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.

Cobalt-doped ZnO nanowires on quartz: Synthesis by simple chemical method and characterization

The synthesis of cobalt-doped ZnO nanowires is achieved using a simple, metal salt decomposition growth technique. A sequence of drop casting on a quartz substrate held at 100 degrees C and annealing results in the growth of nanowires of average (modal) length similar to 200 nm and diameter of 15 +/- 4 nm and consequently an aspect ratio of similar to 13. A variation in the synthesis process, where the solution of mixed salts is deposited on the substrate at 25 degrees C, yields a grainy film structure which constitutes a useful comparator case. X-ray diffraction shows a preferred [0001] growth direction for the nanowires while a small unit cell volume contraction for Co-doped samples and data from Raman spectroscopy indicate incorporation of the Co dopant into the lattice; neither technique shows explicit evidence of cobalt oxides. Also the nanowire samples display excellent optical transmission across the entire visible range, as well as strong photoluminescence (exciton emission) in the near UV, centered at 3.25 eV. (C) 2012 Elsevier B.V. All rights reserved.

Optical and magneto-optical properties of gold core cobalt shell magnetoplasmonic nanowire arrays

In this work we present core–shell nanowire arrays of gold coated with a nanometric layer of cobalt. Despite the extremely small Co volume, these core–shell nanowires display large magneto-optical activity and plasmonic resonance determined by the geometry of the structure. Therefore, we are able to tune both the plasmonic and magneto-optical response in the visible range. Through optical and ellipsometric measurements in transmission, and applying a magnetic field to the sample, it is possible to modulate the value of the phase angle (Del {Δ}) between the S and P polarised components. It was found that the core–shell sample produced an order of magnitude larger variation in Del with changing magnetic field direction, compared with hollow cobalt tubes. The enhancement of magneto optical properties through the plasmonic nature of the gold core is complemented with the ability to induce magnetic influence over optical properties via an externally applied field. Moreover, we demonstrate for the first time the ability to use the remanent magnetisation of the Co, in conjunction with the optical properties defined by the Au, to observe remanent optical states in this uniquely designed structure. This new class of magnetoplasmonic metamaterial has great potential in a wide range of applications, from bio-sensing to data storage due to the tuneable nature of multiple resonance modes and dual functionality.

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.

Density Functional Theory Study of Iron and Cobalt Carbides for Fischer-Tropsch Synthesis

Carbides are important phases in heterogeneous catalysis. However, the understanding of carbide phases is inadequate: Fe and Co are the two commercial catalysts for Fischer-Tropsch (FT) synthesis, and experimental work showed that Fe carbide is the active phase in FT synthesis, whereas the appearance of Co carbide is considered as a possible deactivation cause, TO understand very different catalytic roles of carbides, all the key elementary steps in FT synthesis, that is, CO dissociation, C(1) hydrogenation, and C(1)+C(1) coupling, are extensively investigated on both carbide surfaces using first principles calculations. In particular, the most important issues in FT synthesis, the activity and methane selectivity, on the carbide surfaces are quantitatively determined and analyzed. They are also discussed together with metallic Fe and Co surfaces. It is found that (i) Fe carbide is more active than metallic Fe and has similar methane selectivity to Fe, being consistent with the experiments; and (ii) Co carbide is less active than Co and has higher methane selectivity, providing evidence on the molecular level to support the suggestion that the formation of Co carbide is a cause of relatively high methane selectivity and deactivation on Co catalysts.

Thermochromism and switchable paramagnetism of cobalt(ii) in thiocyanate ionic liquids

Temperature-dependent switching of paramagnetism of a cobalt(ii) complex is observed in an ionic liquid solution. Paramagnetic and thermochromic switching occur simultaneously due to a reversible change in coordination. This reversible switching is possible in the ionic liquid solution, which enables mobility of thiocyanate anions by remaining mobile at low temperatures and acts as an anion reservoir.

Three-dimensional porous carbon nanofiber networks decorated with cobalt-based nanoparticles: A robust electrocatalyst for efficient water oxidation

Electrochemical water splitting used for generating hydrogen has attracted increasingly attention due to energy and environmental issues. It is a major challenge to design an efficient, robust and inexpensive electrocatalyst to achieve preferable catalytic performance. Herein, a novel three-dimensional (3D) electrocatalyst was prepared by decorating nanostructured biological material-derived carbon nanofibers with in situ generated cobalt-based nanospheres (denoted as CNF@Co) through a facile approach. The interconnected porous 3D networks of the resulting CNF@Co catalyst provide abundant channels and interfaces, which remarkably favor both mass transfer and oxygen evolution. The as-prepared CNF@Co shows excellent electrocatalytic activity towards the oxygen evolution reactions with an onset potential of about 0.445 V vs. Ag/AgCl. It only needs a low overpotential of 314 mV to achieve a current density of 10 mA/cm² in 1.0 M KOH. Furthermore, the CNF@Co catalyst exhibits excellent stability towards water oxidation, even outperforming commercial IrO<inf>2</inf> and RuO<inf>2</inf> catalysts.

Temperature and Pressure Induced Structural Changes of Cobalt (II) in a Phosphonium Based Ionic Liquid

In this paper the temperature and pressure induced paramagnetic switching of cobalt (II) complex in binary mixture of phosphonium based ionic liquid [P6,6,6,14]SCN and [Co(NCS)2], is reported. This arises from a structural change in the coordination of the cobalt (II) center from tetrahedral [Co(NCS)4]2- to octahedral [Co(NCS)6]4- when mobile thiocyanate ions are added. These properties are reflected in the abrupt change of conductivity behavior of the magnetic ionic liquid. Therefore, as demonstrated herein the reversible switching in coordination of cobalt from tetrahedral to octahedral can be easily monitored at ambient as well as elevated pressure by tracking the dc-conductivity changes.

High performance cobalt-free Cu1.4Mn1.6O4 spinel oxide as an intermediate temperature solid oxide fuel cell cathode

In this work Cu_1.4Mn_1.6O₄ (CMO) spinel oxide is prepared and evaluated as a novel cobalt-free cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). Single phase CMO powder with cubic structure is identified using XRD. XPS results confirm that mixed Cu⁺/Cu²⁺ and Mn³⁺/Mn⁴⁺ couples exist in the CMO sample, and a maximum conductivity of 78 S cm⁻¹ is achieved at 800 °C. Meanwhile, CMO oxide shows good thermal and chemical compatibility with a 10 mol% Sc₂O₃ stabilized ZrO₂ (ScSZ) electrolyte material. Impedance spectroscopy measurements reveals that CMO exhibits a low polarization resistance of 0.143 Ω cm² at 800 °C. Furthermore, a Ni-ScSZ/ScSZ/CMO single cell demonstrates a maximum power density of 1076 mW cm⁻² at 800 °C under H₂ (3% H₂O) as the fuel and ambient air as the oxidant. These results indicate that Cu_1.4Mn_1.6O₄ is a superior and promising cathode material for IT-SOFCs.

Synthesis of Pr0.6Sr0.4FeO 3-δ -xCe0.9Pr0.1O 2-δ cobalt-free composite cathodes by a one-pot method for intermediate-temperature solid oxide fuel cells

Cobalt-free composite cathodes consisting of Pr_0.6Sr_0.4FeO _3-δ -xCe_0.9Pr_0.1O _2-δ (PSFO-xCPO, x = 0-50 wt%) have been synthesized using a one-pot method. X-ray diffraction, scanning electron microscopy, thermal expansion coefficient, conductivity, and polarization resistance (R _P ) have been used to characterize the PSFO-xCPO cathodes. Furthermore the discharge performance of the Ni-SSZ/SSZ/GDC/PSFO-xCPO cells has been measured. The experimental results indicate that the PSFO-xCPO composite materials fully consist of PSFO and CPO phases and posses a porous microstructure. The conductivity of PSFO-xCPO decreases with the increase of CPO content, but R _P of PSFO-40CPO shows the smallest value amongst all the samples. The power density of single cells with a PSFO-40CPO composite cathode is significantly improved compared with that of the PSFO cathode, exhibiting 0.43, 0.75, 1.08 and 1.30 W cm^-2 at 650, 700, 750 and 800 °C, respectively. In addition, single cells with the PSFO-40CPO composite cathode show a stable performance with no obvious degradation over 100 h when operating at 750 °C.

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.