Electrochemical Control of the Time-Dependent Intensity Fluctuations in Surface-Enhanced Raman Scattering (SERS)

Time-dependent fluctuations in surface-enhanced Raman scattering (SERS) intensities were recorded from a roughened silver electrode immersed in diluted solutions of rhodamine 6G (R6G) and congo red (CR). These fluctuations were attributed to a small number of SERS-active molecules probing regions of extremely high electromagnetic field (hot spots) at the nanostructured surface. The time-dependent distribution of SERS intensities followed a tailed statistics at certain applied potentials, which has been linked to single-molecule dynamics. The shape of the distribution was reversibly tuned by the applied voltage. Mixtures of both dyes, R6G and CR, at low concentrations were also investigated. Since R6G is a cationic dye and CR is an anionic dye, the statistics of the SERS intensity distribution of either dye in a mixture were independently controlled by adjusting the applied potential. The potential-controlled distribution of SERS intensities was interpreted by considering the modulation of the surface coverage of the adsorbed dye by the interfacial electric field. This interpretation was supported by a two-dimensional Monte Carlo simulation that took into account the time evolution of the surface configuration of the adsorbed species and their probability to populate a hypothetical hot spot. The potential-controlled SERS dynamics reported here is a first step toward the spectroelectrochemical investigation of redox processes at the single-molecule level by SERS.

Molecular masses and sedimentation coefficients of extracellular hemoglobin of Glossoscolex paulistus: Alkaline oligomeric dissociation

The giant extracellular hemoglobin of Glossoscolex paulistus (HbGp) has a molecular mass (M) of 3600 +/- 100 kDa and a standard sedimentation coefficient (s(20.w)(0)) of 58 S. estimated by analytical ultracentrifugation (AUC). In the present work, further AUC studies were developed for HbGp, at pH 10.0, which favors oligomeric dissociation into lower M species. The HbGp oligomer is formed by globin chains a, b, c and d plus the linker chains. The pure monomeric fraction, subunit d, and HbGp at pH 10.0, in the presence of beta-mercaptoethanol, were also studied. Our results indicate that for samples of pure subunit d, besides the monomeric species with s(20.w)(0) of 2.0 S, formation of dimer of subunit d is observed with s(20.w)(0) of around 2.9 S. For the whole HbGp at pH 10.0 contributions from monomers, trimers and linkers are observed. No contribution from 58 S species was observed for the sample of oxy-HbGp at pH 10.0, showing its complete dissociation. For cyanomet-HbGp form a contribution of 17% is observed for the un-dissociated oligomer, consistent with data from other techniques that show the cyanomet-form is more stable as compared to oxy-HbGp. Masses of HbGp subunits, especially trimer abc and monomeric chains a, b, c and d, were also estimated from sedimentation equilibrium data, and are in agreement with the results from MALDI-TOF-MS. (C) 2010 Elsevier B.V. All rights reserved.

On the molecular mass of the extracellular hemoglobin of Glossoscolex paulistus: Analytical ultracentrifugation reexamination

The giant extracellular hemoglobin of Glossoscolex paulistus (HbGp) is constituted by Subunits containing heme groups with molecular masses (M) in the range of 15 to 19 kDa, monomers of 16 kDa (d), and trimers of 51 to 52 kDa (abc) linked by nonheme structures named linkers of 24 to 32 kDa (L). HbGp is homologous to Lumbricus terrestris hemoglobin (HbLt). Several reports propose M of HbLt in the range of 3.6 to 4.4 MDa. Based on subunits M determined by mass spectrometry and assuming HbGp stoichiometry of 12(abcd)(3)L(3) (Vinogradov model) plus 144 heme groups, a Value of M for HbGp oligomer of 3560 kDa can be predicted. This Value is nearly 500 kDa higher than the unique HbGp M Value reported in the literature. In the current work, sedimentation velocity analytical ultracentrifugation (AUC) experiments were performed to obtain M for HbGp in oxy and cyano-met forms. s(20,w)(0), values of 58.1 +/- 0.2 S and 59.6 +/- 0.2 S, respectively, for the two oxidation forms were obtained. The ratio between sedimentation and diffusion coefficients supplied values for M of approximately 3600 100 and 3700 100 kDa for oxy and cyano-met HbGp forms, respectively. An independent determination of the partial specific volume, V(bar), for HbGp was performed based on density measurements, providing a value of 0.764 +/- 0.008, in excellent agreement with the estimates from SEDFIT software. Our results show total consistency between M obtained by AUC and recent partial characterization by mass spectrometry. Therefore, HbGp possesses M very close to that of HbLt, suggesting an oligomeric assembly in agreement with the Vinogradov model. (c) 2008 Elsevier Inc. All rights reserved.

Cadmium, copper, mercury, and zinc concentrations in tissues of the King Crab (Pseudocarcinus gigas) from southeast Australian waters

The concentrations of cadmium, copper, mercury, and zinc were determined in muscle (body, claw, and leg), hepatopancreas, and gill tissues of Pseudocarcinus gigas, an exceptionally large, long-lived, and deep-dwelling crab species. The accumulation patterns observed are discussed in terms of both intra- and interspecies variations, with particular attention to the possible consequences of the extreme size and depth range of P. gigas. Metal concentrations did not depend significantly on sex of the crab. Significant differences between tissues were detected for all metals, and the distribution of metal between the tissues was different for each metal. Significant correlations were found between metal concentrations in the various tissues and crab size, and these are discussed and rationalised. The concentrations of mercury and zinc in muscle tissue increased with crab size and were high compared to other crab species. The concentrations of cadmium and copper present in edible tissues were not especially high compared to other crab species, but the concentration of cadmium in the hepatopancreas is of dietary concern.

Complete mitochondrial DNA sequences of the decapod crustaceans pseudocarcinus gigas (Menippidae) and macrobrachium rosenbergii (Palaemonidae)

The complete mitochondrial DNA sequence was determined for the Australian giant crab Pseudocarcinns gigas (Crustacea: Decapoda: Menippidae) and the giant freshwater shrimp Macrobrachium rosenbergii (Crustacea: Decapoda: Palaemonidae). The Pse gigas and Mrosenbergii mitochondrial genomes are circular molecules, 15,515 and 15,772 bp in length, respectively, and have the same gene composition as found in other metazoans. The gene arrangement of M. rosenbergii corresponds with that of the presumed ancestral arthropod gene order, represented by Limulus polyphemus, except for the position of the tRNA^Leu(UUR) gene. The Pse. gigas gene arrangement corresponds exactly with that reported for another brachyuran, Portunus trituberculatus, and differs from the M. rosenbergii gene order by only the position of the tRNA^His gene. Given the relative positions of intergenic nonoding nucleotides, the “duplication/random loss” model appears to be the most plausible mechanism for the translocation of this gene. These data represent the first caridean and only the second brachyuran complete mtDNA sequences, and a source of information that will facilitate surveys of intraspecific variation within these commercially important decapod species.

Culture-based fisheries in non-perennial reservoirs in Sri Lanka: production and relative performance of stocked species

In Sri Lanka, there is a great potential for the development of culture-based fisheries because of the availability of around 12 000 non-perennial reservoirs in the dry zone (<187 cm annual rainfall) of the island. These reservoirs fill during the north-east monsoonal period in October to December and almost completely dry up during August to October. As these non-perennial reservoirs are highly productive, hatchery-reared fish fingerlings can be stocked to develop culture-based fisheries during the water retention period of 7–9 months. The present study was conducted in 32 non-perennial reservoirs in five administrative districts in Sri Lanka. These reservoirs were stocked with fingerlings of Indian (catla Catla catla Hamilton and rohu Labeo rohita Hamilton) and Chinese (bighead carp Aristichthys nobilis Richardson) major carps, common carp Cyprinus carpio L., genetically improved farmed tilapia (GIFT) strain of Nile tilapia, Oreochromis niloticus (L.) and post-larvae of giant freshwater prawn, Macrobrachium rosenbergii De Man, at three different species combinations and overall stocking densities (SD) ranging from 218 to 3902 fingerlings ha⁻¹, during the 2002–2003 culture cycle. Of the 32 reservoirs stocked, reliable data on harvest were obtained from 25 reservoirs. Fish yield ranged from 53 to 1801 kg ha⁻¹ and the yields of non-perennial reservoirs in southern region were significantly (P < 0.05) higher than those in the northern region. Naturally-recruited snakehead species contributed the catches in northern reservoirs. Fish yield was curvilinearly related to reservoir area (P < 0.05), and a negative second order relationship was evident between SD and yield (P < 0.05). Chlorophyll-a and fish yield exhibited a positive second order relationship (P < 0.01). Bighead carp yield impacted positively on the total yield (P < 0.05), whereas snakehead yield impact was negative. Bighead carp, common carp and rohu appear suitable for poly-culture in non-perennial reservoirs. GIFT strain O. niloticus had the lowest specific growth rate among stocked species and freshwater prawn had a low return.

Surface behaviour and lipid interaction of Alzheimer beta-amyloid peptide 1-42: a membrane-disrupting peptide

Amyloid aggregates, found in patients that suffer from Alzheimer's disease, are composed of fibril-forming peptides in a β-sheet conformation. One of the most abundant components in amyloid aggregates is the β-amyloid peptide 1–42 (Aβ 1–42). Membrane alterations may proceed to cell death by either an oxidative stress mechanism, caused by the peptide and synergized by transition metal ions, or through formation of ion channels by peptide interfacial self-aggregation. Here we demonstrate that Langmuir films of Aβ 1–42, either in pure form or mixed with lipids, develop stable monomolecular arrays with a high surface stability. By using micropipette aspiration technique and confocal microscopy we show that Aβ 1–42 induces a strong membrane destabilization in giant unilamellar vesicles composed of palmitoyloleoyl-phosphatidylcholine, sphingomyelin, and cholesterol, lowering the critical tension of vesicle rupture. Additionally, Aβ 1–42 triggers the induction of a sequential leakage of low- and high-molecular-weight markers trapped inside the giant unilamellar vesicles, but preserving the vesicle shape. Consequently, the Aβ 1–42 sequence confers particular molecular properties to the peptide that, in turn, influence supramolecular properties associated to membranes that may result in toxicity, including: 1), an ability of the peptide to strongly associate with the membrane; 2), a reduction of lateral membrane cohesive forces; and 3), a capacity to break the transbilayer gradient and puncture sealed vesicles.

Mid-Holocene vertebrate bone Concentration-Lagerstätte on oceanic island Mauritius provides a window into the ecosystem of the dodo (Raphus cucullatus)

Although the recent history of human colonisation and impact on Mauritius is well documented, virtually no records of the pre-human native ecosystem exist, making it difficult to assess the magnitude of the changes brought about by human settlement. Here, we describe a 4000-year-old fossil bed at Mare aux Songes (MAS) in south-eastern Mauritius that contains both macrofossils (vertebrate fauna, gastropods, insects and flora) and microfossils (diatoms, pollen, spores and phytoliths). With >250 bone fragments/m2 and comprising 50% of all known extinct and extant vertebrate species (ns = 44) of Mauritius, MAS may constitute the first Holocene vertebrate bone Concentration-Lagerstätte identified on an oceanic volcanic island. Fossil remains are dominated by extinct giant tortoises Cylindraspis spp. (63%), passerines (10%), small bats (7.8%) and dodo Raphus cucullatus (7.1%). Twelve radiocarbon ages [four of them duplicates] from bones and other material suggest that accumulation of fossils took place within several centuries. An exceptional combination of abiotic conditions led to preservation of bones, bone collagen, plant tissue and microfossils. Although bone collagen is well preserved, DNA from dodo and other Mauritian vertebrates has proved difficult. Our analysis suggests that from ca 4000 years ago (4 ka), rising sea levels created a freshwater lake at MAS, generating an oasis in an otherwise dry environment which attracted a diverse vertebrate fauna. Subsequent aridification in the south-west Indian Ocean region may have increased carcass accumulation during droughts, contributing to the exceptionally high fossil concentration. The abundance of floral and faunal remains in this Lagerstätte offers a unique opportunity to reconstruct a pre-human ecosystem on an oceanic island, providing a key foundation for assessing the vulnerability of island ecosystems to human impact.

Are Chinese firms innovative or imitative?

In recent time, many Chinese firms have not only operated quite successfully at their home front, competing with those giant multinational companies inside China, they are also moving offshore. The short internationalisation process of Chinese firms looks both sudden and unexpected, causing many to wonder the success factors for Chinese firms. A dynamic innovation that combines strategic, organisational, cost as well as technological change was believed to have contributed to the fast growing Chinese firms in the global stage. This paper reviews the literature related to these areas of innovation. It also discusses reasons for firms to innovate or imitate, using institutional perspective and resource-based view (RBV). Intertwined with these discuss ion, empirical studies of innovative performance among Chinese firms are also analysed. The results show that in fact most Chinese firms still follow an imitative strategy, but there is a clear evidence of strategic cost innovation widely practiced among Chinese firms.

Cultural destruction and identity politics : targeting the history of Iraq

Since its inception in 1921, a number of successive regimes have sought to politicize Iraq‟s cultural history in order to develop national identity and foster social cohesion across this rich and complex nation. Foremost among these were the Baath party, particularly under the rule of Saddam Hussein, who used much of the nation‟s Oil wealth to undergo an extensive nation-building campaign. However, identity in Iraq is far from monolithic and various factions have long resisted the state sanctioned version of “Iraqi” identity and asserted alternative histories and narratives to underpin their own identity politics. With the invasion of Iraq by Coalition forces in 2003, however, came an unprecedented era of cultural destruction. Following the devastation of the battle phase of the war, there were further attacks on Iraq‟s cultural heritage including everything from the carefully choreographed removal of the giant bronze statue of Saddam in Firdos square, through to military bases set up at sensitive archaeological sites such as the ancient city of Babylon. In addition, Iraqi civilians targeted the cultural history of their nation with wanton looting and arson, as well as systematic attacks on sites of archaeological or ethno-religious significance. More recently, the Shia and Kurdish dominated Iraqi Government have organised the “Committee for Removing Symbols of the Saddam Era” and drew up plans to purge the state of its Sunni dominated past.

This paper argues that the unprecedented scale and magnitude of the destruction of Iraq‟s cultural history has played a part in eroding the various intersecting and overlapping versions of identity politics in Iraq. In turn, this has provided fertile ground for terrorists and sectarians to plant the seeds of their own narrow and deadly ideologies. This has brought about the rise of ethno-religious based violence and seen a series of bloody and protracted conflicts emerge between previously peaceful and compatible factions. In this way, Iraq serves as a powerful case study in furthering academic discussion on the complex inter-relationships between cultural and historical destruction and identity politics, sectarianism, violence and democracy.

Behind the mask : the hidden struggle of parenthood

A dvd presentation of the debilitating and often secretive issue of post-natal depression and anxiety, featuring people who have personally experienced and overcome the conditions as well as insights from health professionals.

Mid-Holocene (4200 kyr BP) mass mortalities in Mauritius (Mascarenes): insular vertebrates resilient to climatic extremes but vulnerable to human impact

In the light of the currently increasing drought frequency and water scarcity on oceanic islands, it is crucial for the conservation of threatened insular vertebrates to assess how they will be affected. A 4000 yr old fossil assemblage in the Mare Aux Songes (MAS), southwest Mauritius, Mascarene Islands, contains bones of 100 000+ individual vertebrates, dominated by two species of giant tortoises Cylindraspis triserrata and C. inepta, the dodo Raphus cucullatus, and 20 other vertebrate species (Rijsdijk, Hume, Bunnik, Florens, Baider, Shapiro et al. (2009) Mid-Holocene vertebrate bone Concentration-Lagerstätte on oceanic island Mauritius provides a window into the ecosystem of the dodo (Raphus cucullatus). Quaternary Science Reviews 28: 14–24). Nine radiocarbon dates of bones statistically overlap and suggest mass mortality occurred between 4235 and 4100 cal. yr BP. The mortality period coincides with a widely recognized megadrought event. Our multidisciplinary investigations combining geological, paleontological and hydrological evidence suggests the lake was located in a dry coastal setting and had desiccated during this period. Oxygen isotope data from a Uranium-series dated stalagmite from Rodrigues, an island 560 km east of Mauritius, supports this scenario by showing frequently alternating dry and wet periods lasting for decades between 4122 and 2260 cal. yr BP. An extreme drought resulted in falling water-tables at MAS and elsewhere on the island, perhaps deprived these insular vertebrates of fresh water, which led to natural mass mortalities and possibly to extirpations. In spite of these events, all insular species survived until at least the seventeenth century, confirming their resistance to climatic extremes. Despite this, the generally exponential increase of combined human impacts on islands including loss of geodiversity, habitats, and stocks of fresh water, there will be less environmental safe-haven options for insular endemic and native vertebrates during future megadrought conditions; and therefore will be more prone to extinction.

Intelligent 3D programmable surface

Creating a highly programmable surface operating at relatively high speed and in real time is an area of research with many challenges. Such a system has applications in the field of optical telescopes, product manufacturing, and giant 3D-screens and billboards for advertising and artwork. This paper covers certain aspects of a keynote presentation at ISDT 2010 including system design, modularity, programmability and the system control intelligence. An overview of the system architecture, actuator design, electronics and distributed control will provide an insight into how the system is controlled and self-tuned for a number of applications. A simulation environment that has been developed to streamline system reconfiguration will also be presented, demonstrating translation of complex mathematical functions into 3D shapes virtually before being displayed on the physical surface.

Performance score variation between days at Australian national and Olympic women's artistic gymnastics competition

We determined the inter-day variability in elite-standard women's artistic gymnastics competition scores. National (50 gymnasts for up to three days) and Olympic (24 gymnasts for up to five days) competition scores published in the public domain (‘Giant poster pull-out’, 2010; Gymnastics Australia, 2008) were evaluated using three statistical measures. Analyses of the inter-day differences in the mean scores as a percentage (MDiff%), coefficient of variation percentages for the mean score across both days (CV%), and Pearson correlation coefficients for the inter-day score (r) were interpreted using thresholds from trivial to large. National-class gymnasts' two-day performance variation was trivial for vault, small for floor and beam, and moderate for bars. When senior gymnasts competed for a third day the performance variation increased to moderate for vault. Across five days of Olympic competition there were trivial (e.g. CV%: vault = 0.8) to small (e.g. CV%: bars = 2.0) variations in performances between days on all apparatus. Olympians' performance score consistency is superior to senior, national-class competitors. The performance score consistency required for gymnasts who aspire to participate at the Olympics as a top-24 competitor is better than 3%.