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In this study, nanostructure kazakhstanite-like iron vanadate (FexV3xOy.H2O) was synthesized and calcined at different temperatures (100-800 °C) in a nitrogen atmosphere. The material was used to modify screen-printed carbon electrodes to achieve an electrocatalytic effect on the surface. The relationship between calcination conditions and the catalytic performance of the electrode towards the oxidation of chemotherapeutic drugs, including methotrexate (MTX) and folinic acid (FA), was studied. Various spectroscopic, microscopic, and electrochemical methods were used to characterize the synthesized materials. The results show that calcination induces changes in the electronic structure, nanostructure morphology, electroactive surface area, and electrocatalytic performance of the material. Screen-printed carbon electrode modified with FexV3xOy calcinated at 450 °C (SPC/FexV3xOy-450) was used to develop a voltammetric sensor for the determination of MTX and FA in blood serum. The response of the SPC/FexV3xOy-450 towards the electrooxidation of MTX and FA was the highest in comparison to the bare SPC and SPC/FexV3xOy calcined at other temperatures. The SPC/FexV3xOy-450 exhibited a linear relationship over a wide concentration range: 0.005-200 µM for MTX and 0.05-200 µM for FA. The detection limit was 2.85 nM for MTX and 7.79 nM for FA. Compared to conventional methods, the SPC/FexV3xOy-450 sensor had a short response time (5 min) for simultaneous detection of MTX and FA without signal interferences from coexisting electroactive compounds. The accurate and precise determination of MTX in the presence of FA confirmed the potential clinical applications of SPC/FexV3xOy-450 for therapeutic drug monitoring during chemotherapy.

Surface modification is a hot topic in electrochemistry and material sciences because it affects the way materials are used. In this paper, a method for covalently attaching carboxyphenyl (PhCOOH) groups to a gold electrode is presented. These groups were grafted onto the electrode surface electrochemically via reduction of aryldiazonium salt. The resulting grafted surface was characterized using cyclic voltammetry (CV) before and after the functionalization procedure to validate the presence of the grafted layer. The grafting of PhCOOH groups was confirmed by analyzing electrode thickness and composition by ellipsometry and X-ray photoelectron spectroscopy (XPS). Density functional theory (DFT) calculations indicated that the grafted layers provide a stable platform and resolved, for the first time, their interactions with oxygen.

In this work, a low-cost, light-weight, highly efficient, and durable electrode in which NiFe-layered double hydroxide is electrodeposited on a carbon nanofiber (CNF) core supported on a carbon foam (CF) is introduced. The resulting 3D NiFe-CNFs-CF electrode shows excellent oxygen evolution reaction and hydrogen evolution reaction performance in alkaline media. When used as an anode and a cathode in the same cell, a current density of 10 mA cm−2 is achieved, at a cell voltage of 1.65 V. Moreover, good stability over a long testing time (50 h) is demonstrated. The ternary hybrid electrode gives rise to an excellent performance-to-weight ratio owing to its very low bulk density (≈34 mg cm−3) inherited from super lightweight components composed of CF and CNFs. The developed electrode can potentially be used in large-scale alkaline water electrolysis, in facilities such as offshore hydrogen production platforms, which can complement the variable renewable energy production of wind farms through hydrogen storage and fuel cells.

In this study, we report a 3D structured carbon foam electrode assembled from a bi-functional NiCo catalyst, carbon nanotubes (CNT), and a monolith 3D structured carbon foam (CF) as a highly active and stable electrode for oxygen evolution reaction (OER) and methanol oxidation reaction (MOR). When the NiCo@CNTs/CF electrode was used as an anode in OER, after the anodization step, the electrode required a small overpotential of 320 mV to reach the current density of 10 mA cm−2 and demonstrated excellent stability over a long testing time (total 30 h) in 1 M KOH. The as-prepared NiCo@CNTs/CF electrode also exhibited a good performance towards methanol oxidation reaction (MOR) with high current density, 100 mA cm−2 at 0.6 V vs. Ag/AgCl, and good stability in 1 M KOH plus 0.5 M CH3OH electrolyte. The NiCo@CNTs/CF catalyst/electrode provides a potential for application as an anode in water electrolysis and direct methanol fuel cells.

Grafting of electrodes with diazonium salts using cyclic voltammetry (CV) is a well-established procedure for surface modification. However, little is known about the effect of the concentration of the diazonium salt on the number of layers grafted on the electrode surface. In this work, the impact of concentration on the grafting of 4-carboxybenzenediazonium (4-CBD) onto a glassy carbon electrode (GCE) is elucidated. The number of layers grafted on the GCE was linearly dependent on the concentration of 4-CBD and varied between 0.9 and 4.3 when the concentration was varied between 0.050 and 0.30 mmol/L at 0.10 V.s−1. Characterization of modified glassy carbon surface with X-ray photoelectron spectroscopy (XPS) confirmed the grafting of carboxyphenyl layer on the surface. Grafting with 0.15 mmol/L 4-CBD (1 CV cycle) did not form a detectable amount of carboxyphenyl (CP) moieties at the surface, while a single scan with higher concentration (2.5 mmol/L) or multiple scans (22 cycles) gave detectable signals, indicating formation of multilayers. We also demonstrate the possibility of removing the thin layer grafted on a glassy carbon electrode by applying high oxidation potential +1.40 V.

Finding novel strategies for surface modification is of great interest in electrochemistry and material sciences. In this study, we present a strategy for modification of a gold electrode through covalent attachment of triazole (TA) groups. Triazole groups were electrochemically grafted at the surface of the electrode by a reduction of in situ generated triazolediazonium cations. The resulting grafted surface was characterized before and after the functionalization process by different electrochemical methods (cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS)) confirming the presence of the grafted layer. The grafting of TA on the electrode surface was confirmed using analysis of surface morphology (by atomic force microscopy), the thickness of the grafted layer (by ellipsometry) and its composition (by X-ray photoelectron spectroscopy). Density functional theory (DFT) calculations imply that the grafted triazole offers a stronger platform than the grafted aryl layers.

Surface modification of materials is accomplished using a vast number of molecules that possess a special affinity (SAMS) or are prone to undergo chemical reactions with the surface groups of the substrate-usually hydroxylated oxide layers (phosphonic or carboxylic acids, silanes, etc.). Probably the most direct mode to achieve this task is the use of the diazonium salts. This surface modification permits an easy way for tuning the properties of materials and adding some new interesting functionality that can be explored for: sensor construction, corrosion protection, catalysis, etc. In this work, we explored the use of diazonium heterocyclic compound to graft the surface of the glassy carbon electrode through di electrochemical reaction of the transformed amino heterocyclic moiety into the corresponding diazonium salt. The grafted surface is analyzed by a number of electrochemical and surface analysis techniques.

Surface modification of materials is accomplished using a vast number of molecules that possess a special affinity (SAMS) or are prone to undergo chemical reactions with the surface groups of the substrate-usually hydroxylated oxide layers (phosphonic or carboxylic acids, silanes, etc.). Probably the most direct mode to achieve this task is the use of the diazonium salts. This surface modification permits an easy way for tuning the properties of materials and adding some new interesting functionality that can be explored for: sensor construction, corrosion protection, catalysis, etc. In this work we explored the use of diazonium heterocyclic compound to graft the surface of the glassy carbon electrode through direct grafting (by the isolation of the diazonium salt) and "in situ" electrochemical reaction of the transformed amino heterocylic moiety into the corresponding diazonium salt. The grafted surface is analyzed by a number of electrochemical and surface analysis techniques.

Hypothesis: Electrochemical Impedance Spectroscopy (EIS) can be used to investigate cationic interaction with the choline headgroup in the ternary system of monoolein/dioleoylphosphatidylcholine/water (MO/DOPC/H2O). Experiments: EIS was used to estimate the resistance and capacitance of a freestanding membrane of a lipid cubic phase (LCP). The membrane was formed in a small cylindrical aperture separating two compartments, containing one Pt electrode each. The impedance experiments were carried out in a two electrode setup with electrolyte solutions made of KCl, CsCl, MgCl2 and CaCl2 filling the compartments at two different ionic strength. Small angle X-ray diffraction (SAXRD) was used to establish the structure and cell unit parameters of the LCP. Findings: The interpretation of ionic interaction with phosphatidylcholine was based on estimated membrane resistances and capacitances from EIS measurements. The magnitude of cationic interaction with the lipid headgroup in the water channels is correlated to the membrane resistance that increases in the order Cs+ < K+ < Mg2+ < Ca2+ following the Hofmeister direct series and also reflecting the order of intrinsic binding constants. The membrane capacitance and SAXRD results are discussed as an effect of cationic interaction and it was possible to observe both swelling and condensing effects. The stability of the cubic phase throughout the experiments was confirmed by SAXRD.

Hypothesis: Electrochemical impedance spectroscopy is useful to monitor anionic interactions with a Lipid Cubic Phase, as previously demonstrated for cationic interaction (Khani Meynaq et al., 2016). It was expected that the smaller hydrophilic anions, acetate and chloride, would interact differently than the large tryptophan anion with its hydrophobic tail. Experiment: The impedance measurements enabled estimation of resistances and capacitances of a freestanding lipid cubic phase membrane at exposure to 4 and 40 mM solutions of NaCl, NaOAc and NaTrp. Small-angle X-ray scattering was used for cubic phase identification and to track structural changes within the cubic phase when exposed to the different electrolytes. Findings: The membrane resistance increases at exposure to the electrolytes in the order Cl− < OAc− < Trp−. The membrane resistance decreases with time at exposure to the hydrophilic anions and increases with time at Trp− exposure. The membrane capacitances were lower for NaTrp compared to NaCl and NaOAc at the corresponding concentrations which is consistent with the results from SAXRD. It is concluded that Trp− ions do not enter the aqueous channels of the cubic phase but are strongly adsorbed to the membrane/electrolyte interface leading to large alteration of the lipid phase structure and a high membrane resistance.

The paper describes investigation on bioaccumulation of mineral elementsand identification of plants based on the concentrations of the elements inthe plant leaves. Five native plant species (Elytrigia repens, Plantago major,Urtica dioica, Chelidonium majus, and Taraxacum officinale) were studied. Toexclude the effects from different growth conditions and developmentalstages, the plants were collected simultaneously from the same site (park inSt. Petersburg, Russia). It was found that for all plants high concentrations ofpotassium, sodium, phosphorus and magnesium (K, Na, P, and Mg) weretypical, while concentrations of zinc (Zn) and copper (Cu) were the lowest.The most significant difference was found between concentrations ofelements in monocots and eudicots. Among other species,T. officinalehadthe highest concentrations of almost all elements. Excellent separation of theplants into different groups which was due to different elementconcentrations in the plant leaves was demonstrated.

Hypothesis Electrochemical impedance spectroscopy, EIS, can be used as a complementary technique to investigate ion interaction with the headgroup region in the aqueous channels of a lipid cubic phase, LCP. Experiments A freestanding membrane made of monoolein LCP was formed by filling a small aperture that separates two cell compartments. The cell compartments were filled with electrolyte solutions at two different ionic strengths: i.e.: 10 and 100 mM, of KCl, CsBr and CaCl2. Electrochemical impedance spectroscopy was recorded between two platinum electrodes that were present at each side of the membrane. Findings The membrane resistance and capacitance were estimated from equivalent circuit fitting of the impedance data. It was confirmed that calcium ions interacts strongly with the headgroup region in the aqueous channels giving significantly higher membrane resistances compared to monovalent alkali metal ions. The membrane capacitance with Ca2+(aq) in solution was concentration dependent, which for the first time indicates formation of two different cubic phases at these conditions.

We report experimentally determined first-order rate constants of MeHg photolysis in three waters along a Boreal lake-wetland gradient covering a range of pH (3.8-6.6), concentrations of total organic carbon (TOC 17.5-81 mg L(-1)), total Fe (0.8-2.1 mg L(-1)), specific UV254 nm absorption (3.3-4.2 L mg(-1) m(-1)) and TOC/TON ratios (24-67 g g(-1)). Rate constants determined as a function of incident sunlight (measured as cumulative photon flux of photosynthetically active radiation, PAR) decreased in the order dystrophic lake > dystrophic lake/wetland > riparian wetland. After correction for light attenuation by dissolved natural organic matter (DOM), wavelength-specific (PAR: 400-700 nm, UVA: 320-400 nm and UVB: 280-320 nm) first-order photodegradation rate constants (kpd) determined at the three sites were indistinguishable, with average values (±SE) of 0.0023 ± 0.0002, 0.10 ± 0.024 and 7.2 ± 1.3 m(2) E(-1) for kpdPAR, kpdUVA, and kpdUVB, respectively. The relative ratio of kpdPAR, kpdUVA, and kpdUVB was 1:43:3100. Experiments conducted at varying MeHg/TOC ratios confirm previous suggestions that complex formation with organic thiol groups enhances the rate of MeHg photodegradation, as compared to when O and N functional groups are involved in the speciation of MeHg. We suggest that if the photon fluxes of PAR, UVA, and UVB radiation are separately determined and the wavelength-specific light attenuation is corrected for, the first-order rate constants kpdPAR, kpdUVA, and kpdUVB will be universal to waters in which DOM (possibly in concert with Fe) controls the formation of ROS, and the chemical speciation of MeHg is controlled by the complexation with DOM associated thiols.

A hydrophilic interaction liquid chromatography-UV method was developed for the determination of melamine in milk powder. Sulfobetaine type zwitterionic hydrophilic interaction liquid chromatography stationary phase was used to achieve straightforward separation of melamine in milk powder without any sample derivatization or addition of ion-pair reagent. The sample preparation was simple and fast with the steps of acetonitrile/perchloric acid extraction-centrifugation-filtration. No SPE or other pre-concentration procedure was required. By using large volume sample injection and choosing low UV wavelength (210 nm), the LOD and LOQ were 0.005 and 0.015 mug/mL for melamine standards, and 0.02 and 0.06 mug/mL for the spiked milk extracts. The LOD and LOQ of the latter correspond to 0.95 and 2.2 mug/g melamine in the milk powder. The correlation coefficients for melamine standard, pre-spiked milk extracts and post-spiked milk extracts in the range of 0-0.5 mug/mL were 0.9978, 0.9976 and 0.9995, respectively. This newly developed method is sensitive and cost effective, therefore, suitable for screening of melamine in tainted milk products.

The impact of water saturation level (oxidizing-reducing environment) on As and metal solubility in chromium, copper, arsenic (CCA)-contaminated soil amended with Fe-containing materials was studied. The soil was mixed with 0.1 and 1 wt% of iron grit (Fe(0)) and 1, 7 and 15 wt% of oxygen scarfing granulate (OSG, a by-product of steel processing). Solubility of As and metals was evaluated by a batch leaching test and analysis of soil pore water. Soil saturation with water greatly increased As solubility in the untreated as well as in the Fe-amended soil. This was related to the reductive dissolution of Fe oxides and increased concentration of As(III) species. Fe amendments showed As reducing capacity under both oxic and anoxic conditions. The cytotoxicity of the soil pore water correlated with the concentration of As(III). The Fe-treatments as well as water saturation of soil were less significant for the solubility of Cu, Cr and Zn than for As. The batch leaching test used for waste characterization substantially underestimated As solubility that could occur under water-saturated (anaerobic) conditions. In the case of soil landfilling, other techniques than Fe-stabilization of As containing soil should be considered.