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Linear Response (linear + response)
Terms modified by Linear Response Selected AbstractsElectrochemical Detection of Anions on an Electrophoresis Microchip with Integrated Silver ElectrodeELECTROANALYSIS, Issue 13 2005Jilin Yan Abstract A poly(dimethylsiloxane)/glass hybrid microfluidic chip with integrated silver electrode is described for electrochemical detection of anions. The working electrode was directly fabricated on a glass slide and the chip formed by reversibly sealing of a PDMS slab with microchannels to the slide. Under an alkaline phosphate condition, thiocyanide and three halides were sensitively detected. Factors influencing the separation and detection procedure were discussed and optimized. Linear responses over two magnitudes were obtained with limit of detection at the micromolar level. [source] Prussian Blue-Modified Titanate Nanotubes: A Novel Nanostructured Catalyst for Electrochemical Reduction of Hydrogen PeroxideELECTROANALYSIS, Issue 19 2010Damir Ivekovi Abstract Prussian blue (PB) modified titanate nanotubes (PB-TiNT) have been synthesized by the reaction of Fe2+ -modified TiNT with hexacyanoferrate(III) ions. The rate constant for heterogeneous catalytic reaction between PB-TiNT and H2O2 was found to be k=2×104,dm3,mol,1,s,1, which is an order of magnitude higher than the values of k reported for conventionally prepared, electrochemically deposited PB films. On the PB-TiNT modified electrode with subnanomolar surface concentration of PB (,(PB)=2.8×10,11,mol/cm2), a stable, reproducible and linear response towards H2O2 was obtained in the concentration range 0.02,4,mM, with the sensitivity of 0.10,AM,1,cm,2 at ,150,mV. [source] Tris(2,2,-bipyridyl)ruthenium(II) Electrogenerated Chemiluminescence Sensor Based on Platinized Carbon Nanotube,Zirconia,Nafion Composite FilmsELECTROANALYSIS, Issue 12 2010Hyun Yoon Abstract Mesoporous films of platinized carbon nanotube,zirconia,Nafion composite have been used for the immobilization of tris(2,2,-bipyridyl)ruthenium (II) (Ru(bpy)32+) on an electrode surface to yield a solid-state electrogenerated chemiluminescence (ECL) sensor. The composite films of Pt,CNT,zirconia,Nafion exhibit much larger pore diameter (3.55,nm) than that of Nafion (2.82,nm) and thus leading to much larger ECL response for tripropylamine (TPA) because of the fast diffusion of the analyte within the films. Due to the conducting and electrocatalytic features of CNTs and Pt nanoparticles, their incorporation into the zirconia,Nafion composite films resulted in the decreased electron transfer resistance within the films. The present ECL sensor based on the Pt,CNT,zirconia,Nafion gave a linear response (R2=0.999) for TPA concentration from 3.0,nM to 1.0,mM with a remarkable detection limit (S/N=3) of 1.0,nM, which is much lower compared to those obtained with the ECL sensors based on other types of sol-gel ceramic,Nafion composite films such as silica,Nafion and titania,Nafion. [source] Lactate Biosensor Based on Hydrotalcite-Like Compounds: Performances and Application to Serum SamplesELECTROANALYSIS, Issue 22 2009Irene Carpani Abstract A lactate biosensor based on lactate oxidase supported onto a hydrotalcite, electrochemically deposited on a platinum surface, was developed for the first time. For the best electrode configuration, a linear response up to 0.8,mM, with a limit of detection of 14,,M and a sensitivity of 91,mA M,1,cm,2, was obtained. The influence of some interferents due to the oxidation of hydrogen peroxide (at +0.35,V vs. SCE) was also studied. By controlling carefully the experimental conditions, the determination of lactate in a commercial serum sample in the presence of interferents was successfully accomplished. [source] Double Modification of Electrode Surface for the Selective Detection of Epinephrine and Its Application to Flow Injection Amperometric AnalysisELECTROANALYSIS, Issue 22 2009Guang-Ri Xu Abstract A glassy carbon electrode having two polymer layers has been applied to selectively detect epinephrine. The inner layer formed by electropolymerization of macrocyclic nickel complex functioned as an electrocatalyst for epinephrine oxidation and the outer layer composed of hydrolyzed polyurethane ,-benzyl L -glutamate as a screening layer. Differential pulse voltammetry showed almost 100% recovery of epinephrine even in 100-fold excess of interferents. When applied to a dual glassy carbon electrode as an amperometric detector in flow injection analysis, a linear response over 0.1,,M and 10,,M was obtained. Recovery tested for 5-fold diluted human urine samples was 97.5%. [source] Properties of Poly(sodium 4-styrenesulfonate)-Ionic Liquid Composite Film and Its Application in the Determination of Trace Metals Combined with Bismuth Film ElectrodeELECTROANALYSIS, Issue 5 2008Jianbo Jia Abstract A new kind of bismuth film modified electrode to sensitively detect trace metal ions based on incorporating highly conductive ionic liquids 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIMPF6) in solid matrices at glassy carbon (GC) was investigated. Poly(sodium 4-styrenesulfonate) (PSS), silica, and Nafion were selected as the solid matrices. The electrochemical properties of the mixed films modified GC were evaluated. The electron transfer rate of Fe(CN)64,/Fe(CN)63, can be effectively improved at the PSS-BMIMPF6 modified GC. The bismuth modified PSS-BMIMPF6 composite film electrodes (GC/PSS-BMIMPF6/BiFEs) displayed high mechanical stability and sensitive stripping voltammetric performances for the determination of trace metal cations. The GC/PSS-BMIMPF6/BiFE exhibited well linear response to both Cd(II) and Pb(II) over a concentration range from 1.0 to 50,,g L,1. And the detection limits were 0.07,,g L,1 for Cd(II) and 0.09,,g L,1 for Pb(II) based on three times the standard deviation of the baseline with a preconcentration time of 120,s, respectively. Finally, the GC/PSS-BMIMPF6/BiFEs were successfully applied to the determination of Cd(II) and Pb(II) in real sample, and the results of present method agreed well with those of atomic absorption spectroscopy. [source] Stripping Voltammetry of Cerium(IIl) with a Chemically Modified Carbon Paste Electrode Containing Functionalized Nanoporous Silica GelELECTROANALYSIS, Issue 2 2008Mehran Javanbakht Abstract This research introduces the design of an adsorptive stripping voltammetric method for the cerium(III) determination at a carbon paste electrode, chemically modified with dipyridyl-functionalized nanoporous silica gel (DPNSG-CPE). The electroanalytical procedure comprised two steps: the Ce(III) chemical accumulation at ,200,mV followed by the electrochemical detection of the Ce(III)/dipyridyl complex, using anodic stripping voltammetry. The factors, influencing the adsorptive stripping performance, were optimized including the modifier quantity in the paste, the electrolyte concentrations, the solution pH and the accumulation potential or time. The resulting electrode demonstrated a linear response over a wide range of Ce(III) concentration (1.0,28,ng mL,1). The precision for seven determinations of 4 and 10,ng mL,1 Ce(III) was 3.2% and 2.5% (relative standard deviation), respectively. The prepared electrode was used for the cerium determination in real samples and very good recovery results were obtained. [source] Simultaneous Determination of Quinoline and Pyridine Compounds in Gasoline and Diesel by Differential Pulse VoltammetryELECTROANALYSIS, Issue 6 2007Leonardo Abstract The presence of trace basic organonitrogen compounds such as quinoline and pyridine in derivative petroleum fuels plays an important role in maintaining the engines of vehicles. However, these substances can contaminate the environment and so must be controlled because most of them are potentially carcinogenic and mutagenic. For these reasons, a reliable and sensitive method was developed for the determination of basic nitrogen compounds in fuel samples such as gasoline and diesel. This method utilizes preconcentration on an ion,exchange resin (Amberlyte IR,120,H) followed by differential pulse voltammetry (DPV) on a glassy carbon electrode. The electrochemical behavior of quinoline and pyridine as studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion-controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF4 0.1,mol L,1) for quinoline (,1.95,V) and pyridine (,2.52,V) vs. Ag|AgCl|KClsat reference electrode. The proposed DPV method displayed a good linear response from 0.10 to 300,mg L,1 and a limit of detection (LOD) of 5.05 and 0.25,,g L,1 for quinoline and pyridine, respectively. Using the method of standard additions, the simultaneous determination of quinoline and pyridine in gasoline samples yielded 25.0±0.3 and 33.0±0.7,mg L,1 and in diesel samples yielded 80.3±0.2 and 131±0.4,mg L,1, respectively. Spike recoveries were 94.4±0.3% and 101±0.5% for quinoline and pyridine, respectively, in the fuel determinations. This proposed method was also compared with UV-vis spectrophotometric measurements. Results obtained for the two methods agreed well based on F and t student's tests. [source] Construction and Evaluation of a Gold Tubular Electrode for Flow Analysis: Application to Speciation of Antimony in Water SamplesELECTROANALYSIS, Issue 6 2007Rodrigo Santos Abstract A tubular gold electrode (TGE) is described for the first time by summarizing the important aspects of its construction and evaluation. Applicability of the TGE is evaluated in the speciation of Sb(III) and Sb(V) using anodic stripping voltammetry in a single flow manifold. Studies with surface active interferences and metallic cations were performed. The proposed conditions for antimony determination showed good tolerance towards cationic, anionic and nonionic surface active substances. A linear response for antimony was obtained for solutions containing significant amounts of several metallic cations. Linear calibration curves for Sb(III) were obtained in the range 1,10,ppb with a detection limit of 0.19,ppb (CV=2.91%, n=5, [Sb(III)]=5,ppb). For Sb(V), linear calibration curves were in the range 1,15,ppb with a detection limit of 0.32,ppb (CV=1.41%, n=5, [Sb(V)]=5,ppb). The figures of merit achieved sustain for the good applicability of the proposed method as it allows the determination of antimony at levels below maximum values permitted in consuming waters. Results of antimony concentration determined in water samples were validated against the ICP-MS reference procedure or compared with reference water samples. [source] Low Potential Detection of NADH at Titanium-Containing MCM-41,Modified Glassy Carbon ElectrodeELECTROANALYSIS, Issue 5 2007Zhihui Dai Abstract Titanium-containing MCM-41 (Ti-MCM-41) modified glassy carbon electrode (GCE) can exhibit an excellent electrocatalytic activity towards the oxidation of ,-Nicotinamide adenine dinucleotide (NADH). A dramatic decrease in the over-voltage of NADH oxidation reaction is observed at 0.28,V (vs. SCE). The modified electrode is found to be stable and reproducible. The electrode shows a linear response for a wide range of 10,1200,,M NADH and the detection limit is 8.0,,M. Ti-MCM-41 mesoporous molecular sieves provide an efficient matrix for development of NADH biosensors and the prepared electrode not only can be used to detect the concentration of NADH in biochemical reaction, but also as the potential matrix of the construction of dehydrogenases biosensor. [source] Electrostatic Assembly of a Redox Catalysis System for Detection of GlutamateELECTROANALYSIS, Issue 24 2006Alice Abstract Interfacial assemblies capable of determining glutamate by redox catalysis are prepared by electrostatic assembly of alternating layers of ferrocene poly(allylamine) polymer and glutamate oxidase on a gold electrode. Deposition of the polymer was confirmed in cyclic voltammetry measurements by the presence of a surface wave corresponding to the oxidation of the ferrocene group. In the presence of glutamate in the adjacent electrolyte solution, the current increases and approaches a pseudosteady state, consistent with redox catalysis. Electrodes modified with glutamate oxidase had a linear response to glutamate up to 0.0045,M with sensitivity of 20,,A/cm2 and a limit of detection of 31.4,,M glutamate. An apparent Michaelis,Menten constant of 0.40(±0.13),mM for the confined glutamate oxidase was determined for this assembly. When used in flow-injection experiments, glucose oxidase modified electrodes responded to transient zones of glucose; however, the detection limits of the assemblies to the flowing stream were substantially higher than found for measurements on static solutions. [source] Development of Novel Glucose and Pyruvate Biosensors at Poly(Neutral Red) Modified Carbon Film Electrodes.ELECTROANALYSIS, Issue 8 2006Application to Natural Samples Abstract Amperometric biosensors based on the corresponding oxidase enzyme with poly(neutral red) redox mediator have been developed for the determination of glucose and pyruvate. The enzymes have been immobilized on top of poly(neutral red) modified carbon film electrodes with glutaraldehyde as the cross-linking agent. The biosensors were characterized by cyclic voltammetry and by electrochemical impedance spectroscopy. The glucose biosensor exhibited a linear response in the range 90,,M to 1.8,mM with a detection limit of 22,,M and the pyruvate biosensor in the range 90 to 600,,M with a detection limit of 34,,M. The relative standard deviations were found to be 2.1% (n=3) and 2.8% (n=4) respectively. The interference effects of various compounds were also studied. The glucose content of several types of wine and the amount of pyruvate in onion and garlic were determined and the results were compared with those obtained by standard spectrophotometric methods. [source] Electrochemically-Induced Deposition of Amine-Functionalized Silica Films on Gold Electrodes and Application to Cu(II) Detection in (Hydro)Alcoholic MediumELECTROANALYSIS, Issue 19 2005Alain Walcarius Abstract Well-adherent amine-functionalized porous silica films have been deposited on gold electrodes by combining the self-assembly technology, the sol,gel process, and the electrochemical modulation of pH at the electrode/solution interface. A partial self-assembled monolayer of mercaptopropyl-trimethoxysilane (MPTMS) was first formed on disposable gold electrodes from recordable CDs (Au-CDtrodes). The so pretreated MPTMS-Au-CDtrodes were immersed in a stable sol solution (pH,3) containing (3-aminopropyl)-triethoxysilane (APTES) and tetraethoxysilane (TEOS). Polycondensation of the APTES and TEOS precursors was then achieved by applying a negative potential for a given period of time to generate a local pH increase at the electrode/solution interface and promote the deposition of the amine functionalized silica film adhering well to the electrode surface owing to the MPTMS monolayer acting somewhat as a "molecular glue". Various parameters affecting the electrodeposition process have been studied and the film permeability to redox probes in solution was characterized by cyclic voltammetry. The amine-functionalized silica film electrodes were then applied to the preconcentration of copper(II) species prior to their electrochemical detection by anodic stripping differential pulse voltammetry. Getting high sensitivity has however required the application of an electrochemical pre-activation step as the majority of the organo-functional groups were in the form of ammonium moieties (because the film was prepared from an acidic sol). This was achieved by applying a sufficiently negative potential to the electrode surface to reduce protons and increase consequently the amine-to-ammonium ratio within the film and, thus, the efficiency of the precocentration process. The resulting device was then optimized for copper(II) determination in hydroalcoholic medium, giving rise to a linear response in the 0.1,10,,M concentration range. [source] Microdimensional Polyaniline: Fabrication and Characterization of Dynamics of Charge Propagation at Microdisk ElectrodesELECTROANALYSIS, Issue 17 2004Karolina Caban Abstract We describe fabrication of microdimensional polyanilne films in a controlled manner by voltammetric potential cycling or controlled potential electrolysis on platinum microdisk electrodes. The film grows in a form of hemispherical microdeposits, and its size largely exceeds the size of a Pt microdisk. Consequently, the film covers both the Pt substrate as well as the surrounding glass seal. Since the adhering polyaniline layer is conducting, the latter situation may lead to an increase in the effective electrode surface area. The lateral growth of polyaniline films outside the microdisk has also been demonstrated by performing diagnostic voltammetric experiments with use of a double microdisk set-up in which independent polarization of each disk is feasible. Microelectrode-based chronocoulometry, that involves an uncomplicated well-defined reduction potential step starting from the emeraldine (conducting) form and ending at leucoemeraldine (nonconducting) form, yields (upon application of a sufficiently short pulse) a well-defined linear response of charge versus square root of time that is consistent with the linear effective diffusion as the predominant charge propagation mechanism. When describing the system kinetics in terms of the effective (apparent) diffusion coefficient, we expect this parameter to be on the level of 10,8,cm2 s,1 or lower. The relative changes in dynamics of charge transport are discussed with respect to the polyaniline film loading, the size of microdisk electrode, expansion of the active electrode area, and the choice of electrolyte (strong acid) anion. The results are consistent with the view that when Pt microelectrode is modified with PANI deposit exceeding the size of the microdisk substrate, it behaves in a way as if its surface area is effectively much larger than the geometric area of Pt microdisk. [source] Capillary electrophoretic chiral separation of hydroxychloroquine and its metabolites in the microsomal fraction of liver homogenatesELECTROPHORESIS, Issue 5-6 2006Carmem Dickow Cardoso Abstract A rapid, selective, and low-cost chiral capillary electrophoretic method was developed for the simultaneous analysis of hydroxychloroquine (HCQ) and its three chiral metabolites: desethylchloroquine (DCQ), desethylhydroxychloroquine (DHCQ), and bisdesethylchloroquine (BDCQ) in the microsomal fraction of liver homogenates. After liquid,liquid extraction using toluene as extracting solvent, the drug and metabolites were resolved on a fused-silica capillary (50,,m ID, 50,cm total length, and 42,cm effective length), using 100,mmol/L of Tris/phosphate buffer, pH,9.0 containing 1% w/v sulfated-,-CD and 30,mg/mL hydroxypropyl-,-CD. Detection was carried out at 220,nm. The extraction procedure was efficient in removing endogenous interferents, and low values (,15%) for CVs and deviation from theoretical values were demonstrated for both within-day and between-day assays. The quantitation limit was 125,ng/mL with linear response over the 125,2000,ng/mL of concentration range for all metabolites. After validation, the method was used for an in vitro metabolism study of HCQ. The major HCQ metabolite formed by microsomal enzymes was (,)-(R)-DHCQ. [source] Integration of a carbon microelectrode with a microfabricated palladium decoupler for use in microchip capillary electrophoresis/ electrochemistryELECTROPHORESIS, Issue 1 2005Michelle L. Kovarik Abstract A method to integrate a carbon microelectrode with a microfabricated palladium decoupler for use in microchip capillary electrophoresis (CE) is detailed. As opposed to previous studies with decouplers for microchip CE, the working electrode material, which is made by micromolding of a carbon ink, is different from the decoupling electrode material (palladium). The manner in which the working electrode is made does not add additional etching or lithographic steps to the fabrication of the glass electrode plate. The hybrid poly(dimethylsiloxane)/glass device was characterized with fluorescence microscopy and by monitoring the CE-based separation of dopamine. Hydrodynamic voltammograms exhibited diffusion-limited currents occurring at potentials above +1.0 V. It was also shown that the half-wave potential does not shift as the separation potential is changed, as is the case in nondecoupled systems. Gated injections of dopamine in a 25 mM boric acid buffer (pH 9.2) showed a linear response from 200 to 5 ,M (r2 = 0.9992), with a sensitivity of 5.47 pA/,M and an estimated limit of detection of 2.3 ,M (0.621 fmol, S/N = 3). This is the first report of coupling a carbon electrode with a decoupler in microchip CE. [source] Epifluorescence microscopy and image analysis of high-level polycyclic aromatic hydrocarbon contamination in soilsENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 12 2006J. Chadwick Roper Abstract Interactions between polycyclic aromatic hydrocarbons (PAHs) and soil are an important determinant of their chemical availability and transport. Laboratory examination of microscale PAH,soil interaction is limited by the availability of methods for particle-scale observation. Inverted epifluorescence microscopy, combined with digital photography and computer image analysis, was evaluated for specificity and linearity using dissolved PAHs. A pyrene filter (excitation wavelength, 360,400 nm; emission wavelength, 450,520 nm) gave nonspecific PAH fluorescence, and bias for fluoranthene, benzo[b]fluoranthene, benzo[g, h, i]perylene, and benz[a]anthracene was quantified in comparison to that for pyrene. Concentrations ranging from 1 to 10 mM for anthracene, fluoranthene, and pyrene and from 1 to 50 mM for naphthalene produced a linear response with low interpixel variability. Liquid-phase analyses validated use of the technique for the descriptive analysis of PAH distribution in solid samples, but liquid-phase calibration was not quantitative for spiked or field-contaminated soils. The mean luminance for three field soils was proportional to the values predicted from their chemically measured concentrations and to values from spiked, aged, uncontaminated materials. Image analysis of laboratory- and field-contaminated samples determined the area distribution of fluorescent intensity and the size of fluorescent areas exceeding a threshold luminance. These qualitative descriptions of the microscale spatial distribution of PAH contamination are presented as potential endpoints for future research on biogeochemical interactions in heavily contaminated solids. [source] AN EXACT FORM OF THE BREEDER'S EQUATION FOR THE EVOLUTION OF A QUANTITATIVE TRAIT UNDER NATURAL SELECTIONEVOLUTION, Issue 11 2005John S. Heywood Abstract Starting with the Price equation, I show that the total evolutionary change in mean phenotype that occurs in the presence of fitness variation can be partitioned exactly into five components representing logically distinct processes. One component is the linear response to selection, as represented by the breeder's equation of quantitative genetics, but with heritability defined as the linear regression coefficient of mean offspring phenotype on parent phenotype. The other components are identified as constitutive transmission bias, two types of induced transmission bias, and a spurious response to selection caused by a covariance between parental fitness and offspring phenotype that cannot be predicted from parental phenotypes. The partitioning can be accomplished in two ways, one with heritability measured before (in the absence of) selection, and the other with heritability measured after (in the presence of) selection. Measuring heritability after selection, though unconventional, yields a representation for the linear response to selection that is most consistent with Darwinian evolution by natural selection because the response to selection is determined by the reproductive features of the selected group, not of the parent population as a whole. The analysis of an explicitly Mendelian model shows that the relative contributions of the five terms to the total evolutionary change depends on the level of organization (gene, individual, or mated pair) at which the parent population is divided into phenotypes, with each frame of reference providing unique insight. It is shown that all five components of phenotypic evolution will generally have nonzero values as a result of various combinations of the normal features of Mendelian populations, including biparental sex, allelic dominance, inbreeding, epistasis, linkage disequilibrium, and environmental covariances between traits. Additive genetic variance can be a poor predictor of the adaptive response to selection in these models. The narrow-sense heritability s,2A/s,2P should be viewed as an approximation to the offspring-parent linear regression rather than the other way around. [source] Determination of linear response in the detection of mixtures of aroma compounds by atmospheric pressure ionization,mass spectrometry (API,MS)FLAVOUR AND FRAGRANCE JOURNAL, Issue 1 2008Roberto A. Buffo Abstract The linearity of atmospheric pressure ionization,mass spectrometry (API,MS) response in mixtures of aroma compounds was determined for a ,homogeneous' system (four esters) and a ,heterogeneous' system (five compounds of different chemical functionality). All combinations analysed within each system followed a saturation pattern as concentration increased. Total linear responses were determined by the linear behaviour of individual compounds. Ionization patterns within each mixture were explained by proton affinity data (i.e. the species' ability to accept protons), molecular reaction rates (defined by molecular weight), and product ion distribution (according to fragmentation of the corresponding parent ion). Copyright © 2007 John Wiley & Sons, Ltd. [source] Analysis of a Japanese Black Cattle-rearing system utilizing a bahiagrass (Paspalum notatum Flügge) pasture: 3.GRASSLAND SCIENCE, Issue 3 2006Intake from pasture Abstract A Japanese Black Cattle-rearing system utilizing a bahiagrass (Paspalum notatum Flügge) pasture in coastal Miyazaki, southern Japan, was analyzed in terms of intake from pasture. In a field approach, herbage intake by grazing cattle was measured for nine periods (1,5 days) during a grazing season (May,October) along with some other variables (e.g. air temperature, herbage mass, digestibility of grazed herbage), under varying levels of supplementary feeding. The intake from the pasture was most closely related to the intake of supplement, showing a negative linear response at a substitution rate of 0.736,0.750. The intake under no supplementation, i.e. a maximum intake from the pasture, was lower than the voluntary intake predicted with feeding standards. In a modeling approach, a semi-mechanistic model for predicting grazing intake was developed using information from the literature as well as the field data. The performance of the model was acceptable. The model showed similar substitution rates (0.64,0.69), and considerable intake restriction (nearly 30%) that is not attributable to limitations by herbage mass, herbage allowance, diet digestibility or air temperature. The results indicate that a low maximal intake by the animals due to low grazing motivation is a major characteristic of the system where supplementation is a usual management practice. [source] On Selection of the Perturbation Amplitude Required to Avoid Nonlinear Effects in Impedance MeasurementsISRAEL JOURNAL OF CHEMISTRY, Issue 3-4 2008Bryan Hirschorn Numerical simulations of electrochemical systems were used to explore the influence of large-amplitude potential perturbations on the measured impedance response. The amplitude of the input potential perturbation used for impedance measurements, normally fixed at a value of 10 mV for all systems, should instead be adjusted for each experimental system. Guidelines are developed for selection of appropriate perturbation amplitudes. A characteristic transition frequency is defined that can be used to tailor a frequency-dependent input signal to optimize signal-to-noise levels while maintaining a linear response. [source] Assessing river biotic condition at a continental scale: a European approach using functional metrics and fish assemblagesJOURNAL OF APPLIED ECOLOGY, Issue 1 2006D. PONT Summary 1The need for sensitive biological measures of aquatic ecosystem integrity applicable at large spatial scales has been highlighted by the implementation of the European Water Framework Directive. Using fish communities as indicators of habitat quality in rivers, we developed a multi-metric index to test our capacity to (i) correctly model a variety of metrics based on assemblage structure and functions, and (ii) discriminate between the effects of natural vs. human-induced environmental variability at a continental scale. 2Information was collected for 5252 sites distributed among 1843 European rivers. Data included variables on fish assemblage structure, local environmental variables, sampling strategy and a river basin classification based on native fish fauna similarities accounting for regional effects on local assemblage structure. Fifty-eight metrics reflecting different aspects of fish assemblage structure and function were selected from the available literature and tested for their potential to indicate habitat degradation. 3To quantify possible deviation from a ,reference condition' for any given site, we first established and validated statistical models describing metric responses to natural environmental variability in the absence of any significant human disturbance. We considered that the residual distributions of these models described the response range of each metric, whatever the natural environmental variability. After testing the sensitivity of these residuals to a gradient of human disturbance, we finally selected 10 metrics that were combined to obtain a European fish assemblage index. We demonstrated that (i) when considering only minimally disturbed sites the index remains invariant, regardless of environmental variability, and (ii) the index shows a significant negative linear response to a gradient of human disturbance. 4Synthesis and applications. In this reference condition modelling approach, by including a more complete description of environmental variability at both local and regional scales it was possible to develop a novel fish biotic index transferable between catchments at the European scale. The use of functional metrics based on biological attributes of species instead of metrics based on species themselves reduced the index sensitivity to the variability of fish fauna across different biogeographical areas. [source] Facile synthesis, characterization, and potential applications of two kinds of polymeric pH indicators: Phenolphthalein formaldehyde and o -cresolphthalein formaldehydeJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 5 2005Zhihong Liu Abstract Two kinds of applicable polymeric pH indicators were synthesized by the reaction of phenolphthalein and o -cresolphthalein with formaldehyde under alkaline conditions by a one-pot method. The synthesized products were fully characterized with Fourier transform infrared, 1H NMR, ultraviolet,visible spectroscopy, and gel permeation chromatography. The results indicated that the reaction was a typical phenol formaldehyde reaction. The dosage of formaldehyde and the reaction time were well controlled to obtain soluble polymers, instead of crosslinked products. The polymeric-pH-indicator-immobilized poly(vinyl alcohol) (PVA) membranes were easily fabricated and had good long-term stability under highly basic conditions and a fast equilibrium response. Moreover, the phenolphthalein formaldehyde immobilized PVA membrane had a linear response from pH 10.0 to 14.0, and so it has promise as a optical transducer for high pH value determinations. The o -cresolphthalein formaldehyde immobilized PVA membrane had a nonlinear response from pH 9.0 to 13.0. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1019,1027, 2005 [source] Headspace single-drop microextraction of herbal essential oilsJOURNAL OF SEPARATION SCIENCE, JSS, Issue 2 2008Martin Adam Abstract A method employing the headspace single-drop microextraction (HS-SDME) is presented for the determination of essential oils in dried herbal leaves. By optimising the key experimental parameters, a linear response for the individual target compounds was obtained in the concentration range from LOQ to 4 mg/mL (r2 = 0.9912,0.9998), with LODs from 3.3 up to 20.5 ,g per 100 g of dried leaves, and the repeatability within the RSD of 2.1,8.9%. The HS-SDME-based procedure, enabling a rapid and simple analysis of essential oils in herbs, was applied to selected real samples (nine essential oils in four different samples) in combination with GC-FID identification and quantification of the target volatiles. [source] Analysis of alkaloids in Ipecacuanhae radix and preparations by capillary zone electrophoresisJOURNAL OF SEPARATION SCIENCE, JSS, Issue 12-13 2003Sonja Sturm Abstract A capillary zone electrophoresis method for quantitation of the alkaloids emetine and cephaeline in Ipecacuanhae radix fluid extract and Ipecac syrup using papaverine as internal standard is described. Baseline separation was achieved within 10 min using a fused silica capillary and a running electrolyte consisting of citric acid (50 mM), disodium hydrogenphosphate (100 mM), and 2.5% methanol (pH 4.4). Regression equations revealed a linear response from 0.05 to 1.9 mg/mL for cephaeline and emetine (correlation coefficients 0.9991,0.9993). The lowest quantitation limits were determined as 0.03 mg/mL for both alkaloids, and the limit of detection was 0.012 mg/mL. The day-to-day variations of retention times were < 1.3% for both compounds. Whereas no sample pre-treatment was necessary for analysis of the fluid extract, SPE had to be applied before CE analysis of the syrup. The recovery rate for emetine in this case was > 99.8%. [source] Effects of plant phenology, nutrients and herbivory on growth and defensive chemistry of plantain, Plantago lanceolataOIKOS, Issue 2 2000C. M. Jarzomski To assess the combined effect of herbivory, nutrient availability and plant phenology on plant mass and defensive chemistry, we conducted a field experiment with plantain (Plantago lanceolata: Plantaginaceae) using three levels of herbivory, three levels of fertilizer and two harvest dates. Shoot mass of the no-herbivory plants showed a nonlinear response to increased fertilizer such that mass with high fertilizer was no greater than that with low fertilizer. In contrast, shoot mass of the low-herbivory plants (12% damage) was not influenced by fertilizer, but for high-herbivory plants (23% damage), there was a positive linear response to increased fertilizer. Increasing nutrient levels caused a decrease in iridoid glycoside concentration. Herbivory did not induce higher iridoid glycoside concentration in leaves of any age. But increasing herbivory resulted in a decrease in the concentration of catalpol in new leaves. Another experiment assessed how leaf age and plant age affected plant defensive chemistry. Total iridoid glycosides increased over 5 weeks, but catalpol only increased in new leaves. Overall, the order of importance in determining variation in iridoid glycoside concentration was plant phenology, nutrient availability and, to a much lesser extent, herbivory. [source] Non-invasive in vivo determination of UVA efficacy of sunscreens using diffuse reflectance spectroscopyPHOTODERMATOLOGY, PHOTOIMMUNOLOGY & PHOTOMEDICINE, Issue 4 2003R. Gillies Background: Evaluation of sunscreen efficacy is most relevant when measured on the surface it is meant to protect, namely on human skin in vivo. Application of any material to the surface of the skin alters its optical properties. Diffuse reflectance spectroscopy (DRS) is a non-invasive technique to measure changes in the optical properties of the skin decoupled from its biological responses following sunscreen application. Methods: This study compared measurements of UVA efficacy of oxybenzone and avobenzone at different concentrations (0,5%) using DRS, human phototest and an in vitro technique. Twenty subjects were enrolled for each product measured by DRS and 10 different subjects were enrolled for each product measured by human phototest. Six areas 5 cm × 10 cm were outlined on each subject's back. DRS measurements were performed on four subsites within each area before and 20 min after sunscreen application. UVA efficacy for each concentration of product was calculated from the measured transmission spectrum of a given product convoluted with the spectrum of a Xenon light source adequately filtered to obtain the UVA spectrum from 320 to 400 nm and the erythema action spectrum. Phototesting was performed using the same light source and persistent pigment darkening as the biological endpoint. Measurements were made with sunscreen coverage of 2 mg/cm2. In vitro measurements were performed using an Optometrics instrument. Results: All three techniques showed a linear response between calculated UVA efficacy and product concentration. Conclusions: This study showed that DRS is a rapid and reproducible method to calculate UVA efficacy of sunscreen materials and that its results correlate closely with those obtained by human phototesting. [source] Synthesis and characterization of Li2SO4:P, RE (RE = Dy or Eu), low Z, TLD phosphorsPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 1 2003S. J. Dhoble Abstract Li2SO4 : P, Dy and Li2SO4 : P, Eu, low Z phosphors (Zeff = 11.19) are reported. These are shown to be more sensitive than the commercially used LiF-TLD 100 phosphor (Zeff = 8.4). The phosphors have a linear response, negligible fading and excellent reusability. These properties make these phosphors a suitable replacement for LiF-TLD 100 which is currently used for the dosimetry of the ionising radiations using thermoluminescence. [source] Elasticity, electronic structure, and dielectric property of cubic SrHfO3 from first-principlesPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 1 2009Z. F. Hou Abstract Recently, SrHfO3 compound was proposed as a potential gate dielectric to fabricate metal,oxide,semiconductor field-effect transistors (MOSFET) with equivalent oxide thickness (EOT) below 1 nm. Here we report the elasticity, electronic structure, and dielectric property of cubic SrHfO3 from first-principle study based on the plane-wave pseudopotential method within the local density approximation (LDA). The independent elastic constants of cubic SrHfO3 are derived from the derivative of total energy as a function of lattice strain. The elastic modulus is predicted from Voight-Hill bounds. The Born effective charges, electronic dielectric tensors, long wavelength phonon frequencies, and LO,TO splitting of cubic SrHfO3 are computed by linear response with density functional perturbation theory (DFPT). The calculated lattice constant and bulk modulus of cubic SrHfO3 are in good agreement with the available experimental data and other theoretical results. Our results show cubic SrHfO3 is a ductile insulator with an indirect band gap of 3.74 eV (LDA value) and electric dielectric tensor of 4.43, Hf 5d states and O 2p states exhibit a strong hybridization, and cubic SrHfO3 can be mechanically stable. In addition, the phonon frequency of ,soft mode' at zone-center also agrees well with previous theoretical value. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Development and validation of a gas chromatography/mass spectrometry method for the metabolic profiling of human colon tissueRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 4 2009Mainak Mal In this study, a gas chromatography/mass spectrometry (GC/MS) method was developed and validated for the metabolic profiling of human colon tissue. Each colon tissue sample (20,mg) was ultra-sonicated with 1,mL of a mixture of chloroform/methanol/water in the ratio of 20:50:20 (v/v/v), followed by centrifugation, collection of supernatant, drying, removal of moisture using anhydrous toluene and finally derivatization using N -methyl- N -trifluoroacetamide (MSTFA) with 1% trimethylchlorosilane (TMCS). A volume of 1,µL of the derivatized mixture was injected into the GC/MS system. A total of 53 endogenous metabolites were separated and identified in the GC/MS chromatogram, all of which were selected to evaluate the sample stability and precision of the method. Of the identified endogenous metabolites 19 belonging to diverse chemical classes and covering a wide range of the GC retention times (Rt) were selected to investigate the quantitative linearity of the method. The developed GC/MS method demonstrated good reproducibility with intra- and inter-day precision within relative standard deviation (RSD) of ±15%. The metabolic profiles of the intact tissue were determined to be stable (100,±,15%) for up to 90 days at ,80°C. Satisfactory results were also obtained in the case of other stability-indicating studies such as freeze/thaw cycle stability, bench-top stability and autosampler stability. The developed method showed a good linear response for each of the 19 analytes tested (r2,>,0.99). Our GC/MS metabolic profiling method was successfully applied to discriminate biopsied colorectal cancer (CRC) tissue from their matched normal tissue obtained from six CRC patients using orthogonal partial least-squares discriminant analysis [two latent variables, R2Y,=,0.977 and Q2 (cumulative),=,0.877]. Copyright © 2009 John Wiley & Sons, Ltd. [source] | ||||||||||||||||||||||||||||||||||