Electrochemical characterization of Prussian blue type nickel hexacyanoferrate redox mediator for potential application as charge relay in dye-sensitized solar cells

A polynuclear electronically/ionically (redox) conducting mixed-valent inorganic material such as nickel(II) hexacyanoferrate(II,III), NiHCF, was considered for potential application as a redox mediator (charge relay) in dye-sensitized solar cell (DSSC). The NiHCF redox reactions were found fast and reversible not only when the system was studied as thin film exposed to an aqueous supporting electrolyte but also as bulk material (pasted powder) in solid state, i.e., in the absence of contact with external liquid electrolyte phase. Usefulness of NiHCF material was diagnosed using conventional electroanalytical approaches, solid-state voltammetric methodology, as well as the dynamic electrochemical impedance spectroscopy technique that permitted monitoring of impedance spectra under potentiodynamic conditions. The material was utilized in a mixed-valent state, i.e., as a mixture of K₄Ni^II[Fe^II(CN)₆] and K₃Ni^II[Fe^III(CN)₆] in which iron(II) and iron(III) sites were at the 1:1 ratio. Under such conditions, dynamics of electron-hopping between mixed-valent iron sites was maximized. Our DSSC utilized cis–dithiocyanoatobis(4,4′-dicarboxylic acid-2,2′-bipyridine) ruthenium(II) dye (N3) adsorbed onto TiO₂ semiconductor and NiHCF as redox mediator. Although performance of our DSSC was not optimized in terms of the NiHCF film thickness and morphology, as well as lower photocurrents in comparison to those characteristic of the iodine/iodide based DSSC were obtained, our system yielded readily fairly high open-circuit photovoltages on the level of 800 mV. An important issue was that the formal potential of NiHCF was more positive relative to the potential of the iodide/triiodide couple while being still more negative than that equivalent to the ground state of the N3 dye. Thus, NiHCF mediator was able to regenerate the dye.

     

Natural radioactivity in groundwater – a review

The issue of natural radioactivity in groundwater is reviewed, with emphasis on those radioisotopes which contribute in a significant way to the overall effective dose received by members of the public due to the intake of drinking water originating from groundwater systems. The term ‘natural radioactivity’ is used in this context to cover all radioactivity present in the environment, including man-made (anthropogenic) radioactivity. Comprehensive discussion of radiological aspects of the presence of natural radionuclides in groundwater, including an overview of current regulations dealing with radioactivity in drinking water, is provided. The presented data indicate that thorough assessments of the committed doses resulting from the presence of natural radioactivity in groundwater are needed, particularly when such water is envisaged for regular intake by infants. They should be based on a precise determination of radioactivity concentration levels of the whole suite of radionuclides, including characterisation of their temporal variability. Equally important is a realistic assessment of water intake values for specific age groups. Only such an evaluation may provide the basis for possible remedial actions.     

Preparation and characterization of microporous fibers for sample preparation and LC‐MS determination of drugs

The aim of this study was the preparation of polypyrrole (PPy) fibers for solid phase microextraction (SPME). PPy coatings were obtained during the electrochemical polymerization process. The utility of various metal wires (Fe, Cu, Ag, Cu/Ag, kanthal and medical stainless steel) as a support for polymers was compared. Various experimental conditions of the synthesis process such as scan rate, voltage limits and number of scans and deposition time were applied. The average polymer thickness was in the range of 7–125 μm and its weight was in the scope of 0.65–5.6 mg. Different techniques, mainly elemental analysis, Fourier transform infrared spectroscopy, microscopy, and chromatography were performed for the characterization of obtained fibers with microporous structure. The extraction efficiency of cardiovascular drugs (metoprolol, propranolol, oxprenolol, propafenone and mexiletine) by means of fibers was tested. The concentration of mentioned compounds in standard solution was in the span of 10–150 ng/mL. LC‐MS was employed for determination of drugs in desorption solution. LODs varied from 0.013 to 1.51 ng/mL for metoprolol and mexiletine respectively. The repeatability of extraction was obtained with the RSD values lower than 10%.     

Kinetic and galvanostatic studies of a polymer electrolyte for lithium-ion batteries

Quaternary polymer electrolyte (PE) based on poly(acrylonitrile) (PAN), 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid (EMImBF₄), sulfolane (TMS) and lithium hexafluorophosphate salt (LiPF₆) (PAN-EMImBF₄-sulfolane-LIPF₆) was prepared by the casting technique. Obtained PE films of ca. 0.2–0.3 mm in thickness showed good mechanical properties. They were examined using scanning electron microscopy (SEM), thermogravimetry (TGA, DSC), the flammability test, electrochemical impedance spectroscopy (EIS) and galvanostatic charging/discharging. SEM images revealed a structure consisting of a polymer network (PAN) and space probably occupied by the liquid phase (LiPF₆ + EMImBF₄ + sulfolane). The polymer electrolyte in contact with an outer flame source did not ignite; it rather underwent decomposition without the formation of flammable products. Room temperature specific conductivity was ca. 2.5 mS cm^?1. The activation energy of the conding process was ca. 9.0 kJ mol^?1. Compatibility of the polymer electrolyte with metallic lithium and graphite anodes was tested applying the galvanostatic method. Charge transfer resistance for the C₆Li → Li⁺ + e^? anode processes, estimated from EIS curve, was ca. 48 Ω. The graphite anode capacity stabilizes at ca. 350 mAh g^?1 after the 30th cycle (20 mA g^?1).     

The Use of Lypolitic Microorganisms Pseudomonas fluorescens and Penicillium citrinum for the Preparation of Optically Active 1 -Hydroxyalkylphosphonates

Abstract

Lipases are perhaps the most widely used biocatalysts in organic synthesis. In this study lipases were found to catalyse the acetylation of diethyl 1-hydroxyalkylphosphonates, as well as 1-aminoalkylphosphonates. Unfortunately the lack of enantioselectivity was observed despite of the source of enzyme, as well as the type of organic solvent used as the reaction medium. Also the use of lipases for the enantioselective hydrolysis of diethyl O-butyryloxyalkylphosphonates in aqueous media was unsucceful. Qulte oppositively the hydrolysis of these substrates by wide-type strain of Pseudomonas fluorescens yielded optically active diethyl 1-hydroxyalkylphosphonates with moderate or good yields and of satisfactory optical purity, as determined by means of n.m.r. analysis of Mosher derivatives. The use of other lypolitic microorganism - Penicillium citrinum -was also succesful providing enantiomeric forms of the products obtained from the reaction catalyzed by Pseudomoms fluorescens. The substrate specificity of these two microorganisms, is discussed in some detail.     

Feedback stabilization of a class of nonlinear second-order systems

The goal of this paper is to study stabilization techniques for a system described by nonlinear second-order differential equations. The problem is to determine the feedback control as a function of the state variables. It is shown that the following controllers can asymptotically stabilize the system: linear position feedback, linear velocity feedback and a group of nonlinear feedbacks. The stability of the corresponding closed-loop system is proved by imposing a suitable Lyapunov function and then using LaSalle’s invariance principle. The results of numerical computations are included to verify theoretical analysis and mathematical formulation. Some application examples from robotics, mechanics and electronics are presented.