eucalypts, as well as amenity plantings, including the first confirmed report of Q. eucalypti from Eucalyptus plantations in Australia. Symptom descriptions and morphological studies were coupled with phylogenetic studies using ITS rDNA sequence data. Quambalaria pitereka was the causal agent of blight symptoms on species and hybrids in the Corymbia complex. Quambalaria eucalypti was identified from Eucalyptus species and a single Corymbia hybrid. Quambalaria cyanescens was detected from native and plantation Corymbia spp.

The original native pasture ecosystems of the eastern and western Darling Downs - Can they be restored?

The original pasture ecosystems of southern inland Queensland ranged from treeless grasslands on cracking clays through grassy woodlands of varying density on a great range of soil types to those competing at the dynamic edges of forests and scrubs. Fire, both wild and aboriginal-managed, was a major factor, along with rainfall extremes, in shaping the pastures and tree:grass balance. Seedling recruitment was driven by rainfall extremes, availability of germinable seed and growing space, with seed availability and space being linked to the timing and intensity of recent fires and rain. The impact of insects, diseases, severe wind and hailstorms on recruitment should not be underestimated. The more fertile soils had denser grass growth, greater fire frequency and thinner tree cover than infertile soils, except where trees were so dense that grass growth was almost eliminated. The pastures were dominated by perennial tussock grasses of mid-height but included a wide array of minor herbaceous species whose abundance was linked to soil type and recent seasonal conditions. Many were strongly perennial with Asteraceae, Fabaceae, Malvaceae, Cyperaceae and Goodeniaceae most common in an environment, which can experience effective rainfall at any time of year. The former grassland communities that are now productive farming lands are not easily returned to their original composition. However, conservation of remnant examples of original pasture types is very achievable provided tree density is controlled, prescribed burning and grazing are used and rigorous control of invasive, exotic species is undertaken. This should be done with a clear understanding that significant short-and medium-term fluctuations in botanical composition are normal.