Tryptophan oxidation by singlet molecular oxygen [O-2 ((1)Delta(g))]: Mechanistic studies using O-18-labeled hydroperoxides, mass spectrometry, and light emission measurements

Proteins have been considered important targets for reactive oxygen species. Indeed, tryptophan (W) has been shown to be a highly susceptible amino acid to many oxidizing agents, including singlet molecular oxygen [O-2 ((1)Delta(g))]. In this study, two cis- and trans-tryptophan hydroperoxide (WOOH) isomers were completely characterized by HPLC/mass spectrometry and NMR analyses as the major W-oxidation photoproducts. These photoproducts underwent thermal decay into the corresponding alcohols. Additionally, WOOHs were shown to decompose under heating or basification, leading to the formation of N-formylkynurenine (FMK). Using O-18-labeled hydroperoxides ((WOOH)-O-18-O-18), it was possible to confirm the formation of two oxygen-labeled FMK molecules derived from (WOOH)-O-18-O-18 decomposition. This result demonstrates that both oxygen atoms in FMK are derived from the hydroperoxide group. In addition, these reactions are chemiluminescent (CL), indicating a dioxetane cleavage pathway. This mechanism was confirmed since the CL spectrum of the WOOH decomposition matched the FMK fluorescence spectrum, unequivocally identifying FMK as the emitting species.

Room Temperature Ionic Liquid-Lithium Salt Mixtures: Optical Kerr Effect Dynamical Measurements

The addition of lithium salts to ionic liquids causes an increase in viscosity and a decrease in ionic mobility that hinders their possible application as an alternative solvent in lithium ion batteries. Optically heterodyne-detected optical Kerr effect spectroscopy was used to study the change in dynamics, principally orientational relaxation, caused by the addition of lithium bis(trifluoromethylsulfonyl)imide to the ionic liquid 1-buty1-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Over the time scales studied (1 ps-16 ns) for the pure ionic liquid, two temperature-independent power laws were observed: the intermediate power law (1 ps to similar to 1 ns), followed by the von Schweidler power law. The von Schweidler power law is followed by the final complete exponential relaxation, which is highly sensitive to temperature. The lithium salt concentration, however, was found to affect both power laws, and a discontinuity could be found in the trend observed for the intermediate power law when the concentration (mole fraction) of lithium salt is close to chi(LiTf(2)N) = 0.2. A mode coupling theory (MCT) schematic model was also used to fit the data for both the pure ionic liquid and the different salt concentration mixtures. It was found that dynamics in both types of liquids are described very well by MCT.

Chemical modification of a nanocrystalline TiO(2) film for efficient electric connection of glucose oxidase

A novel biosensor for glucose was prepared by adsorption of 1,1`-bis(4-carboxybenzyl)-4,4`-bipyridinium di-bromide compound (H(2)BpybcBr(2)) onto the surface of a nanocrystalline TiO(2) film deposited onto FTO glasses, which was used as a platform to assemble the enzyme glucose oxidase to the electrode surface. The H(2)BpybcBr(2)/TiO(2)/FTO modified electrode was characterized by scanning electron microscopy, X-ray fluorescence image, cyclic voltammograms and spectroelectrochemical measurements. The immobilization of GOD on functionalized TiO(2) film led to stable amperometric biosensing for glucose with a linear range from 153 mu mol L(-1) to 1.30 mmol L(-1) and a detection limit of 51 mu mol L(-1). The apparent Michaelis-Menten constant (K(m)) was estimated to be 3.76 mmol L(-1), which suggested a high enzyme-substrate affinity. The maximum electrode sensitivity was 1.25 mu A mmol L(-1). The study proved that the combination of viologen mediators with TiO(2) film retains the electrocatalytic activity of the enzyme, and also enhances the electron transfer process, and hence regenerating the enzyme in the reaction with glucose. (C) 2010 Elsevier Inc. All rights reserved.

Nickel hydroxide electrodes as amperometric detectors for carbohydrates in flow injection analysis and liquid chromatography

The present paper describes the utilization of nickel hydroxide modified electrodes toward the catalytic oxidation of carbohydrates (glucose, fructose, lactose and sucrose) and their utilization as electrochemical sensor. The modified electrodes were employed as a detector in flow injection analysis for individual carbohydrate detection, and to an ionic column chromatography system for multi-analyte samples aiming a prior separation step. Kinetic studies were performed on a rotating disk electrode (RDE) in order to determine both the heterogeneous rate constant and number of electrons transferred for each carbohydrate. Many advantages were found for the proposed system including fast and easy handling of the electrode modification, low cost procedure, a wide range of linearity (0.5-50 ppm), low detection limits (ppb level) and high sensitivities. (C) 2009 Elsevier B.V. All rights reserved.

Flow injection amperometric determination of hydrogen peroxide in household commercial products with a ruthenium oxide hexacyanoferrate modified electrode

Hydrogen peroxide was determined in oral antiseptic and bleach samples using a flow-injection system with amperometric detection. A glassy carbon electrode modified by electrochemical deposition of ruthenium oxide hexacyanoferrate was used as working electrode and a homemade Ag/AgCl (saturated KCl) electrode and a platinum wire were used as reference and counter electrodes, respectively. The electrocatalytic reduction process allowed the determination of hydrogen peroxide at 0.0 V. A linear relationship between the cathodic peak current and concentration of hydrogen peroxide was obtained in the range 10-5000 mu mol L(-1) with detection and quantification limits of 1.7 (S/N = 3) and 5.9 (S/N = 10) mu mol L(-1), respectively. The repeatability of the method was evaluated using a 500 mu mol L(-1) hydrogen peroxide solution, the value obtained being 1.6% (n = 14). A sampling rate of 112 samples h(-1) was achieved at optimised conditions. The method was employed for the quantification of hydrogen peroxide in two commercial samples and the results were in agreement with those obtained by using a recommended procedure.

Urea amperometric biosensors based on a multifunctional bipolymeric layer: Comparing enzyme immobilization methods

This paper outlines the results obtained with biosensors designed for urea amperometric detection. The incorporation of urease into a bipolymeric substrate consisting of poly(pyrrole) and poly(5-amino-1-naphthol) was performed through four different approaches: direct adsorption, entrapment in cellulose acetate layer. cross-linking with glutaraldehyde, and also covalent attachment to the polymeric matrix. Poly(pyrrole) acts as amperometric transducer in these biosensors, while poly(5-amino-1-naphthol) drastically reduces the interference signal of agents such as ascorbic and uric acids. The biosensors containing urease covalently attached to the substrate provided interesting results in terms of sensitivity towards urea (0.50 mu A cm(-2) mmol(-1) L), lifetime (20 days) and short response times, due to the enzyme immobilization method used. All biosensors analyzed showed also a wide linear concentration range (up to 100 mmol L(-1)) and low detection limits (0.22-0.58 mmol L(-1)). (C) 2009 Elsevier B.V. All rights reserved.

Fast and reliable analyses of sulphite in fruit juices using a supramolecular amperometric detector encompassing in flow gas diffusion unit

A new compact system encompassing in flow gas diffusion unit and a wall-jet amperometric FIA detector, coated with a supramolecular porphyrin film, was specially designed as an alternative to the time-consuming Monier-Williams method, allowing fast, reproducible and accurate analyses of free sulphite species in fruit juices. In fact, a linear response between 0.64 and 6.4 ppm of sodium sulphite. LOD = 0.043 ppm, relative standard deviation of +/- 1.5% (n = 10) and analytical frequency of 85 analyses/h were obtained utilising optimised conditions. That superior analytical performance allows the precise evaluation of the amount of free sulphite present in foods, providing an important comparison between the standard addition and the standard injection methods. Although the first one is most frequently used, it was strongly influenced by matrix effects because of the unexpected reactivity of sulphite ions with the juice matrixes, leading to its partial consumption soon after addition. In contrast, the last method was not susceptible to matrix effects yielding accurate results, being more reliable for analytical purposes. (C) 2011 Elsevier Ltd. All rights reserved.

Immobilization of Catalysts of Biological Interest on Porous Oxidized Silicon Surfaces

The present paper deals with the immobilization of redox mediators and proteins onto protected porous silicon surfaces to obtain their direct electrochemical reactions and to retain their bioactivities. This paper shows that MP-11 and viologens are able to establish chemical bonds with 3-aminopropyltriethoxylsilane-modified porous silicon surface. The functionalization of the surfaces have been fully characterized by energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS) to examine the immobilization of these mediators onto the solid surface. Amperometric and open circuit potential measurements have shown the direct electron transfer between glucose oxidase and the electrode in the presence of the viologen mediator covalently linked to the 3-aminopropyltriethoxylsilane (APTES)-modified porous silicon surfaces.

Under flow impedimetric measurements using magnetic particles for label-free detection affinity target

The necessity to adapt sensors based on electrochemical techniques for high throughput analysis control increases the interest to develop new analytical systems able to perform measurements under buffer now. In this report we explored the possibility of employing a new system to make impedimetric measurements to detect the interaction between proteins and small molecules. The well-known biotin-streptavidin interaction was adopted to evaluate the proposed assembly. This system allows us to perform experiments under flow. Magnetic beads functionalized with streptavidin were used and first characterized using AFM and FTIR. Non-faradic impedance spectroscopy allowed the detection of the biotin-streptavidin interaction. Using our new system and under a flow of PBS buffer, 5 10-5 M of biotin was detected with a stable signal. (c) 2007 Elsevier B.V. All rights reserved.

Flow injection analysis using carbon film resistor electrodes for amperometric determination of ambroxol

Flow injection analysis (FIA) using a carbon film sensor for amperometric detection was explored for ambroxol analysis in pharmaceutical formulations. The specially designed flow cell designed in the lab generated sharp and reproducible current peaks, with a wide linear dynamic range from 5 x 10(-7) to 3.5 x 10(-4) mol L-1, in 0.1 mol L-1 sulfuric acid electrolyte, as well as high sensitivity, 0.110 A mol(-1) L cm(-2) at the optimized flow rate. A detection limit of 7.6 x 10(-8) mol L-1 and a sampling frequency of 50 determinations per hour were achieved, employing injected volumes of 100 mu L and a flow rate of 2.0 mL min(-1). The repeatability, expressed as R.S.D. for successive and alternated injections of 6.0 x 10(-6) and 6.0 x 10(-5) mol L-1 ambroxol solutions, was 3.0 and 1.5%, respectively, without any noticeable memory effect between injections. The proposed method was applied to the analysis of ambroxol in pharmaceutical samples and the results obtained were compared with UV spectrophotometric and acid-base titrimetric methods. Good agreement between the results utilizing the three methods and the labeled values was achieved, corroborating the good performance of the proposed electrochemical methodology for ambroxol analysis. (C) 2008 Elsevier B.V. All rights reserved.

A novel nanostructured composite formed by interaction of copper octa(3-aminopropyl)octasilsesquioxane with azide ligands: Preparation, characterization and a voltammetric application

This study presents the preparation, characterization and application of copper octa(3-aminopropyl)octasilsesquioxane following its subsequent reaction with azide ions (ASCA). The precursor (AC) and the novel compound (ASCA) were characterized by Fourier transform infrared spectra (FTIR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), scanning electronic microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric analyses and voltammetric technique. The cyclic voltammogram of the modified graphite paste electrode with ASCA (GPE-ASCA), showed one redox couple with formal potential (E(1/2)(ox)) = 0.30 V and an irreversible process at 1.1 V (vs. Ag/AgCl; NaCl 1.0 M; v = 20 mV s(-1)). The material is very sensitive to nitrite concentrations. The modified graphite paste electrode (GPE-ASCA) gives a linear range from 1.0 x 10(-4) to 4.0 x 10(-3) mol L(-1) for the determination of nitrite, with a detection limit of 2.1 x 10(-4) mol L(-1) and the amperometric sensitivity of 8.04 mA/mol L(-1). (C) 2010 Elsevier Ltd. All rights reserved.

TCA Evaluation : Lab Measurements, Modelling and System Simulations

The study reported here is part of a large project for evaluation of the Thermo-Chemical Accumulator (TCA), a technology under development by the Swedish company ClimateWell AB. The studies concentrate on the use of the technology for comfort cooling. This report concentrates on measurements in the laboratory, modelling and system simulation. The TCA is a three-phase absorption heat pump that stores energy in the form of crystallised salt, in this case Lithium Chloride (LiCl) with water being the other substance. The process requires vacuum conditions as with standard absorption chillers using LiBr/water. Measurements were carried out in the laboratories at the Solar Energy Research Center SERC, at Högskolan Dalarna as well as at ClimateWell AB. The measurements at SERC were performed on a prototype version 7:1 and showed that this prototype had several problems resulting in poor and unreliable performance. The main results were that: there was significant corrosion leading to non-condensable gases that in turn caused very poor performance; unwanted crystallisation caused blockages as well as inconsistent behaviour; poor wetting of the heat exchangers resulted in relatively high temperature drops there. A measured thermal COP for cooling of 0.46 was found, which is significantly lower than the theoretical value. These findings resulted in a thorough redesign for the new prototype, called ClimateWell 10 (CW10), which was tested briefly by the authors at ClimateWell. The data collected here was not large, but enough to show that the machine worked consistently with no noticeable vacuum problems. It was also sufficient for identifying the main parameters in a simulation model developed for the TRNSYS simulation environment, but not enough to verify the model properly. This model was shown to be able to simulate the dynamic as well as static performance of the CW10, and was then used in a series of system simulations. A single system model was developed as the basis of the system simulations, consisting of a CW10 machine, 30 m2 flat plate solar collectors with backup boiler and an office with a design cooling load in Stockholm of 50 W/m2, resulting in a 7.5 kW design load for the 150 m2 floor area. Two base cases were defined based on this: one for Stockholm using a dry cooler with design cooling rate of 30 kW; one for Madrid with a cooling tower with design cooling rate of 34 kW. A number of parametric studies were performed based on these two base cases. These showed that the temperature lift is a limiting factor for cooling for higher ambient temperatures and for charging with fixed temperature source such as district heating. The simulated evacuated tube collector performs only marginally better than a good flat plate collector if considering the gross area, the margin being greater for larger solar fractions. For 30 m2 collector a solar faction of 49% and 67% were achieved for the Stockholm and Madrid base cases respectively. The average annual efficiency of the collector in Stockholm (12%) was much lower than that in Madrid (19%). The thermal COP was simulated to be approximately 0.70, but has not been possible to verify with measured data. The annual electrical COP was shown to be very dependent on the cooling load as a large proportion of electrical use is for components that are permanently on. For the cooling loads studied, the annual electrical COP ranged from 2.2 for a 2000 kWh cooling load to 18.0 for a 21000 kWh cooling load. There is however a potential to reduce the electricity consumption in the machine, which would improve these figures significantly. It was shown that a cooling tower is necessary for the Madrid climate, whereas a dry cooler is sufficient for Stockholm although a cooling tower does improve performance. The simulation study was very shallow and has shown a number of areas that are important to study in more depth. One such area is advanced control strategy, which is necessary to mitigate the weakness of the technology (low temperature lift for cooling) and to optimally use its strength (storage).

Characterization of residential chimney conditions for flue gas flow measurements

A literature survey and a theoretical study were performed to characterize residential chimney conditions for flue gas flow measurements. The focus is on Pitot-static probes to give sufficient basis for the development and calibration of a velocity pressure averaging probe suitable for the continuous dynamic (i.e. non steady state) measurement of the low flow velocities present in residential chimneys. The flow conditions do not meet the requirements set in ISO 10780 and ISO 3966 for Pitot-static probe measurements, and the methods and their uncertainties are not valid. The flow velocities in residential chimneys from a heating boiler under normal operating condi-tions are shown to be so low that they in some conditions result in voiding the assumptions of non-viscous fluid justifying the use of the quadratic Bernoulli equation. A non-linear Reynolds number dependent calibration coefficient that is correcting for the viscous effects is needed to avoid significant measurement errors. The wide range of flow velocity during normal boiler operation also results in the flow type changing from laminar, across the laminar to turbulent transition region, to fully turbulent flow, resulting in significant changes of the velocity profile during dynamic measurements. In addition, the short duct lengths (and changes of flow direction and duct shape) used in practice are shown to result in that the measurements are done in the hydrodynamic entrance region where the flow velocity profiles most likely are neither symmetrical nor fully developed. A measurement method insensitive to velocity profile changes is thus needed, if the flow velocity profile cannot otherwise be determined or predicted with reasonable accuracy for the whole measurement range. Because of particulate matter and condensing fluids in the flue gas it is beneficial if the probe can be constructed so that it can easily be taken out for cleaning, and equipped with a locking mechanism to always ensure the same alignment in the duct without affecting the calibration. The literature implies that there may be a significant time lag in the measurements of low flow rates due to viscous effects in the internal impact pressure passages of Pitot probes, and the significance in the discussed application should be studied experimentally. The measured differential pressures from Pitot-static probes in residential chimney flows are so low that the calibration and given uncertainties of commercially available pressure transducers are not adequate. The pressure transducers should be calibrated specifically for the application, preferably in combination with the probe, and the significance of all different error sources should be investigated carefully. Care should be taken also with the temperature measurement, e.g. with averaging of several sensors, as significant temperature gradients may be present in flue gas ducts.

Measurements of income inequality: a critique. Inflation and income inequality: a link through the job- search process

In this paper I claim that, in a long-run perspective, measurements of income inequality, under any of the usual inequality measures used in the literature, are upward biased. The reason is that such measurements are cross-sectional by nature and, therefore, do not take into consideration the turnover in the job market which, in the long run, equalizes within-group (e.g., same-education groups) inequalities. Using a job-search model, I show how to derive the within-group invariant-distribution Gini coefficient of income inequality, how to calculate the size of the bias and how to organize the data in arder to solve the problem. Two examples are provided to illustrate the argument.