Influence of oxidation and reduction conditions upon the morphology of silica-supported polycrystalline silver catalysts

The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.

Morphology of osteocyte cells in normal and hyper-gravity

Osteocyte cells are the most abundant cells in human bone tissue. Due to their unique morphology and location, osteocyte cells are thought to act as regulators in the bone remodelling process, and are believed to play an important role in astronauts’ bone mass loss after long-term space missions. There is increasing evidence showing that an osteocyte’s functions are highly affected by its morphology. However, changes in an osteocyte’s morphology under an altered gravity environment are still not well documented. Several in vitro studies have been recently conducted to investigate the morphological response of osteocyte cells to the microgravity environment, where osteocyte cells were cultured on a two-dimensional flat surface for at least 24 hours before microgravity experiments. Morphology changes of osteocyte cells in microgravity were then studied by comparing the cell area to 1g control cells. However, osteocyte cells found in vivo are with a more 3D morphology, and both cell body and dendritic processes are found sensitive to mechanical loadings. A round shape osteocyte’s cells support a less stiff cytoskeleton and are more sensitive to mechanical stimulations compared with flat cellular morphology. Thus, the relative flat and spread shape of isolated osteocytes in 2D culture may greatly hamper their sensitivity to a mechanical stimulus, and the lack of knowledge on the osteocyte’s morphological characteristics in culture may lead to subjective and noncomprehensive conclusions of how altered gravity impacts on an osteocyte’s morphology. Through this work empirical models were developed to quantitatively predicate the changes of morphology in osteocyte cell lines (MLO-Y4) in culture, and the response of osteocyte cells, which are relatively round in shape, to hyper-gravity stimulation has also been investigated. The morphology changes of MLO-Y4 cells in culture were quantified by measuring cell area and three dimensionless shape features including aspect ratio, circularity and solidity by using widely accepted image analysis software (ImageJTM). MLO-Y4 cells were cultured at low density (5×103 per well) and the changes in morphology were recorded over 10 hours. Based on the data obtained from the imaging analysis, empirical models were developed using the non-linear regression method. The developed empirical models accurately predict the morphology of MLO-Y4 cells for different culture times and can, therefore, be used as a reference model for analysing MLO-Y4 cell morphology changes within various biological/mechanical studies, as necessary. The morphological response of MLO-Y4 cells with a relatively round morphology to hyper-gravity environment has been investigated using a centrifuge. After 2 hours culture, MLO-Y4 cells were exposed to 20g for 30mins. Changes in the morphology of MLO-Y4 cells are quantitatively analysed by measuring the average value of cell area and dimensionless shape factors such as aspect ratio, solidity and circularity. In this study, no significant morphology changes were detected in MLO-Y4 cells under a hyper-gravity environment (20g for 30 mins) compared with 1g control cells.

Variation in leaf morphology of the invasive cat's claw creeper Dolichandra unguis-cati (Bignoniaceae)

The invasive liana cat’s claw creeper Dolichandra unguis-cati (L.) L.G. Lohmann (syn. Macfadyena unguis-cati (L.) A.H. Gentry) exhibits intraspecific variation in leaf morphology, but this is rarely noted in the published literature. The present study documents variation in leaf morphology in two forms of the species that occur in Australia (long pod and short pod). Leaf morphology is compared between the two forms and the position of the shoots (trunk and ground) at the only two sites in which they co-occur. Leaves were categorised on the basis of leaflet number and the presence or absence of tendrils. Simple leaves were produced mainly on shoots growing along the ground and were more abundant in the short-pod form. Long-pod plants were dominated by bifoliate leaves with tendrils. Cat’s claw creeper exhibits considerably wider variation in leaf morphology than recorded previously. Variations in leaf morphology may be linked to differences in the genotype, developmental stage and plastic responses of the plants. Understanding these variations may have implications for taxonomic delimitation and improved management, particularly biological control involving leaf-feeding insects.

Zeta-potential and morphology of electrospun nano- and microfibers from biopolymers and their blends used as scaffolds in tissue engineering

Electrostatic spinning or electrospinning is a fiber spinning technique driven by a high-voltage electric field that produces fibers with diameters in a submicrometer to nanometer range.1 Nanofibers are typical one-dimensional colloidal objects with an increased tensile strength, whose length can achieve a few kilometers and the specific surface area can be 100 m2 g–1 or higher.2 Nano- and microfibers from biocompatible polymers and biopolymers have received much attention in medical applications3 including biomedical structural elements (scaffolding used in tissue engineering,2,4–6 wound dressing,7 artificial organs and vascular grafts8), drug and vaccine delivery,9–11 protective shields in speciality fabrics, multifunctional membranes, etc. Other applications concern superhydrophobic coatings,12 encapsulation of solid materials,13 filter media for submicron particles in separation industry, composite reinforcement and structures for nano-electronic machines.

YBa2Cu3O7-x films on yttria-stabilized ZrO2 substrates : influence of the substrate morphology

c-axis-oriented YBa2Cu3O7-x (YBCO) thin films were laser deposited on (001) yttria-stabilized ZrO2 (YSZ) substrates with different surface morphologies. The in-plane orientation of the films on smooth substrates was sensitive to the deposition conditions, often resulting in mixed orientations. However, a strongly dominating [110] YBCO//[110]YSZ orientation was obtained at a deposition temperature of 770°C. Films on substrates with surface steps, induced by depositing a homoepitaxial buffer layer or by thermally annealing the substrate, had a [110]YBCO//[100]YSZ orientation when deposited at the same temperature. It was concluded that the [110]YBCO//[100] YSZ orientation was promoted by a graphoepitaxial mechanism. Films prepared under identical conditions on smooth and stepped substrates grew with extended c axes on the former. It is proposed that the extension can be induced by disorder, invoked by a low oxygen pressure and a low density of adsorption sites. The disorder may be eliminated by either an increase of the oxygen pressure or an increase of the density of adsorption sites in the form of steps. The film microstructure influenced the microwave surface resistance, which was similar for films with one exclusive in-plane orientation and higher for films with mixed orientations. The films on the stepped surfaces had superior superconducting properties; inductive measurements gave a Tc onset of 88 K, a ΔT(90%-10%) c of 0.2 K, and the transport jc was 1.5×106 A/cm2 at 83 K, for films on substrates with homoepitaxial buffer layers.

Morphology changes and mechanistic aspects of the electrochemically-induced reversible solid-solid transformation of microcrystalline TCNQ into Co TCNQ 2-based materials (TCNQ= 7, 7, 8, 8-Tetracyanoquinodimethane)

The chemically reversible solid−solid phase transformation of a TCNQ-modified glassy carbon, indium tin oxide, or metal electrode into Co\[TCNQ]2(H2O)2 material in the presence of Co2+(aq) containing electrolytes has been induced and monitored electrochemically. Voltammetric data reveal that the TCNQ/Co\[TCNQ]2(H2O)2 interconversion process is independent of electrode material and identity of cobalt electrolyte anion. However, a marked dependence on electrolyte concentration, scan rate, and method of electrode modification (drop casting or mechanical attachment) is found. Cyclic voltammetric and double potential step chronoamperometric measurements confirm that formation of Co\[TCNQ]2(H2O)2 occurs through a rate-determining nucleation and growth process that initially involves incorporation of Co2+(aq) ions into the reduced TCNQ crystal lattice at the TCNQ|electrode|electrolyte interface. Similarly, the reverse (oxidation) process, which involves transformation of solid Co\[TCNQ]2(H2O)2 back to parent TCNQ crystals, also is controlled by nucleation−growth kinetics. The overall chemically reversible process that represents this transformation is described by the reaction:  2TCNQ0(s) + 2e- + Co2+(aq) + 2H2O \[Co(TCNQ)2(H2O)2](s). Ex situ SEM images illustrated that this reversible TCNQ/Co\[TCNQ]2(H2O)2 conversion process is accompanied by drastic size and morphology changes in the parent solid TCNQ. In addition, different sizes of needle-shaped nanorod/nanowire crystals of Co\[TCNQ]2(H2O)2 are formed depending on the method of surface immobilization.

An investigation of silver electrodeposition from ionic liquids : influence of atmospheric water uptake on the silver electrodeposition mechanism and film morphology

The electrodeposition of silver from two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) and N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide ([C4mPyr][TFSI]), and an aqueous KNO3 solution on a glassy carbon electrode was undertaken. It was found by cyclic voltammetry that the electrodeposition of silver proceeds through nucleation–growth kinetics. Analysis of chronoamperometric data indicated that the nucleation–growth mechanism is instantaneous at all potentials in the case of [BMIm][BF4] and [C4mPyr][TFSI], and instantaneous at low overpotentials tending to progressive at high overpotentials for KNO3. Significantly, under ambient conditions, the silver electrodeposition mechanism changes to progressive nucleation and growth in [C4mPyr][TFSI], which is attributed to the uptake of atmospheric water in the IL. It was found that these differences in the growth mechanism impact significantly on the morphology of the resultant electrodeposit which is characterised ex situ by scanning electron microscopy and X-ray diffraction.

Effect of Imidazolium-based Ionic Liquids on the nanoscale morphology of CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane) metal-organic semiconductors

We demonstrate for the first time the ionic-liquid-mediated synthesis of nanostructured CuTCNQ by the simple immersion of copper in a solution of TCNQ where the viscosity of the medium significantly impacts the corrosion–crystallization process and the final morphology of the material.

Promising interventions for reducing Indigenous juvenile offending

Indigenous juveniles (those aged 10 to 16 years in Queensland and 10 to 17 years in all other jurisdictions) are over-represented at all stages of the criminal justice system, and their over-representation becomes more pronounced at the most severe end of the system (ie in detention). Recent figures show that Indigenous juveniles are 24 times as likely to be detained in a juvenile correctional facility as non-Indigenous juveniles (Richards & Lyneham 2010). A variety of explanations for this over-representation have been proposed, including: • lack of access or disparate access to diversionary programs (Allard et al. 2010; Cunneen 2008; Snowball 2008); • systemic discrimination against Indigenous juveniles (eg police bias against Indigenous juveniles) (Cunneen 2008; Kenny & Lennings 2007); • inadequate resourcing of Aboriginal legal services (Cunneen & Schwartz 2008); and • genuinely higher levels of offending by Indigenous juveniles (Kenny & Lennings 2007; Weatherburn et al. 2003). A range of measures (including diversion and juvenile conferencing programs) has recently been implemented to reduce the over-representation of Indigenous juveniles in detention, and minimise the contact of juveniles with the formal criminal justice system. Diversionary measures can only have a limited impact, however, and reducing offending and reoffending have been identified as critical factors to address if the over-representation of Indigenous juveniles is to be reduced (Allard et al. 2010; Weatherburn et al. 2003). While acknowledging that other measures designed to reduce the over-representation of Indigenous juveniles are important, this paper reviews the evidence on policies and programs that reduce offending by Indigenous juveniles in Australia. Where relevant, research from comparable jurisdictions, such as New Zealand and Canada, is also discussed.

What makes juvenile offenders different from adult offenders?

Historically, children in criminal justice proceedings were treated much the same as adults and subject to the same criminal justice processes as adults. Until the early twentieth century, children in Australia were even subjected to the same penalties as adults, including hard labour and corporal and capital punishment (Carrington & Pereira 2009). Until the mid-nineteenth century, there was no separate category of ’juvenile offender’ in Western legal systems and children as young as six years of age were incarcerated in Australian prisons (Cunneen & White 2007). It is widely acknowledged today, however, both in Australia and internationally, that juveniles should be subject to a system of criminal justice that is separate from the adult system and that recognises their inexperience and immaturity. As such, juveniles are typically dealt with separately from adults and treated less harshly than their adult counterparts. The United Nations’ (1985: 2) Standard Minimum Rules for the Administration of Juvenile Justice (the ‘Beijing Rules’) stress the importance of nations establishing a set of laws, rules and provisions specifically applicable to juvenile offenders and institutions and bodies entrusted with the functions of the administration of juvenile justice and designed to meet the varying needs of juvenile offenders, while protecting their basic rights. In each Australian jurisdiction, except Queensland, a juvenile is defined as a person aged between 10 and 17 years of age, inclusive. In Queensland, a juvenile is defined as a person aged between 10 and 16 years, inclusive. In all jurisdictions, the minimum age of criminal responsibility is 10 years. That is, children under 10 years of age cannot be held legally responsible for their actions.

Trends in juvenile detention in Australia

This paper provides an overview of key trends in juvenile detention in Australia, based on data contained in the Australian Institute of Criminology’s (AIC’s) Juveniles in Detention in Australia Monitoring Program database and then provides a discussion of two key trends in juvenile detention—the national increase in the proportion of juvenile detainees that is remanded (rather than sentenced) and the increase in the over-representation of Indigenous juveniles in detention.

Beyond the ‘three dogmas of juvenile justice’ : a response to Weatherburn, McGrath and Bartels

In 'Three Dogmas of Juvenile Justice', Weatherburn, McGrath and Bartels identify three 'assumptions' or 'dogmas' about youth justice, on which they claim 'juvenile justice policy in Australia currently rests'.