Comparison of nanostructures obtained from galvanic replacement in water and an ionic liquid for applications in electrocatalysis and SERS

We demonstrate potential applications for unusual dendrite like Au–Ag alloy nanoparticles formed via a galvanic replacement reaction in the ionic liquid [BMIM][BF4]. In comparison to Au–Ag alloy nanoshells synthesised via a similar reaction in water, the unusual branched structure of the dendritic materials led to increased electrocatalytic activity for the oxidation of both formaldehyde and hydrazine, and increased sensitivity and spectral resolution for the surface enhanced Raman scattering (SERS) of 4,4-bipyridal.

New evidence of the reproductive organs of Glossopteris based on permineralized fossils from Queensland, Australia. II: pollen-bearing organ Ediea gen. nov

Ediea homevalensis H. Nishida, Kudo, Pigg & Rigby gen. et sp. nov. is proposed for permineralized pollen-bearing structures from the Late Permian Homevale Station locality of the Bowen Basin, Queensland, Australia. The taxon represents unisexual fertile shoots bearing helically arranged leaves on a central axis. The more apical leaves are fertile microsporophylls bearing a pair of multi-branched stalks on their adaxial surfaces that each supports a cluster of terminally borne pollen sacs. Proximal to the fertile leaves there are several rows of sterile scale-like leaves. The pollen sacs (microsporangia) have thickened and dark, striate walls that are typical of the Arberiella type found in most pollen organs presumed to be of glossopterid affinity. An examination of pollen organs at several developmental stages, including those containing in situ pollen of the Protohaploxypinus type, provides the basis for a detailed analysis of these types of structures, which bear similarities to both compression/impression Eretmonia-type glossopterid microsporangiate organs and permineralized Eretmonia macloughlinii from Antarctica. These fossils demonstrate that at least some Late Permian pollen organs were simple microsporophyll-bearing shoot systems and not borne directly on Glossopteris leaves.

SERS-barcoded colloidal gold NP assemblies as imaging agents for use in biodiagnostics

There is a growing need for new biodiagnostics that combine high throughput with enhanced spatial resolution and sensitivity. Gold nanoparticle (NP) assemblies with sub-10 nm particle spacing have the benefits of improving detection sensitivity via Surface enhanced Raman scattering (SERS) and being of potential use in biomedicine due to their colloidal stability. A promising and versatile approach to form solution-stable NP assemblies involves the use of multi-branched molecular linkers which allows tailoring of the assembly size, hot-spot density and interparticle distance. We have shown that linkers with multiple anchoring end-groups can be successfully employed as a linker to assemble gold NPs into dimers, linear NP chains and clustered NP assemblies. These NP assemblies with diameters of 30-120 nm are stable in solution and perform better as SERS substrates compared with single gold NPs, due to an increased hot-spot density. Thus, tailored gold NP assemblies are potential candidates for use as biomedical imaging agents. We observed that the hot-spot density and in-turn the SERS enhancement is a function of the linker polymer concentration and polymer architecture. New deep Raman techniques like Spatially Offset Raman Spectroscopy (SORS) have emerged that allow detection from beneath diffusely scattering opaque materials, including biological media such as animal tissue. We have been able to demonstrate that the gold NP assemblies could be detected from within both proteinaceous and high lipid containing animal tissue by employing a SORS technique with a backscattered geometry.

Synthesis of a multimodal molecular imaging probe based on a hyperbranched polymer architecture

Molecular imaging is utilised in modern medicine to aid in the diagnosis and treatment of disease by allowing its spatiotemporal state to be examined in vivo. This study focuses on the development of novel multimodal molecular imaging agents based on hyperbranched polymers that combine the complementary capabilities of optical fluorescence imaging and positron emission tomography-computed tomography (PET/CT) into one construct. RAFT-mediated polymerisation was used to prepare two hydrophilic hyperbranched polymers that were differentiated by their size and level of branching. The multiple functional end-groups facilitated covalent attachment of both near infrared fluorescent dyes for optical imaging, as well as a copper chelator allowing binding of 64Cu as a PET radio nuclei. In vivo multimodal imaging of mice using PET/CT and planar optical imaging was first used to assess the biodistribution of the polymeric materials and it was shown that the larger and more branched polymer had a significantly longer circulation time. The larger constructs were also shown to exhibit enhanced accumulation in solid tumours in a murine B16 melanoma model. Importantly, it was demonstrated that the PET modality gave rise to high sensitivity immediately after injection of the agent, while the optical modality facilitated extended longitudinal studies, thus highlighting how the complementary capabilities of the molecular imaging agents can be useful for studying various diseases, including cancer.

Structures of three different neutral polysaccharides of Acinetobacter baumannii, NIPH190, NIPH201, and NIPH615, assigned to K30, K45, and K48 capsule types, respectively, based on capsule biosynthesis gene clusters

Neutral capsular polysaccharides (CPSs) were isolated from Acinetobacter baumannii NIPH190, NIPH201, and NIPH615. The CPSs were found to contain common monosaccharides only and to be branched with a side-chain 1→3-linked β-d-glucopyranose residue. Structures of the oligosaccharide repeat units (K units) of the CPSs were elucidated by 1D and 2D 1H and 13C NMR spectroscopy. Novel CPS biosynthesis gene clusters, designated KL30, KL45, and KL48, were found at the K locus in the genome sequences of NIPH190, NIPH201, and NIPH615, respectively. The genetic content of each gene cluster correlated with the structure of the CPS unit established, and therefore, the capsular types of the strains studied were designated as K30, K45, and K48, respectively. The initiating sugar of each K unit was predicted, and glycosyltransferases encoded by each gene cluster were assigned to the formation of the linkages between sugars in the corresponding K unit.

Pre-operative nutritional support in children with end-stage liver disease accepted for liver transplantation: An approach to management

Pre-operative nutritional support was studied in 28 children with end-stage liver disease awaiting orthotopic liver transplantation. Nasogastric supplemental administration of a standard semi-elemental enteral nutritional formula was compared with a similar formula enriched with branched chain amino acids, and with a group receiving oral nutrition only. The duration of treatment in all groups was similar (mean 90 days). Energy intakes in the supplemented groups were 120-150% of recommended daily intakes (RDI), whereas ad libitum intakes in the oral group ranged 58-100% RDI. A significant improvement in mean Z-score for body weight (denoting catch-up) was noted only in those children who received nasogastric supplements enriched with branched-chain amino acids. The standard enterally-fed group maintained their body weight and Z-scores did not change significantly. In contrast, body weight Z-scores in those fed orally declined significantly. Nutritional supportive therapy of malnourished children with end-stage liver disease can minimize or improve nutritional status in children awaiting liver transplantation. The use of nutritional formulae rich in branche-chain amino acids may have nutritional advantages in children with chronic liver disease which require further study and evaluation.

Structural determination of the K14 capsular polysaccharide from an ST25 Acinetobacter baumannii isolate, D46

The structure of the capsular polysaccharide (CPS) recovered from D46, an extensively antibiotic resistant ST25 Acinetobacter baumannii clinical isolate, was elucidated. The structure was resolved on the basis of NMR spectroscopy and chemical analyses, and was found to contain a branched neutral pentasaccharide with a backbone composed of GalpNAc and Galp residues, all d configured, and a d-Glcp side group. The KL14 gene cluster found in the D46 genome includes genes for four glycosyltransferases but no modules for synthesis of complex sugars, and this is consistent with the structure of K14. The K14 structure and KL14 sequence clarify the relationship between the structure and K locus sequence for A. nosocomialis isolate LUH5541. The identity of the first sugar of the K14 repeat unit (K unit), and the functions of the four encoded glycosyltransferases and Wzy polymerase were predicted.

On Coloration of Polyacrylonitrile: A Nuclear Magnetic Resonance Study

Coloration in polyacrylonitrile can be induced in three distinct ways: by heat treatment, by treatment with base, or during synthesis of the polymer itself using ionic initiators at relatively higher temperatures. The present investigation employing 'H and NMR spectroscopy has revealed some common features in colored polyacrylonitrile irrespective of ita mode of coloration. All colored polyacrylonitriles give an additional peak around S 2.7 in 'H NMR spectra and, except for heat-treated polyacrylonitrile, one extra group of peaks in the region 8 12-16 in 13C NMR spectra. The former peak has been attributed to methine and/or methylene protons in branched and/or cyclized structures, while the latter peak has been attributed to methylene carbon atoms in the branched structure. Colorless polyacrylonitriles have been found to be predominantly heterotactic, while colored polyacrylonitriles have been found to have appreciable isotactic contribution.

Ruminal protein degradability of a range of tropical pastures

The rumen degradability parameters of the diet selected by two to four oesophageal-fistulated Brahman steers grazing a range of tropical pastures were determined by incubation of extrusa in nylon bags suspended in the rumen of rumen-fistulated (RF) Brahman steers. The effective protein degradability (Edg) was determined by measuring the rate of disappearance of neutral detergent insoluble nitrogen (NDIN) less acid detergent insoluble nitrogen (ADIN) in the incubated extrusa. Six to eight RF steers also grazed each of the pastures along with the oesophageal-fistulated steers, to allow determination of key rumen parameters and rumen particulate matter fractional outflow rates (FOR). The seven pastures studied included: native tropical grass (C4) pasture (major species Heteropogon contortus and Bothriochloa bladhii), studied in the early wet (NPEW), the wet/dry transition (NPT) and the dry (NPD) seasons; introduced tropical grass (C4) pasture (Bothriochloa insculpta), studied in the mid wet season (BB); the introduced tropical legumes (C3), Lablab purpureus (LL) and Clitoria ternatea (BP); and the temperate grass (C3) pasture, ryegrass (Lolium multiflorum, RG). Using the measured particle FOR values in calculations, the Edg estimates were very high for both C4 and C3 species: 0.82–0.91 and 0.95–0.98 g/g crude protein (CP), respectively. Substitution of an assumed FOR (kp = 0.02/h) for the measured values for each pasture type did not markedly affect estimates of Edg. However, C4 tropical grasses had much lower effective rumen degradable protein (ERDP) fractions (23–66 g/kg DM) than the C3 pasture species RG and LL (356 and 243 g/kg DM, respectively). This was associated with a lower potential degradability and degradation rate of organic matter (OM) in sacco, lower in vitro organic matter digestibility (IVOMD) and CP concentrations in the extrusa, and lower ammonia-N and branched-chain fatty acid concentrations in rumen fluid for the tropical grasses. As tropical grass pastures senesced, there was a decline in Edg, the ERDP and rumen undegradable protein (UDP) fractions, the potential degradability and degradation rate of OM and the IVOMD. These results provide useful data for estimating protein supply to cattle grazing tropical pastures.

Estimating and influencing the duration of weed eradication programmes

1. Weed eradication efforts often must be sustained for long periods owing to the existence of persistent seed banks, among other factors. Decision makers need to consider both the amount of investment required and the period over which investment must be maintained when determining whether to commit to (or continue) an eradication programme. However, a basis for estimating eradication programme duration based on simple data has been lacking. Here, we present a stochastic dynamic model that can provide such estimates. 2. The model is based upon the rates of progression of infestations from the active to the monitoring state (i.e. no plants detected for at least 12 months), rates of reversion of infestations from monitoring to the active state and the frequency distribution of time since last detection for all infestations. Isoquants that illustrate the combinations of progression and reversion parameters corresponding to eradication within different time frames are generated. 3. The model is applied to ongoing eradication programmes targeting branched broomrape Orobanche ramosa and chromolaena Chromolaena odorata. The minimum periods in which eradication could potentially be achieved were 22 and 23 years, respectively. On the basis of programme performance until 2008, however, eradication is predicted to take considerably longer for both species (on average, 62 and 248 years, respectively). Performance of the branched broomrape programme could be best improved through reducing rates of reversion to the active state; for chromolaena, boosting rates of progression to the monitoring state is more important. 4. Synthesis and applications. Our model for estimating weed eradication programme duration, which captures critical transitions between a limited number of states, is readily applicable to any weed.Aparticular strength of the method lies in its minimal data requirements. These comprise estimates of maximum seed persistence and infested area, plus consistent annual records of the detection (or otherwise) of the weed in each infestation. This work provides a framework for identifying where improvements in management are needed and a basis for testing the effectiveness of alternative tactics. If adopted, our approach should help improve decision making with regard to eradication as a management strategy.

Molecular Background of Common Dyslipidemias

The leading cause of death in the Western world continues to be coronary heart disease (CHD). At the root of the disease process is dyslipidemia an aberration in the relevant amounts of circulating blood lipids. Cholesterol builds up in the arterial wall and following rupture of these plaques, myocardial infarction or stroke can occur. Heart disease runs in families and a number of hereditary forms are known. The leading cause of adult dyslipidemia presently however is overweight and obesity. This thesis work presents an investigation of the molecular genetics of common, hereditary dyslipidemia and the tightly related condition of obesity. Familial combined hyperlipidemia (FCHL) is the most common hereditary dyslipidemia in man with an estimated population prevalence of 1-6%. This complex disease is characterized by elevated levels of serum total cholesterol, triglycerides or both and is observed in about 20% of individuals with premature CHD. Our group identified the disease to be associated with genetic variation in the USF1 transcription factor gene. USF1 has a key role in regulating other genes that control lipid and glucose metabolism as well as the inflammatory response all central processes in the progression of atherosclerosis and CHD. The first two works of this thesis aimed at understanding how these USF1 variants result in increased disease risk. Among the many, non-coding single-nucleotide polymorphisms (SNPs) that associated with the disease, one was found to have a functional effect. The risk-enhancing allele of this SNP seems to eradicate the ability of the important hormone insulin to induce the expression of USF1 in peripheral tissues. The resultant changes in the expression of numerous USF1 target genes over time probably enhance and accelerate the atherogenic processes. Dyslipidemias often represent an outcome of obesity and in the final work of this thesis we wanted to address the metabolic pathways related to acquired obesity. It is recognized that active processes in adipose tissue play an important role in the development of dyslipidemia, insulin resistance and other pathological conditions associated with obesity. To minimize the confounding effects of genetic differences present in most human studies, we investigated a rare collection of identical twins that differed significantly in the amount of body fat. In the obese, but otherwise healthy young adults, several notable changes were observed. In addition to chronic inflammation, the adipose tissue of the obese co-twins was characterized by a marked (47%) decrease in amount of mitochondrial DNA (mtDNA) a change associated with mitochondrial dysfunction. The catabolism of branched chain amino acids (BCAAs) was identified as the most down-regulated process in the obese co-twins. A concordant increase in the serum level of these insulin secretagogues was identified. This hyperaminoacidemia may provide the feed-back signal from insulin resistant adipose tissue to the pancreas to ensure an appropriately augmented secretory response. The down regulation of BCAA catabolism correlated closely with liver fat accumulation and insulin. The single most up-regulated gene (5.9 fold) in the obese co-twins was osteopontin (SPP1) a cytokine involved in macrophage recruitment to adipose tissue. SPP1 is here implicated as an important player in the development of insulin resistance. These studies of exceptional study samples provide better understanding of the underlying pathology in common dyslipidemias and other obesity associated diseases important for future improvement of intervention strategies and treatments to combat atherosclerosis and coronary heart disease.

Sensory Systems in Sawfishes. 2. The Lateral Line.

The lateral line system allows elasmobranchs to detect hydrodynamic movements in their close surroundings. We examined the distribution of pit organs and lateral line canals in 4 species of sawfish (Anoxypristis cuspidata, Pristis microdon, P. clavata and P. zijsron). Pit organs could only be located in A. cuspidata, which possesses elongated pits that are lined by dermal denticles. In all 4 pristid species, the lateral line canals are well developed and were separated into regions of pored and non-pored canals. In all species the tubules that extend from pored canals form extensive networks. In A. cuspidata, P. microdon and P. clavata, the lateral line canals on both the dorsal and ventral surfaces of the rostrum possess extensively branched and pored tubules. Based on this morphological observation, we hypothesized that these 3 species do not use their rostrum to search in the substrate for prey as previously assumed. Other batoids that possess lateral line canals adapted to perceive stimuli produced by infaunal prey possess non-pored lateral line canals, which also prevent the intrusion of substrate particles. However, this hypothesis remains to be tested behaviourally in pristids. Lateral line canals located between the mouth and the nostrils are non-pored in all 4 species of sawfish. Thus this region is hypothesized to perceive stimuli caused by direct contact with prey before ingestion. Lateral line canals that contain neuromasts are longest in P. microdon, but canals containing neuromasts along the rostrum are longest in A. cuspidata.

Simulation of parthenium weed canopy under changing climate using L-systems

Parthenium weed (Parthenium hysterophorus L.) is an erect, branched, annual plant of the family Asteraceae. It is native to the tropical Americas, while now widely distributed throughout Africa, Asia, Oceania, and Australasia. Due to its allelopathic and toxic characteristics, parthenium weed has been considered to be a weed of global significance. These effects occur across agriculture (crops and pastures), within natural ecosystems, and has impacts upon health (human and animals). Although integrated weed management (IWM) for parthenium weed has had some success, due to its tolerance and good adaptability to temperature, precipitation, and CO2, this weed has been predicted to become more vigorous under a changing climate resulting in an altered canopy architecture. From the viewpoint of IWM, the altered canopy architecture may be associated with not only improved competitive ability and replacement but also may alter the effectiveness of biocontrol agents and other management strategies. This paper reports on a preliminary study on parthenium weed canopy architecture at three temperature regimes (day/night 22/15 °C, 27/20 °C, and 32/25 °C in thermal time 12/12 hours) and establishes a threedimensional (3D) canopy model using Lindenmayer-systems (L-systems). This experiment was conducted in a series of controlled environment rooms with parthenium weed plants being grown in a heavy clay soil. A sonic digitizer system was used to record the morphology, topology, and geometry of the plants for model construction. The main findings include the determination of the phyllochron which enables the prediction of parthenium weed growth under different temperature regimes and that increased temperature enhances growth and enlarges the plants canopy size and structure. The developed 3D canopy model provides a tool to simulate and predict the weed growth in response to temperature, and can be adjusted for studies of other climatic variables such as precipitation and CO2. Further studies are planned to investigate the effects of other climatic variables, and the predicted changes in the pathogenic biocontrol agent effectiveness.

Estimating the duration and cost of weed eradication programmes

Two prerequisites for realistically embarking upon an eradication programme are that cost-benefit analysis favours this strategy over other management options and that sufficient resources are available to carry the programme through to completion. These are not independent criteria, but it is our view that too little attention has been paid to estimating the investment required to complete weed eradication programmes. We deal with this problem by using a two-pronged approach: 1) developing a stochastic dynamic model that provides an estimation of programme duration; and 2) estimating the inputs required to delimit a weed incursion and to prevent weed reproduction over a sufficiently long period to allow extirpation of all infestations. The model is built upon relationships that capture the time-related detection of new infested areas, rates of progression of infestations from the active to the monitoring stage, rates of reversion of infestations from the monitoring to active stage, and the frequency distribution of time since last detection for all infestations. This approach is applied to the branched broomrape (Orobanche ramosa) eradication programme currently underway in South Australia. This programme commenced in 1999 and currently 7450 ha are known to be infested with the weed. To date none of the infestations have been eradicated. Given recent (2008) levels of investment and current eradication methods, model predictions are that it would take, on average, an additional 73 years to eradicate this weed at an average additional cost (NPV) of $AU67.9m. When the model was run for circumstances in 2003 and 2006, the average programme duration and total cost (NPV) were predicted to be 159 and 94 years, and $AU91.3m and $AU72.3m, respectively. The reduction in estimated programme length and cost may represent progress towards the eradication objective, although eradication of this species still remains a long term prospect.

Improving decisions for invasive species management: Reformulation and extensions of the Panetta-Lawes eradication graph

Aim: Effective decisions for managing invasive species depend on feedback about the progress of eradication efforts. Panetta & Lawes. developed the eradograph, an intuitive graphical tool that summarizes the temporal trajectories of delimitation and extirpation to support decision-making. We correct and extend the tool, which was affected by incompatibilities in the units used to measure these features that made the axes impossible to interpret biologically. Location: Victoria, New South Wales and Queensland, Australia. Methods: Panetta and Lawes' approach represented delimitation with estimates of the changes in the area known to be infested and extirpation with changes in the mean time since the last detection. We retain the original structure but propose different metrics that improve biological interpretability. We illustrate the methods with a hypothetical example and real examples of invasion and treatment of branched broomrape (Orobanche ramosa L.) and the guava rust complex (Puccinia psidii (Winter 1884)) in Australia. Results: These examples illustrate the potential of the tool to guide decisions about the effectiveness of search and control activities. Main conclusions: The eradograph is a graphical data summary tool that provides insight into the progress of eradication. Our correction and extension of the tool make it easier to interpret and provide managers with better decision support. © 2013 John Wiley & Sons Ltd.