Perovskite lead zirconium titanate nanorings: Towards nanoscale ferroelectric

Rings of perovskite lead zirconium titanate (PZT) with internal diameters down to similar to 5 nm and ring thicknesses of similar to 5-10 nm have been fabricated and structurally, crystallographically, and chemically characterized using an analytical transmission electron microscope. Ring fabrication involved conformal solution deposition of a thin layer of PZT on the inside of a thin film of anodized aluminum oxide nanopores, and subsequent sectioning of the coated pores perpendicular to their cylinder axes. Although the starting solution used for the solution deposition was made from morphotropic phase boundary PZT, the nanorings were found to be on the zirconium-rich side of the PZT phase diagram. Nevertheless, coatings were found to be of perovskite crystallography. The dimensions of these nanorings are such that they have the potential to demonstrate polarization vortices, as modeled by Naumov [Nature (London) 432, 737 (2004)], and moreover represent the perfect morphology to allow vortex alignment and the creation of the ferroelectric "solenoid" as modeled by Gorbatsevich and Kopaev [Ferroelectrics 161, 321 (1994)].

Ordered arrays of lead zirconium titanate nanorings

Periodic arrays of nanorings of morphotropic phase boundary lead zirconium titanate ( PZT) have been successfully fabricated using a novel self-assembly technique: close-packed monolayers of latex nanospheres were deposited onto Pt-coated silicon substrates, and then plasma cleaned to form ordered arrays of isolated nanospheres, not in contact with each other. Subsequent pulsed laser deposition of PZT, high angle argon ion etching and thermal annealing created the arrays of isolated nanorings, with diameters of similar to 100 nm and wall thicknesses of similar to 10 nm. Energy dispersive x-ray analysis confirms that the rings are compositionally morphotropic phase boundary PZT, and high resolution transmission electron microscopy imaging of lattice fringes demonstrates some periodicities consistent with perovskite rather than pyrochlore material. The dimensions of these nanorings, and the expected 'soft' behaviour of the ferroelectric material from which they are made, means that they offer the most likely opportunity to date for observing whether or not vortex arrangements of electrical dipoles, analogous to those seen in ferromagnetic nanostructures, actually exist.

Mid-infrared a-b plane response of YBa2Cu3O7-delta as a function of doping and temperature determined by attenuated total reflection

The mid-infrared optical response of c-axis thin films of YBa2Cu3O7-delta has been studied using Otto-configuration attenuated total reflectance. The measured reflectance-angle characteristics are dominated by a strong absorption feature due to the excitation of surface plasmons, and can be modeled to determine the a-b plane dielectric function. The results show that while epsilon(i,) and therefore sigma(r), are temperature independent, \epsilon(r)\ exhibits a moderate decrease with generalized Drude analysis shows that the plasma frequency is independent of temperature, but decreases with decreasing doping. The scattering rate increases with temperature, and also increases with decreasing doping, consistent with stronger coupling in the underdoped regime. The mass-enhancement is small but increases to 30-40% at delta = 0.6. Difficulties in reconciling the results with some current theories of high-T-c materials are discussed. Finally, the surface plasmon propagation lengths and penetration depths are shown to vary systematically with doping. (C) 2003 Elsevier B.V. All rights reserved.

Doping, sport and the law: time for repeal of prohibition?

This article concerns the legal issues that surround the prohibition of doping in sport. The current policy on the use of performance enhancing drugs (PEDs) in sport is underpinned by both a paternalistic desire to protect athletes’ health and the long-term integrity or ‘spirit’ of sport. The policy is put into administrative effect globally by the World Anti-Doping Agency (WADA), which provides the regulatory and legal framework through which the vast majority of international sports federations harmonise their anti-doping programmes. On outlining briefly both the broad administrative structures of international sport’s various anti-doping mechanisms, and specific legal issues that arise in disciplinary hearings involving athletes accused of doping, this article questions the sustainability of the current ‘zero tolerance’ approach, arguing, by way of analogy to the wider societal debate on the criminalisation of drugs, and as informed by Sunstein and Thaler’s theory of libertarian paternalism, that current policy on anti-doping has failed. Moreover, rather than the extant moral and punitive panic regarding doping in sport, this article, drawing respectively on Seddon’s and Simon’s work on the history of drugs and crime control mentality, contends that, as an alternative, harm reductionist measures should be promoted, including consideration of the medically supervised use of certain PEDs.

Synthesis and NMR Characterization of Titanium and Zirconium Oxides Incorporated in SBA-15

Single oxides of Ti and Zr incorporated SBA-15 were prepared and characterized by N-2 adsorption, NMR, and XPS techniques. Si-29 MAS NMR results suggest the formation of Si-O-X linkages (X: Ti or Zr) by an increase in the ratio of Q(3)/Q(4) in the presence of Ti or Zr. XPS analysis of Ti-SBA-15 catalysts indicate the presence of Ti-O-Si bonds in addition to Ti-O-Ti and Si-O-Si bonds, supporting the NMR evidence.

Improved diffusive gradients in thin films (DGT) measurement of total dissolved inorganic arsenic in waters and soils using a hydrous zirconium oxide binding layer

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A high-capacity diffusive gradients in thin films (DGT) technique has been developed for measurement of total dissolved inorganic arsenic (As) using a long shelf life binding gel layer containing hydrous zirconium oxide (Zr-oxide). Both As(III) and As(V) were rapidly accumulated in the Zr-oxide gel and could be quantitatively recovered by elution using 1.0 M NaOH for freshwater or a mixture of 1.0 M NaOH and 1.0 M H2O2 for seawater. DGT uptake of As(III) and As(V) increased linearly with deployment time and was independent of pH (2.0–9.1), ionic strength (0.01–750 mM), the coexistence of phosphate (0.25–10 mg P L–1), and the aging of the Zr-oxide gel up to 24 months after production. The capacities of the Zr-oxide DGT were 159 μg As(III) and 434 μg As(V) per device for freshwater and 94 μg As(III) and 152 μg As(V) per device for seawater. These values were 5–29 times and 3–19 times more than those reported for the commonly used ferrihydrite and Metsorb DGTs, respectively. Deployments of the Zr-oxide DGT in As-spiked synthetic seawater provided accurate measurements of total dissolved inorganic As over the 96 h deployment, whereas ferrihydrite and Metsorb DGTs only measured the concentrations accurately up to 24 and 48 h, respectively. Deployments in soils showed that the Zr-oxide DGT was a reliable and robust tool, even for soil samples heavily polluted with As. In contrast, As in these soils was underestimated by ferrihydrite and Metsorb DGTs due to insufficient effective capacities, which were likely suppressed by the competing effects of phosphate.

LC- HRMS based metabolomics in food safety and doping control – DeTECH21

Issues surrounding the misuse of prohibited and licensed substances in animals destined for food production and performance sport competition continue to be an enormous challenge to regulatory authorities charged with enforcing their control. Efficient analytical strategies are implemented to screen and confirm the presence of a wide range of exogenous substances in various biological matrices. However, such methods rely on the direct measurement of drugs and/or their metabolites in a targeted mode, allowing the detection of restricted number of compounds. As a consequence, emerging practices, in particular the use of natural hormones, designer drugs and low-dose cocktails, remain difficult to handle from a control point of view. A new SME-led FP7 funded project, DeTECH21, aims to overcome current limitations by applying an untargeted metabolomics approach based on liquid chromatography coupled to high resolution mass spectrometry and bioinformatic data analysis to identify bovine and equine animals which have been exposed to exogenous substances and assist in the identification of administered compounds. Markerbased strategies, dealing with the comprehensive analysis of metabolites present in a biological sample (urine/plasma/tissue), offer a reliable solution in the areas of food safety and animal sport doping control by effective, high-throughput and sensitive detection of exogenously administered agents. Therefore, the development of the first commercially available forensic test service based on metabolomics profiling will meet 21st century demands in animal forensics.

Theoretical Study of Heteroatom Doping in Tuning the Catalytic Activity of Graphene for Triiodide Reduction

Graphene with heteroatom doping has found increasing applications in a broad range of catalytic reactions. However, the doping effects accounting for the enhanced catalytic activity still remain elusive. In this work, taking the triiodide electroreduction reaction as an example, we study systematically the intrinsic activity of graphene and explore the origin of doping-induced activity variation using first-principles calculations, in which two typical N and S dopants are tested. The most common graphene structures, basal plane, armchair edge, and zigzag edge, are considered, and it is found that the former two structures show a weak adsorption ability for the iodine atom (the key intermediate in the triiodide electroreduction reaction), corresponding to a low catalytic activity. Doping either N or S can strengthen the adsorption and thus increase the activity, and the codoping of N and S (NS-G) exhibits a synergistic effect. A detailed investigation into the whole process of the triiodide electroreduction reaction at the CH3CN/NS-G interface is also carried out to verify these activity trends. It is found that the zigzag edges which contain spin electrons show a relatively stronger adsorption strength compared with the basal plane and armchair edge, and initial doping would result in the spin disappearance that evidently weakens the adsorption; with the disappearance of spin, however, further doping can increase the adsorption again, suggesting that the spin electrons may play a preliminary role in affecting the intrinsic activity of graphene. We also analyzed extensively the origin of doping-induced adsorption enhancement of graphene in the absence of spin; it can be rationalized from the electronic and geometric factors. Specifically, N doping can result in a more delocalized “electron-donating area” to enhance I adsorption, while S doping provides a localized structural distortion, which activates the nearest sp2-C into coordinatively unsaturated sp3-C. These results explain well the improved activity of the doping and the synergistic effect of the codoping. The understandings are generalized to provide insight into the enhanced activity of the oxygen reduction reaction on heteroatom doped graphene. This work may be of importance toward the design of high-activity graphene based material.