Abstract: Forensic drug laboratories are confronted with increasing amounts of drugs and a demand for faster results that are directly available on-site. In addition, the drug market is getting more complex with hundreds of new psychoactive substances (NPS) entering the market in recent years. Rapid and on-scene presumptive drug testing therefore faces a shift from manual colorimetric tests towards approaches that can detect a wider range of components and process results automatically. Electrochemical detection offers these desired characteristics, making it a suitable candidate for on-site drug detection. In this study, a two-step electrochemical sensor is introduced for the detection of MDMA and 2C-B. Firstly, a direct electrochemical analysis was performed to detect MDMA. Validation experiments on over 70 substances revealed that 2C-B was the only frequently encountered drug that gave a false positive result for MDMA in this first analysis. A second step using in-situ derivatization was subsequently introduced. To this end, formaldehyde was used for N-methylation of 2C-B thereby enhancing its electrochemical profile. The enriched electrochemical fingerprint in the second step allowed for clear differentiation between MDMA and 2C-B. The applicability of this approach was demonstrated with 71 ecstasy tablets seized by the Amsterdam Police. The MDMA/2C-B sensor correctly identified all 39 MDMA-containing tablets and 10 out of 11 tablets containing 2C-B. Most notably, correct results were also obtained for dark colored tablets in which both spectroscopic analysis and colorimetric tests failed due to obscured signals.

Abstract: An aptamer-based electrochemical sensor, wherein said aptamer is covalently bonded to or chemisorbed on an electrode, said aptamer forming a robust complex with a target molecule and is encapsulated by a gelatin B matrix; a method of manufacturing an aptamer-based electrochemical sensor for determining a concentration of a target molecule comprising the steps of: selecting an aptamer to form a robust complex with a target molecule using the SELEX procedure; synthesizing said aptamer; adsorbing said aptamer on or covalently coupling said aptamer with an electrode; and providing a gelatin B matrix for said aptamer on said electrode thereby realising said aptamer-based potentiometric or amperometric sensor; and the use of the aptamer-based electrochemical sensor produced according to the above method for the electrochemical determination of a concentration of 15 the target molecule.

Abstract: Iridium oxide (IrOx) is one of the most efficient electrocatalysts for water oxidation reaction (WOR). Here, WOR electrocatalysis by 1.6 nm IrOx nanoparticles (NPs) electrophoretically deposited onto spectroscopic graphite (Gr) and basal plane highly ordered pyrolytic graphite (HOPG) was studied as a function of NPs' capping ligands and electrodeposition substrate. On Gr, OH-- and H2O-capped NPs exhibited close sub-monolayer surface coverages and specific electrocatalytic activity of 18.9-23.5 mA nmol(-1) of Ir-IV/V sites, at 1 V and pH 7. On HOPG, OH--capped NPs produced films with a diminished WOR activity of 5.17 +/- 2.40 mA nmol(-1). Electro-wettability-induced changes impeded electrophoretic deposition of H2O-capped NPs on HOPG, WOR currents being 25-fold lower than observed for OH--capped ones. The electrocatalysis efficiency correlated with hydrophilic properties of the substrate electrodes, affecting morphological and as a result catalytic properties of the formed IrOx films. These results, important both for studied and related carbon nanomaterials systems, allow fine-tuning of electrocatalysis by a proper choice of the substrate electrode.

Abstract: Nowadays, the burning of fossil fuels, particularly petroleum, natural gas, and coal, meets the rising need for power and fuels for automobiles and industries. This has given rise to ecological and climate challenges. This thesis explores these issues from three distinct perspectives: (i) experimental, (ii) computational, and (iii) process simulation, with a focus on studying CO2 as an alternative and economically viable raw material. Firstly, the experimental study is focused on the synthesis, characterization, and testing of novel catalysts for electroreduction of CO2 and oxalic acid, an intermediate product of CO2. Electrocatalysts based on Cu supported by citrus (orange and lemon) peel biomass are prepared. These catalysts exhibit activity in the electrochemical reduction of CO2, emphasizing the effectiveness of biomasses, particularly orange peels, as environmentally friendly precursors for sustainable and efficient electrocatalysts. In addition, graphitic carbon nitrides/TiO2 nanotubes (g-C3N4/TiNT) composites are prepared for the electrocatalytic reduction of oxalic acid to glycolic acid, revealing superior electrocatalytic properties compared to pristine TiNT. Characterization by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electronic microscopy were performed for all the prepared electrocatalysts. Delving into the reduction of CO2 on Cu catalysts, a computational study about the synthesis of methanol on Cu(111) surface is performed by using the Vienna Ab initio Simulation Package. A systematic study is carried out to define the activation energies of the elementary reactions by using mGGA DF. Consequently, it is shown that the rate-controlling step is CH3O* hydrogenation and the formate pathway on Cu(111) proceeds through the HCOOH* intermediate. Finally, the process simulation, performed by using the software Aspen Plus 11 from AspenTech Inc., is based on the comparison of a catalytic (oxidation of ethylene glycol) and an electrocatalytic process (CO2 electroreduction chain) to synthesize glycolic acid. An economic analysis of the operational and investment costs reveals that the catalytic process is more cost-effective due to the current instability of electrocatalysts and proton exchange membranes, resulting in increased maintenance costs and, consequently, higher prices for the product.

Abstract: A first-principles study of the electric field gradient (EFG) calculated for ideal and In-111(Cd-111) implanted ZnO samples is reported in the present work. The study was made for ZnO ideal hexagonal structures and supercells were introduced in order to consider the possible implantation environments. The calculation was done using the “WIEN2k” code within the density functional theory, the exchange and correlation effects were determined by the GGA approximation. Three possible In-111(Cd-111) implantation configurations were studied, one substitutional incorporation at cation site and two interstitials. The obtained EFG values for the ideal structure and the substitutional site are in good agreement with the experimental reports measured by perturbed angular correlation (PAC) and high precision nuclear magnetic resonance (NMR). Thus, the ascription of substitutional incorporation of In-111(Cd-111) probe atom at the ZnO cation site after annealing was confirmed. (C) 2011 Elsevier Ltd. All rights reserved.

Abstract: The quantum electrostatic heterostructure (QEH) model allows for efficient computation of the dielectric screening properties of layered van der Waals (vdW)-bonded heterostructures in terms of the dielectric functions of the individual two-dimensional (2D) layers. Here, we extend the QEH model by including (1) contributions to the dielectric function from infrared active phonons in the 2D layers, (2) screening from homogeneous bulk substrates, and (3) intraband screening from free carriers in doped 2D semiconductor layers. We demonstrate the potential of the extended QEH model by calculating the dispersion of coupled phonons in multilayer stacks of hexagonal boron-nitride (hBN), the strong hybridization of plasmons and optical phonons in graphene/hBN heterostructures, the effect of substrate screening on the exciton series of monolayer MoS2, and the properties of hyperbolic plasmons in a doped phosphorene sheet. The new QEH code is distributed as a Python package with a simple command line interface and a comprehensive library of dielectric building blocks for the most common 2D materials, providing an efficient open platform for dielectric modeling of realistic vdW heterostructures.

Abstract: An investigation was made to determine the influence of the dumping of a 1000 ton day−1, on the average, of acid-iron waste from the titanium dioxide industry into the shallow but turbulent Southern Bight of the North Sea. This waste contains some 20% sulfuric acid and 2% iron. After the passage of the barge that discharges 10 ton of waste min−1 into its wake, the vertical and horizontal distributions of the pH, iron-concentration and turbidity were measured as a function of time. It appeared that a few seconds after the discharge and for a very brief period, the pH was down to approx. 4 and the Fe-concentration was 13 mg l−1. More than 1 min after the discharge a pH below 6 and an iron-level above 3 mg l−1 could not be detected anywhere. The measured factor for waste dilution by sea water, based on the observed acid and iron concentration in the waste and in the discharge track, were around 5000 after 5 min, 9000 after 10 min and 80,000 after 20 min. Before and long after the dumping, the total iron-concentration in this Southern Bight area was around 100 μg l−1, but this high level might be due to natural causes.

Abstract: The spatial distribution and temporal concentration variation of a set of gaseous air components (e.g., CO2, CO, H2CO, H2O) have been monitored with a multi-channel photoacoustic gas-analyzer in an urban church ( Saint Catherine's, Cracow) and a mountain church ( Saint Michaels Archangel, Szalowa) of Poland, in order to assess the likely effects of air pollution indoors under the influence of provisory electrical infrared (IR) heaters and without heating. Likewise, the ventilation characteristic and the leakage of these buildings with different constructions (i.e., plastered stone and wooden structures) with the assistance of decay curves of SF6 tracer gas was evaluated and compared. The wooden building in Szalowa, due to its more open structure, developed about one order higher ventilation rates (e.g., 0.9-1.3 h(-1)) than the stone church in Cracow (e.g., 0.1 h(-1)). The IR-heating affected only modestly the ventilation rate of the wooden church (e.g., 1.2-1.6 h(-1)), but it increased significantly that of the plastered stone church (e.g., 0.27 h(-1)). The ventilation rates were also assessed with the use of the CO2 curve decay method, and satisfactory agreement was found with those observed by the use of SF6 tracer. The spatial distribution of the studied gaseous pollutants (CO2, H2O) was found to be in some occasions nonhomogeneous in both buildings, due to the active usage of the IR-heating, especially, during a couple of consecutive liturgical services. Besides the pollution events due to ingress of gaseous air pollutants, present at enhanced levels outdoors, increased CO, CO2 and H2CO peaks were observed indoors too, which, in most cases, could be associated with incense burning. (C) 2018 Elsevier Masson SAS. All rights reserved.