Recent advances in graphite powder-based electrodes

Graphite powder-based electrodes have the electrochemical performance of quasi-noble metal electrodes with intrinsic advantages related to the possibility of modification to enhance selectivity and their easily renewable surface, with no need for hazardous acids or bases for their cleaning. In contrast with commercial electrodes, for example screen-printed or sputtered-chip electrodes, graphite powder-based electrodes can also be fabricated in any laboratory with the form and characteristics desired. They are also readily modified with advanced materials, with relatively high reproducibility. All these characteristics make them a very interesting option for obtaining a large variety of electrodes to resolve different kinds of analytical problems. This review summarizes the state-of-the-art, advantages, and disadvantages of graphite powder-based electrodes in electrochemical analysis in the 21st century. It includes recent trends in carbon paste electrodes, devoting special attention to the use of emergent materials as new binders and to the development of other composite electrodes. The most recent advances in the use of graphite powder-modified sol–gel electrodes are also described. The development of sonogel–carbon electrodes and their use in electrochemical sensors and biosensors is included. These materials extend the possibilities of applications, especially for industrial technology-transfer purposes, and their development could affect not only electroanalytical green chemistry but other interesting areas also, for example catalysis and energy conversion and storage.     

Comparative study of bulk and partial digestion methods for airborne PM10-bound elements in a high mineral dust urban site in Constantine,Algeria

When high mineral loads in atmospheric particulate matter (PM) are present, particular attention should be paid to the selection of appropriate acidic digestion protocols for wet chemical analysis. We report on a comparative study of elemental recovery yields from five different pre-analytical acid digestion procedures for mineral-rich urban background PM₁₀ samples collected in the city of Constantine (Northeastern Algeria). Five reference materials (NIST 1633b, UPM 1648, NAT-7, SO-2 and SO-4) were also digested according to the same protocols. The selected acidic digestion/extraction procedures are widely used for PM chemical analysis and comprise P1 (HNO₃/HF/HCl), P2 (HCl/HNO₃), P3 (HCl/H₂O₂/HNO₃), P4 (HNO₃/HF/HClO₄) and P5 (HNO₃/H₂O₂); the latter assisted with microwave digestion. Elemental recovery yields were compared for major and trace elements typically determined in PM for source apportionment analysis and the results evidenced large differences. For most elements, the bulk extraction procedures (requiring the use of HF) allowed a full elemental recovery, particularly for elements that are associated with aluminium silicate species and oxides that are resistant to mild acid attack. In contrast, in the extraction protocols without HF low recovery yields were obtained for elements such as Al, Ti, Zr, Sc and other aluminium silicate-related elements in PM₁₀ samples with high mineral dust load. We highlight that the European standard digestion method EN-14902:2005 should be applied specifically for the metals for which this method was developed, but caution should be taken when the analysis of other elements in PM is required, especially in urban areas where road and vehicle wear dust is likely to be a major component of ambient PM. When using wet chemistry analysis for PM source apportionment studies, we strongly recommend HF bulk dissolution of samples to ensure the reliability of the geochemical information when coupled with an appropriate analytical tool.     

Magnetic–fluorescent Langmuir–Blodgett films of fluorophore-labeled ferritin nanoparticles

We have covalently coupled fluorophore 4-(2-hydroxyethoxy)-7-nitro-2,1,3-benzoxadiazole (NBD) to the external ferritin shell through lysine residues. An increase in the luminescence quantum yield of the fluorescent ferritin particles and a blue shift in its emission peak compared to individual fluorophore were observed. The study of the particles by transmission electron microscopy showed that the native iron core ferritin is intact and that no degradation occurs during chemical functionalization of the protein shell. The NBD-labeled ferritin particles are water soluble, which allowed their controlled deposition by the Langmuir–Blodgett (LB) technique. Superparamagnetic and fluorescent properties of the particles are preserved within the LB film.     

Preparation and Characterization of Compositions Based on PbO-MgO-Nb2O5 Using the Sol-Gel Method

Lead Magnesium Niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), is an important relaxor ferroelectric material. A significant problem exists, however, in the preparation of this material: it is very difficult to prepare pure phase, without the presence of a pyrochlore impurity phase which degrades the dielectric properties. Depending on the processing conditions, the amount of pyrochlore phase varies.Considering the ternary diagram PbO-MgO-Nb₂O₅, different compositions have been prepared by a simple sol-gel method at room temperature using Pb(CH₃COO)₂, Mg(CH₃COO)₂, Nb(OC₂H₅)₅ as precursors. After the heat treatment, the samples obtained were analyzed by XRD and EPMA with the purpose of studying the compositions formed.From the analysis of these results, it seems to be that the appearance of pyrochlore can be related to the reactivity of the MgO and/or the presence of other phases of the binary system PbO-Nb₂O₅. An excess of Pb and Mg is necessary for compositions to be formed near the PMN. The control of the amount of these two elements is very important because an excess of MgO would lead to rich compositions in Mg as a secondary phase.     

Nanoscale organization of a phthalocyanine-fullerene system: remarkable stabilization of charges in photoactive 1-D nanotubules

Induction of self-organization between zinc phthalocyanine (ZnPc) and C60 moieties in a novel amphiphilic ZnPc-C60 salt results in uniformly nanostructured 1-D nanotubules. Their photoreactivity, in terms of ultrafast charge separation (i.e., approximately 1012 s-1) and ultraslow charge recombination (i.e., approximately 103 s-1), is remarkable. In addition, the observed ZnPc*+-C60*- lifetime of 1.4 ms implies, relative to that of the monomeric ZnPc-C60 ( approximately 3 ns), an impressive stabilization of 6 orders of magnitude.     

Use of gas chromatography/mass spectrometry with positive chemical ionization for the determination of opiates in human oral fluid

An analytical method for the simultaneous determination of codeine, morphine and 6-acetylmorphine (6AM) in human oral fluid was developed. The method involves liquid-liquid extraction in Toxitubes A, derivatization with 99:1 (v/v) N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA)/trimethylchlorosilane (TMCS), and gas chromatography/mass spectrometry with positive chemical ionization (GC/PCI-MS) determination. The detector response was linear over the concentration range 30-500 ng/mL with coefficients of correlation higher than 0.99. The precision was acceptable with coefficients of variation less than 7.5%. The limits of detection achieved were 0.7 ng/mL for codeine, 2.0 ng/mL for morphine, and 0.6 ng/mL for 6AM. The method proposed was applied to 80 oral fluid samples from opiates users, 98% of which were positive for the three analytes. Human oral fluid is a suitable biological fluid for the determination of opiates by GC/PCI-MS.     

Structure–Function Relationships in Unsymmetrical Zinc Phthalocyanines for Dye‐Sensitized Solar Cells

Let it shine! The impact of the anchoring group on photovoltaic performance by a series of phthalocyanine sensitisers (see figure) has been demonstrated.

     

The Antipode and the (co)invariants of a Finite Hopf (co)quasigroup

If $\mathcal{C}$ is a strict braided monoidal category in which the idempotent morphisms have a canonical split, we find conditions under which the antipode of a Hopf (co)quasigroup is an isomorphism. We also prove that the object of (co)invariants of a finite Hopf (co)quasigroup in $\mathcal{C}$ is an invertible object.