Ultrafast Electrochemical Self-Doping of Anodic Titanium Dioxide Nanotubes for Enhanced Electroanalytical and Photocatalytic Performance

This study explores an ultrarapid electrochemical self-doping procedure applied to anodic titanium dioxide (TiO2) nanotube arrays in an alkaline solution to boost their performance for electroanalytical and photocatalytic applications. The electrochemical self-doping process (i.e., the creation of surface Ti3+ states by applying a negative potential) is recently emerging as a simpler and cleaner way to improve the electronic properties of TiO2 compared to traditional chemical and high-temperature doping strategies. Here, self-doping was carried out through varying voltages and treatment times to identify the most performing materials without compromising their structural stability. Interestingly, cyclic voltammetry characterization revealed that undoped TiO2 shows negligible activity, whereas all self-doped materials demonstrate their suitability as electrode materials: an outstandingly short 10 s self-doping treatment leads to the highest electrochemical activity. The electrochemical detection of hydrogen peroxide was assessed as well, demonstrating a good sensitivity and a linear detection range of 3–200 µM. Additionally, the self-doped TiO2 nanotubes exhibited an enhanced photocatalytic activity compared to the untreated substrate: the degradation potential of methylene blue under UV light exposure increased by 25% in comparison to undoped materials. Overall, this study highlights the potential of ultrafast electrochemical self-doping to unleash and improve TiO2 nanotubes performances for electroanalytical and photocatalytic applications

Zooplankton as an indicator of the status of contamination of the Mediterranean Sea and temporal trends

Zooplankton has been intensively used as bioindicators of water pollution at global level, however, only few comprehensive studies have been conducted from the Mediterranean Sea and manly dated back to the 1970s. To redress the urgent need for updated data, this study provides information on the presence and levels of contaminants in zooplankton from the Tyrrhenian Sea. Although banned, both PCBs (46.9 +/- 37.2 ng g-1) and DDT (8.9 +/- 10.7 ng g-1) are still present and widespread, but their contamination appears to be a local problem and to be declining over the past 50 years. Zooplankton accumulates high levels of certain TEs, including Zn (400 +/- 388 ppm) and Pb (35.3 +/- 45.5 ppm), but shows intermediate concentrations of other TEs, including Cd (1.6 +/- 0.9 ppm) and Hg (0.1 +/- 0.1 ppm), comparing with both strongly polluted and more pristine marine habitats, which may reflect a general improvement

Dynamic surface electromyography using stretchable screen-printed textile electrodes

Objective. Wearable devices have created new opportunities in healthcare and sport sciences by unobtrusively monitoring physiological signals. Textile polymer-based electrodes proved to be effective in detecting electrophysiological potentials but suffer mechanical fragility and low stretch resistance. The goal of this research is to develop and validate in dynamic conditions cost-effective and easily manufacturable electrodes characterized by adequate robustness and signal quality. Methods. We here propose an optimized screen printing technique for the fabrication of PEDOT:PSS-based textile electrodes directly into finished stretchable garments for surface electromyography (sEMG) applications. A sensorised stretchable leg sleeve was developed, targeting five muscles of interest in rehabilitation and sport science. An experimental validation was performed to assess the accuracy of signal detection during dynamic exercises, including sit-to-stand, leg extension, calf raise, walking, and cycling. Results. The electrodes can resist up to 500 stretch cycles. Tests on five subjects revealed excellent contact impedance, and cross-correlation between sEMG envelopes simultaneously detected from the leg muscles by the textile and Ag/AgCl electrodes was generally greater than 0.9, which proves that it is possible to obtain good quality signals with performance comparable with disposable electrodes. Conclusions. An effective technique to embed polymer-based electrodes in stretchable smart garments was presented, revealing good performance for dynamic sEMG detections. Significance. The achieved results pave the way to the integration of unobtrusive electrodes, obtained by screen printing of conductive polymers, into technical fabrics for rehabilitation and sport monitoring, and in general where the detection of sEMG in dynamic conditions is necessary

How to clean and safely remove HF from acid digestion solutions for ultra-trace analysis: a microwave-assisted vessel-inside-vessel protocol

The complete dissolution of silicate-containing materials, often necessary for elemental determination, is generally performed by microwave-assisted digestion involving the forced use of hydrofluoric acid (HF). Although highly efficient in dissolving silicates, this acid exhibits many detrimental effects (e.g., formation of precipitates, corrosiveness to glassware) that make its removal after digestion essential. The displacement of HF is normally achieved by evaporation in open-vessel systems: atmospheric contamination or loss of analytes can occur when fuming-off HF owing to the non-ultraclean conditions necessarily adopted for safety reasons. This aspect strongly hinders determination at the ultra-trace level. To overcome this issue, we propose a clean and safe microwaveassisted procedure to induce the evaporative migration of HF inside a sealed \u201cvessel-inside-vessel\u201d system: up to 99.9% of HF can be removed by performing two additional microwave cycles after sample dissolution. HF migrates from the digestion solution to a scavenger (ultrapure H2O) via a simple physical mechanism, and then, it can be safely dismissed/recycled. The procedure was validated by a soil reference material (NIST 2710), and no external or cross-contamination was observed for the 27 trace elements studied. The results demonstrate the suitability of this protocol for ultra-trace analysis when the utilization of HF is mandatory

Exploring the Adsorption of Pb on Microalgae-Derived Biochar: A Versatile Material for Environmental Remediation and Electroanalytical Applications

Biochar, a carbon material obtained by pyrolysis of biomasses, is increasingly applied in environmental remediation and sensing thanks to its functional properties, cost-effectiveness and eco-friendliness. The adsorption capacity of biochar, strictly dependent on its specific surface area, heteroatom doping and surface functional groups, is crucial for these applications. Here, biochar produced at low temperature (350◦ C) from a marine microalga (Nannochloropsis sp.) is proposed as an efficient adsorbent of lead (II) ions in aqueous solution; this production strategy promotes the natural self-doping of biochar without requiring harsh conditions. The kinetics and thermodynamics of the adsorption process, as well as the effect of pH, ionic strength and dissolved organic matter on the adsorption efficiency were systematically assessed. The microalgae-derived biochar shows superior adsorption performances compared to a nutshell-derived one (used as a reference of lignocellulosic feedstocks) under all the tested conditions. The microalgae-derived biochar was finally used to decorate screen-printed carbon electrodes to improve the electroanalytical performances towards the voltammetric detection of lead (II) ions. A two-fold increase in sensitivity was obtained compared to the unmodified electrode thanks to the enhanced electron transfer and adsorption properties provided by biochar. These results highlight the potentialities of microalgae-derived biochar for environmental and sensing applications

Weakly frustrated two-dimensional Heisenberg antiferromagnets: thermodynamic properties from a non-perturbative approach

We analyze the thermodynamic properties of the spin-S two-dimensional quantum Heisenberg antiferromagnet on a square lattice with nearest and next-nearest neighbor couplings in the Neel phase (J_2/J_1<0.4) employing the quantum hierarchical reference theory (QHRT), a non-perturbative implementation of the renormalization group method to quantum systems. We investigate the staggered susceptibility, the structure factors and the correlation length at finite temperature and for different values of the frustration ratio. From the finite temperature results, we also extrapolate ground state properties, such as spin stiffness and spontaneous staggered magnetization, providing an estimate of the extent of quantum corrections. The behavior of these quantities as a function of frustration may provide some hint on the breakdown of the Neel phase at zero temperature for larger values of J_2

Parylene C-based, breathable tattoo electrode for high-quality biopotential measurements

A breathable tattoo electrode for bio-potential recording based on a Parylene C nanofilm is presented in this study. The proposed approach allows for the fabrication of micro-perforated epidermal submicrometer-thick electrodes that conjugate the unobtrusiveness of Parylene C nanofilms and the very important feature of breathability. The electrodes were fully validated for electrocardiography (ECG) measurements showing performance comparable to that of conventional disposable gelled Ag/AgCl electrodes, with no visible negative effect on the skin even many hours after their application. This result introduces interesting perspectives in the field of epidermal electronics, particularly in applications where critical on-body measurements are involved

Spin dynamics in molecular ring nanomagnets: Significant effect of acoustic phonons and magnetic anisotropies

The nuclear spin-lattice relaxation rate 1/T_1_ is calculated for magnetic ring clusters by fully diagonalizing their microscopic spin Hamiltonians. Whether the nearest-neighbor exchange interaction J is ferromagnetic or antiferromagnetic, 1/T_1_ versus temperature T in ring nanomagnets may be peaked at around k_B_T=|J| provided the lifetime broadening of discrete energy levels is in proportion to T^3^. Experimental findings for ferromagnetic and antiferromagnetic Cu^II^ rings are reproduced with crucial contributions of magnetic anisotropies as well as acoustic phonons.Comment: 5 pages with 5 figures embedded, to be published in J. Phys. Soc. Jpn. 75, No. 10 (2006