A combined scanning electron micrograph and electrochemical study of the effect of chemical interaction on the cyclability of lithium electrodes in an ionic liquid electrolyte

The effect of storage time on the cyclability of lithium electrodes in an ionic liquid electrolyte, namely 0.5 m LiBF4 in N-methyl-N-propyl pyrrolidinium bis(fluorosulfonyl)imide, [C3mpyr+][FSI–], was investigated. A chemical interaction was observed which is time dependent and results in a morphology change of the Li surface due to build up of passivation products over a 12-day period. The formation of this layer significantly impacts on the Li electrode resistance before cycling and the charging/discharging process for symmetrical Li|0.5 m LiBF4 in [C3mpyr+][FSI–]|Li coin cells. Indeed it was found that introducing a rest period between cycling, and thereby allowing the chemical interaction between the Li electrode and electrolyte to take place, also impacted on the charging/discharging process. For all Li surface treatments the electrode resistance decreased after cycling and was due to significant structural rearrangement of the surface layer. These results suggest that careful electrode pretreatment in a real battery system will be required before operation.

Reusable surface confined semi-conducting metal-TCNQ and metal-TCNQF4 catalysts for electron transfer reactions

The synthesis of organic semiconducting materials based on silver and copper-TCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) and their fluorinated analogues has received a significant amount of attention due to their potential use in organic electronic applications. However, there is a scarcity in the identification of different applications for which these interesting materials may be suitable candidates. In this work, we address this by investigating the catalytic properties of such materials for the electron transfer reaction between ferricyanide and thiosulphate ions in aqueous solution, which to date has been almost solely limited to metallic nanomaterials. Significantly it was found that all the materials investigated, namely CuTCNQ, AgTCNQ, CuTCNQF4 and AgTCNQF4, were catalytically active and, interestingly, the fluorinated analogues were superior. AgTCNQF4 demonstrated the highest activity and was tested for its stability and re-usability for up to 50 cycles without degradation in performance. The catalytic reaction was monitored via UV-vis spectroscopy and open circuit potential versus time measurements, as well as an investigation of the transport properties of the films via electrochemical impedance spectroscopy. It is suggested that morphology and bulk conductivity are not the limiting factors, but rather the balance between the accumulated surface charge from electron injection via thiosulphate ions on the catalyst surface and transfer to the ferricyanide ions which controls the reaction rate. The facile fabrication of re-usable surface confined organic materials that are catalytically active may have important uses for many more electron transfer reactions.

The electrochemical corrosion behaviour of quaternary gold alloys when exposed to 3.5% NaCl solution

Lower carat gold alloys, specifically 9 carat gold alloys, containing less than 40 % gold, and alloying additions of silver, copper and zinc, are commonly used in many jewellery applications, to offset high costs and poor mechanical properties associated with pure gold. While gold is considered to be chemically inert, the presence of active alloying additions raises concerns about certain forms of corrosion, particularly selective dissolution of these alloys. The purpose of this study was to systematically study the corrosion behaviour of a series of quaternary gold–silver–copper–zinc alloys using dc potentiodynamic scanning in saline (3.5 % NaCl) environment. Full anodic/cathodic scans were conducted to determine the overall corrosion characteristics of the alloy, followed by selective anodic scans and subsequent morphological and compositional analysis of the alloy surface and corroding media to determine the extent of selective dissolution. Varying degrees of selective dissolution and associated corrosion rates were observed after anodic polarisation in 3.5 % NaCl, depending on the alloy composition. The corrosion behaviour of the alloys was determined by the extent of anodic reactions which induce (1) formation of oxide scales on the alloy surface and or (2) dissolution of Zn and Cu species. In general, the improved corrosion characteristics of alloy #3 was attributed to the composition of Zn/Cu in the alloy and thus favourable microstructure promoting the formation of protective oxide/chloride scales and reducing the extent of Cu and Zn dissolution.

Direct electrochemical formation of alloyed AuPt nanostructured electrocatalysts for the oxidation of formic acid

The formation of highly anisotropic AuPt alloys has been achieved via a simple electrochemical approach without the need for organic surfactants to direct the growth process. The surface and bulk properties of these materials were characterised by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and electrochemically by cyclic voltammetry to confirm alloy formation. It was found that AuPt materials are highly active for both the model hydrogen evolution reaction and the fuel cell relevant formic acid oxidation reaction. In particular for the latter case the preferred dehydrogenation pathway was observed at AuPt compared to nanostructured Pt prepared under identical electrochemical conditions which demonstrated the less preferred dehydration pathway. The enhanced performance is attributed to both the ensemble effect which facilitates CO(ads) removal from the surface as well as the highly anisotropic nanostructure of AuPt.

Taguchi optimized synthesis of graphene films by copper catalyzed ethanol decomposition

Taguchi method is for the first time applied to optimize the synthesis of graphene films by copper-catalyzed decomposition of ethanol. In order to find the most appropriate experimental conditions for the realization of thin high-grade films, six experiments suitably designed and performed. The influence of temperature (1000–1070 °C) and synthesis duration (1–30 min) and hydrogen flow (0–100 sccm) on the number of graphene layers and defect density in the graphitic lattice was ranked by monitoring the intensity of the 2D- and D-bands relative to the G-band in the Raman spectra. After critical examination and adjusting of the conditions predicted to give optimal results, a continuous film consisting of 2–4 nearly defect-free graphene layers was obtained.

Synthesis and spectroscopic characterization of magnesium oxalate nano-crystals

Synthesis of MgC2O4⋅2H2O nano particles was carried out by thermal double decomposition of solutions of oxalic acid dihydrate (C2H2O4⋅2H2O) and Mg(OAc)2⋅4H2O employing CATA-2R microwave reactor. Structural elucidation was carried out by employing X-ray diffraction (XRD), particle size and shape were studied by transmission electron microscopy (TEM) and nature of bonding was investigated by optical absorption and near-infrared (NIR) spectral studies. The powder resulting from this method is pure and possesses distorted rhombic octahedral structure. The synthesized nano rod is 80 nm in diameter and 549 nm in length.

Synthesis of complementary RNA by RNA-dependent RNA polymerases in plant extracts is independent of an RNA primer

RNA-dependent RNA polymerase (RDR) activities were readily detected in extracts from cauliflower and broccoli florets, Arabidopsis thaliana (L.) Heynh callus tissue and broccoli nuclei. The synthesis of complementary RNA (cRNA) was independent of a RNA primer, whether or not the primer contained a 3′ terminal 2′-O-methyl group or was phosphorylated at the 5′ terminus. cRNA synthesis in plant extracts was not affected by loss-of-function mutations in the DICER-LIKE (DCL) proteins DCL2, DCL3, and DCL4, indicating that RDRs function independently of these DCL proteins. A loss-of-function mutation in RDR1, RDR2 or RDR6 did not significantly reduce the amount of cRNA synthesis. This indicates that these RDRs did not account for the bulk RDR activities in plant extracts, and suggest that either the individual RDRs each contribute a fraction of polymerase activity or another RDR(s) is predominant in the plant extract. © CSIRO 2008.

Electrochemical formation of Cu/Ag surfaces and their applicability as heterogeneous catalysts

In this work the electrochemical formation of porous Cu/Ag materials is reported via the simple and quick method of hydrogen bubble templating. The bulk and surface composition ratio between Ag and Cu was varied in a systematic manner and was readily controlled by the concentration of precursor metal salts in the electrolyte. The incorporation of Ag within the Cu scaffold only affected the formation of well-defined pores at high Ag loading whereas the internal pore wall structure gradually transformed from dendritic to cube like and finally needle like structures, which was due to the concomitant formation of Cu2O within the structure. The materials were characterised by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Their surface properties were further investigated by surface enhanced Raman spectroscopy (SERS) and electrochemically probed by recording the hydrogen evolution reaction (HER) which is highly sensitive to the nature of the surface. The effect of surface composition was then investigated for its influence on two catalytic reactions namely the reduction of ferricyanide ions with thiosulphate ions and the reduction of 4-nitrophenol with NaBH4 in aqueous solution where it was found that the presence of Ag had a beneficial effect in both cases but more so in the case of nitrophenol reduction. It is believed that this material may have many more potential applications in the area of catalysis, electrocatalysis and photocatalysis.

Visible light photocatalysts for synthesis of fine organic chemicals on supported nanostructures

This thesis is focus on developing new photocatalysts for synthesis of fine organic chemicals on supported nanostructures. These photocatalysts can facilitate reactions by using visible light, moderate temperature and atmospheric pressure which is suitable for a sustainable, green and eco-friendly modern chemical industry. Both Semiconductor Photocatalyst and Noble Metal Photocatalysts are designed to facilitate the homocouplings reaction of imine generation by amines.

Design, synthesis and spectroscopic characterisation of a focused library based on the polyandrocarpamine natural product scaffold

A focused library based on the marine natural products polyandrocarpamines A (1) and B (2) has been designed and synthesised using parallel solution-phase chemistry. In silico physicochemical property calculations were performed on synthetic candidates in order to optimise the library for drug discovery and chemical biology. A library of ten 2-aminoimidazolone products (3–12) was prepared by coupling glycocyamidine and a variety of aldehydes using a one-step stereoselective aldol condensation reaction under microwave conditions. All analogues were characterised by NMR, UV, IR and MS. The library was evaluated for cytotoxicity towards the prostate cancer cell lines, LNCaP, PC-3 and 22Rv1.

Mesoporous titania microspheres composed of exposed active faceted nanosheets and their catalytic activities for solvent-free synthesis of azoxybenzenes

Mesoporous titania microspheres composed of nanosheets with exposed active facets were prepared by hydrothermal synthesis in the presence of hexafluorosilicic acid. They exhibited superior catalytic activity in the solvent-free synthesis of azoxybenzene by oxidation of aniline and could be used for 7 cycles with slight loss of activity.

Alcohol ingestion impairs maximal post-exercise rates of myofibrillar protein synthesis following a single bout of concurrent training

Introduction The culture in many team sports involves consumption of large amounts of alcohol after training/competition. The effect of such a practice on recovery processes underlying protein turnover in human skeletal muscle are unknown. We determined the effect of alcohol intake on rates of myofibrillar protein synthesis (MPS) following strenuous exercise with carbohydrate (CHO) or protein ingestion. Methods In a randomized cross-over design, 8 physically active males completed three experimental trials comprising resistance exercise (8×5 reps leg extension, 80% 1 repetition maximum) followed by continuous (30 min, 63% peak power output (PPO)) and high intensity interval (10×30 s, 110% PPO) cycling. Immediately, and 4 h post-exercise, subjects consumed either 500 mL of whey protein (25 g; PRO), alcohol (1.5 g·kg body mass−1, 12±2 standard drinks) co-ingested with protein (ALC-PRO), or an energy-matched quantity of carbohydrate also with alcohol (25 g maltodextrin; ALC-CHO). Subjects also consumed a CHO meal (1.5 g CHO·kg body mass−1) 2 h post-exercise. Muscle biopsies were taken at rest, 2 and 8 h post-exercise. Results Blood alcohol concentration was elevated above baseline with ALC-CHO and ALC-PRO throughout recovery (P<0.05). Phosphorylation of mTORSer2448 2 h after exercise was higher with PRO compared to ALC-PRO and ALC-CHO (P<0.05), while p70S6K phosphorylation was higher 2 h post-exercise with ALC-PRO and PRO compared to ALC-CHO (P<0.05). Rates of MPS increased above rest for all conditions (~29–109%, P<0.05). However, compared to PRO, there was a hierarchical reduction in MPS with ALC-PRO (24%, P<0.05) and with ALC-CHO (37%, P<0.05). Conclusion We provide novel data demonstrating that alcohol consumption reduces rates of MPS following a bout of concurrent exercise, even when co-ingested with protein. We conclude that alcohol ingestion suppresses the anabolic response in skeletal muscle and may therefore impair recovery and adaptation to training and/or subsequent performance.

Tuning the surface structure of nitrogen-doped TiO2Nanofibres : an effective method to rnhance photocatalytic activities of visible-light-driven green synthesis and degradation

Nitrogen-doped TiO2 nanofibres of anatase and TiO2(B) phases were synthesised by a reaction between titanate nanofibres of a layered structure and gaseous NH3 at 400–700 °C, following a different mechanism than that for the direct nitrogen doping from TiO2. The surface of the N-doped TiO2 nanofibres can be tuned by facial calcination in air to remove the surface-bonded N species, whereas the core remains N doped. N-Doped TiO2 nanofibres, only after calcination in air, became effective photocatalysts for the decomposition of sulforhodamine B under visible-light irradiation. The surface-oxidised surface layer was proven to be very effective for organic molecule adsorption, and the activation of oxygen molecules, whereas the remaining N-doped interior of the fibres strongly absorbed visible light, resulting in the generation of electrons and holes. The N-doped nanofibres were also used as supports of gold nanoparticle (Au NP) photocatalysts for visible-light-driven hydroamination of phenylacetylene with aniline. Phenylacetylene was activated on the N-doped surface of the nanofibres and aniline on the Au NPs. The Au NPs adsorbed on N-doped TiO2(B) nanofibres exhibited much better conversion (80 % of phenylacetylene) than when adsorbed on undoped fibres (46 %) at 40 °C and 95 % of the product is the desired imine. The surface N species can prevent the adsorption of O2 that is unfavourable for the hydroamination reaction, and thus, improve the photocatalytic activity. Removal of the surface N species resulted in a sharp decrease of the photocatalytic activity. These photocatalysts are feasible for practical applications, because they can be easily dispersed into solution and separated from a liquid by filtration, sedimentation or centrifugation due to their fibril morphology.

Informing healthy building design with biophilic urbanism design principles : a review and synthesis of current knowledge and research

Links between human health and wellbeing, and contact with nature are well understood in the fields of health and psychology, and more recently are gaining attention in the built environment industry. In 1984, E.O. Wilson coined the term ‘biophilia’ to describe the tendency for humans to have an innately emotional response to other living organisms. A growing number of researchers around the world are now exploring the impact of nature in urban environments (i.e. biophilic urbanism) on the human condition, including many indicators of human physical and mental health, recovery and performance. There is also an emergence of research on the potential for biophilic urbanism to address other challenges related to climate change mitigation and adaptation. This paper presents key findings from a review of key literature to date, discussing opportunities for biophilic urbanism to both improve occupant experience and performance, as well as addressing other sustainability objectives including climate change mitigation and adaptation. The paper presents an emerging framework for considering biophilic design opportunities and highlights implications for the built environment industry. This research draws on an Australian project considering biophilic urbanism in the response to climate change, within the Sustainable Built Environment National Research Centre. This includes findings from a literature review, a survey pilot study and two workshops undertaken in Perth and Brisbane with a variety of industry and government stakeholders.

Tethering for Selective Synthesis of 2,2′-Biphenols : the Acetal Method

2,2'-Biphenols are a large and diverse group of compounds with exceptional properties both as ligands and bioactive agents. Traditional methods for their synthesis by oxidative dimerisation are often problematic and lead to mixtures of ortho- and para-connected regioisomers. To compound these issues, an intermolecular dimerisation strategy is often inappropriate for the synthesis of heterodimers. The ‘acetal method’ provides a solution for these problems: stepwise tethering of two monomeric phenols enables heterodimer synthesis, enforces ortho regioselectivity and allows relatively facile and selective intramolecular reactions to take place. The resulting dibenzo[1,3]dioxepines have been analysed by quantum chemical calculations to obtain information about the activation barrier for ring flip between the enantiomers. Hydrolytic removal of the dioxepine acetal unit revealed the 2,2′-biphenol target.