π-Selective stationary phases: (III) Influence of the propyl phenyl ligand density on the aromatic and methylene selectivity of aromatic compounds in reversed phase liquid chromatography

The retention characteristics of phenyl type stationary phases for reversed phase high performance liquid chromatography are still largely unknown. This paper explores the retention process of these types of stationary phases by examining the retention behaviour of linear PAHs and n-alkylbenzenes on a series of propyl phenyl stationary phases that have changes in their ligand density (1.23, 1.31, 1.97, 2.50 μmol m⁻²). The aromatic and methylene selectivities increased with increasing ligand density until a point where a plateau was observed, overall the propyl phenyl phases had a higher degree of aromatic selectivity than methylene selectivity indicating that these columns are suitable for separations involving aromatic compounds. Also, retention characteristics relating to the size of the solute molecule were observed to be influenced by the ligand density. It is likely that the changing retention characteristics are caused by the different topologies of the stationary phases at different ligand densities. At high ligand densities, the partition coefficient became constant.

π-Selective stationary phases: (I) Influence of the spacer chain length of phenyl type phases on the aromatic and methylene selectivity of aromatic compounds in reversed phase high performance liquid chromatography

Phenyl type stationary phases of increasing spacer chain length (phenyl, methyl phenyl, ethyl phenyl, propyl phenyl and butyl phenyl, with 0–4 carbon atoms in the spacer chain, respectively) were synthesised and packed in house to determine the impact that the spacer chain length has on the retention process. Two trends in the aromatic selectivity, q_aromatic, were observed, depending on whether the number of carbon atoms in the spacer chain is even or odd. Linear log k′ vs ϕ plots were obtained for each stationary phase and the S coefficient was determined from the gradient of these plots. For the phenyl type phases, the S vs n_c plots of the retention factors of linear polycyclic aromatic hydrocarbons vs the number of rings exhibit a distinct discontinuity that between 3 and 4 rings, which increases with increasing spacer chain length for even phases but decreases for odd phases. Accordingly, we suggest that the retention factors depend differently on the number of carbon atoms in the spacer chain depending on whether this number is even or odd and that this effect is caused by different orientations of the aromatic ring relative to the silica surface.

Assessing effects of diel period, gear selectivity and predation on patterns of microhabitat use by fish in a mangrove dominated system in SE Australia

The relative value of temperate mangroves to fish, and the processes driving patterns of microhabitat use within this habitat, are unknown. There are 3 quickly identifiable microhabitats within temperate Australian mangroves: (1) forest (the area of mangroves with trees); (2) pneumatophores (the area directly seaward of the forest without trees but with pneumatophores [aerial roots]); and (3) channel (the area directly seaward of the pneumatophores without gross structural attributes such as trees or pneumatophores). Duplicate fyke and gill nets were both initially used to sample fish in the 3 microhabitats described above. Sampling took place across the seaward edge of mangroves on 10 sampling occasions (5 night and 5 day), in a large estuarine system in SE Australia. Fish assemblages (693 fish from 20 species and 15 families) varied significantly (p < 0.05) between the forest and the channel, and between diel periods for each gear (net type), but there was little difference in the assemblage structure of fish between forest–pneumatophore or pneumatophore–channel microhabitats. Juvenile lifestages (61% of all fish) and commercially important taxa (76%) were common. Abundance, biomass and species richness of fish were generally lower in the forest than the other microhabitats, but this pattern varied significantly (p < 0.05) between diel periods, among sampling occasions, and with water depth. Highly quantitative pop nets provided a preliminary assessment of whether differential gear selectivity caused patterns between microhabitats, but less rich fish assemblages were again recorded in forests than in pneumatophores. The importance of predation in structuring fish assemblages across microhabitats was assessed by measuring survival of juvenile fish tethered in 3 predation treatments (predator exclusion, cage control, and uncaged). Survival rates were high across the predator treatments and did not vary among microhabitats. The variation in fish assemblages across microhabitats within mangroves was not consistent with a model of mangrove structure providing a refuge for juvenile fish from predation, but instead could indicate differences in efficiency of gear types among microhabitats and/or other ‘edge effect’-driven processes such as the provision of food and/or shelter.

Open scholarship : research and publication

Introduction: Sue Owen, Associate University Librarian, Deakin University Library.

Presentations:
Using Creative Commons licences to provide open access in the education and research sectors / Professor Anne Fitzgerald ;
Elsevier and open access / Macy Lee and David Tempest ;
Electronic rights  in academic publishing; a researcher's perspective / Professor Christoph Antons.

Panel discussion, Question and answer.

Includes audio/visual recording of whole Symposium

Investigating retention characteristics of a mixed-mode stationary phase and the enhancement of monolith selectivity for high-performance liquid chromatography

The synthesis and chromatographic behavior of an analytical size mixed-mode bonded silica monolith was investigated. The monolith was functionalized by an in situ modification process of a bare silica rod with chloro(3-cyanopropyl)dimethyl silane and chlorodimethyl propyl phenyl silane solutions. These ligands were selected in order to combine both resonance and nonresonance π-type bonding within a single separation environment. Selectivity studies were undertaken using n-alkyl benzenes and polycyclic aromatic hydrocarbons in aqueous methanol and acetonitrile mobile phases to assess the methylene and aromatic selectivities of the column. The results fit with the linear solvent strength theory suggesting excellent selectivity of the column was achieved. Comparison studies were performed on monolithic columns that were functionalized separately with cyano and phenyl ligands, suggesting highly conjugated molecules were able to successfully exploit both of the π-type selectivities afforded by the two different ligands on the mixed-mode column.

Characterisation of lipase fatty acid selectivity using novel omega-3 pNP-acyl esters

 Lipases have applications for the industrial processing of lipids, including concentrating and/or modifying fish oil derived omega-3 fatty acids, widely used as nutritional supplement and functional food ingredients. A range of para-nitrophenol (pNP) acyl esters were synthesised as a means to rapidly screen lipases for fatty acid selectivity using spectrophotometric detection. The chosen esters were based primarily on the most abundant fatty acids present in anchovy and tuna oils. pNP derivatives of C16:1 n-7, C18:1 n-9 (OA), C18:2 n-6 (LA), C18:3 n-3 (ALA), C20:5 n-3 (EPA) and C22:6 n-3 (DHA) were synthesised. Storage stability of these pNP derivatives was shown to be at least 6 months and all pNP derivatives, including those of EPA and DHA, were shown to be stable throughout the conditions of the assay. We applied the new assay substrates for the determination of fatty acid selectivity of five widely utilised lipases. Results showed that the lipase from Candida rugosa was the most selective in terms of omega-3 specificity, preferentially hydrolysing all other medium– long chain substrates. Lipases from Rhizomucor miehei and Thermomyces lanuginosa also showed selectivity, with a significant preference for saturated fatty acids. Candida Antarctica lipase B and Aspergillus niger lipase were the least selective.

Comparative study of materials-binding peptide interactions with gold and silver surfaces and nanostructures : A thermodynamic basis for biological selectivity of inorganic materials

Controllable 3D assembly of multicomponent inorganic nanomaterials by precisely positioning two or more types of nanoparticles to modulate their interactions and achieve multifunctionality remains a major challenge. The diverse chemical and structural features of biomolecules can generate the compositionally specific organic/inorganic interactions needed to create such assemblies. Toward this aim, we studied the materials-specific binding of peptides selected based upon affinity for Ag (AgBP1 and AgBP2) and Au (AuBP1 and AuBP2) surfaces, combining experimental binding measurements, advanced molecular simulation, and nanomaterial synthesis. This reveals, for the first time, different modes of binding on the chemically similar Au and Ag surfaces. Molecular simulations showed flatter configurations on Au and a greater variety of 3D adsorbed conformations on Ag, reflecting primarily enthalpically driven binding on Au and entropically driven binding on Ag. This may arise from differences in the interfacial solvent structure. On Au, direct interaction of peptide residues with the metal surface is dominant, while on Ag, solvent-mediated interactions are more important. Experimentally, AgBP1 is found to be selective for Ag over Au, while the other sequences have strong and comparable affinities for both surfaces, despite differences in binding modes. Finally, we show for the first time the impact of these differences on peptide mediated synthesis of nanoparticles, leading to significant variation in particle morphology, size, and aggregation state. Because the degree of contact with the metal surface affects the peptide's ability to cap the nanoparticles and thereby control growth and aggregation, the peptides with the least direct contact (AgBP1 and AgBP2 on Ag) produced relatively polydispersed and aggregated nanoparticles. Overall, we show that thermodynamically different binding modes at metallic interfaces can enable selective binding on very similar inorganic surfaces and can provide control over nanoparticle nucleation and growth. This supports the promise of bionanocombinatoric approaches that rely upon materials recognition.

Exploring two-dimensional chromatography and chemiluminescence selectivity for complex sample analysis

 Human, animal and plant samples contain a considerable number of chemical substances critical for supporting their existence. This thesis presents improved techniques to find and analyse these components to help us understand more about their roles in the complex jigsaw of life.

Facet selectivity in gold binding peptides: exploiting interfacial water structure

Peptide sequences that can discriminate between gold facets under aqueous conditions offer a promising route to control the growth and organisation of biomimetically-synthesised gold nanoparticles. Knowledge of the interplay between sequence, conformations and interfacial properties is essential for predictable manipulation of these biointerfaces, but the structural connections between a given peptide sequence and its binding affinity remain unclear, impeding practical advances in the field. These structural insights, at atomic-scale resolution, are not easily accessed with experimental approaches, but can be delivered via molecular simulation. A current unmet challenge lies in forging links between predicted adsorption free energies derived from enhanced sampling simulations with the conformational ensemble of the peptide and the water structure at the surface. To meet this challenge, here we use an in situ combination of Replica Exchange with Solute Tempering with Metadynamics simulations to predict the adsorption free energy of a gold-binding peptide sequence, AuBP1, at the aqueous Au(111), Au(100)(1 × 1) and Au(100)(5 × 1) interfaces. We find adsorption to the Au(111) surface is stronger than to Au(100), irrespective of the reconstruction status of the latter. Our predicted free energies agree with experiment, and correlate with trends in interfacial water structuring. For gold, surface hydration is predicted as a chief determining factor in peptide-surface recognition. Our findings can be used to suggest how shaped seed-nanocrystals of Au, in partnership with AuBP1, could be used to control AuNP nanoparticle morphology.

Rising Publication Delays Inflate Journal Impact Factors

Journal impact factors have become an important criterion to judge the quality of scientific publications over the years, influencing the evaluation of institutions and individual researchers worldwide. However, they are also subject to a number of criticisms. Here we point out that the calculation of a journal’s impact factor is mainly based on the date of publication of its articles in print form, despite the fact that most journals now make their articles available online before that date. We analyze 61 neuroscience journals and show that delays between online and print publication of articles increased steadily over the last decade. Importantly, such a practice varies widely among journals, as some of them have no delays, while for others this period is longer than a year. Using a modified impact factor based on online rather than print publication dates, we demonstrate that online-to-print delays can artificially raise a journal’s impact factor, and that this inflation is greater for longer publication lags. We also show that correcting the effect of publication delay on impact factors changes journal rankings based on this metric. We thus suggest that indexing of articles in citation databases and calculation of citation metrics should be based on the date of an article’s online appearance, rather than on that of its publication in print.

Selectivity of the herbicide flazasulfuron applied after postemergence in sugarcane (Saccharum spp. L.) crop

The selectivity of the herbicide flazasulfaron was evaluated when applied at two rates (50 and 100 g/ha) with and without surfactants (Aterbane or Agral at 0.2% v/v). The treatment was applied at early (three leaves) and late (five to six leaves) stages of the postemergence of sugarcane plants (var. RB845257) grown in two soils (sandy and clay) with good moisture status before and after application. Despite the toxicity symptoms, especially at the late stage with the higher rate of application in the sandy soil, the herbicide did not affect the growth nor the stalk yield. The presence of the surfactants had no effect on the toxicity symptoms.