Response Standardization for Drift Correction and Multivariate Calibration Transfer in "Electronic Tongue" Studies.

The procedures for response standardization in "electronic tongue" (ET) studies are described. The construction of reliable multivariate calibration for "electronic tongue" requires the analysis of a large number of representative samples both with ET and reference techniques. This is a laborious and expensive process. Long-term sensor array operation leads to the changes in sensor response characteristics and thus invalidates the multivariate predictive models. Moreover, due to the individual parameters of each sensor in different sensor arrays, it is not possible to use the calibration model for one system together with the data acquired by another system, even if they have the same sensors. Both of these issues lead to the necessity of frequent sensor array calibration which would be ideal to avoid. Instead of recalibration, these two problems can be handled using mathematical methods intended for sensor response standardization. This chapter describes two popular methods of standardization which can be used for both drift correction and calibration transfer. Thus, significant efforts on measuring representative sample sets for sensor array recalibration can be avoided.

Analytical Eco-Scale for Assessing the Greenness of a Developed Potentiometric Method for Lomefloxacin Hydrochloride Determination in its Different Dosage Forms, Plasma, and Dissolution Medium.

Background: Traditional methods for Lomefloxacin hydrochloride (LOM) determination involve pretreatment steps, which extend analysis time and use hazardous chemicals. Objective: The ability to provide a rapid route without sample pretreatment for quantitative determination of compounds via a low-cost instrument is a challenging task. In this work, a simple potentiometric method was developed to determine the antibacterial LOM via in-house fabricated ion selective electrodes. Methods: Different sensors were fabricated using a poly vinyl chloride-based membrane, potassium tetrakis(4-chlorophenyl) borate as a cation exchanger, and 2-Nitrophenyl octyl ether as a plasticizer (sensor 1). To increase the selectivity of sensor 1, a selective molecular recognition component 2-hydroxypropyl-ß-cyclodextrin was used as ionophore (sensor 2). Results: The proposed method was validated according to International Union of Pure and Applied Chemistry recommendations, in which the proposed sensors show a linear dynamic range from 1 × 10-5 to 1 × 10-2 mol/L, with Nernstian slopes of 55.829 and 58.229 mV/decade for sensors 1 and 2, respectively. It was applied to determine LOM in bulk powder, in different dosage forms, and in plasma with no sample pretreatment. Also, the suggested method can be used as a green, in-line bench top real-time analyzer for in-process monitoring of LOM release from its tablets, under U.S. Food and Drug Administration dissolution regulations, with clear discrimination from common excipients. Results obtained by the proposed potentiometric method were compared with those obtained by a reported HPLC method. Conclusions: The proposed method is considered as a perfect alternative to traditional reported methods for LOM determination.

Determination of Chloride in Infant Formula and Adult/Pediatric Nutritional Formula by Automated Potentiometry: Single-Laboratory Validation, First Action 2015.08.

A direct potentiometric method involving titration against a standard volumetric silver nitrate solution using a silver electrode to detect the end point was evaluated for the determination of chloride in infant formula and adult/pediatric nutritional formula. It was assessed for compliance against AOAC Standard Method Performance Requirements (SMPR®) established by the AOAC Stakeholder Panel on Infant Formula and Adult Nutritionals (SPIFAN). A single-laboratory validation (SLV) study was conducted as a first step in the process to validate the method. In this SLV, 17 SPIFAN matrixes representing a range of infant formula and adult nutritional products were evaluated for their chloride content. The analytical range was found to be between 1.4 and 1060 mg/100 g reconstituted product or ready-to-feed (RTF) liquid. The LOQ was estimated as 1.4 mg/100 g. Method repeatability was between 0.03 and 1.60% in the range of 20 to 167 mg/100 g RTF, and intermediate precision was between 0.09 and 2.77% in the same range. Recovery values based on spiking experiments at two different levels of chloride ranged from 99.0 to 103% for 15 different SPIFAN products. Evaluation of trueness was performed on National Institute of Standards and Technology Standard Reference Material 1849a (Infant/Adult Nutritional Formula) and showed 97.2% of the theoretical value, with no bias at the 95% confidence level. Based on the results of the SLV, the method met the SMPR and was approved as a First Action method by the AOAC Expert Review Panel on Infant Formula and Adult Nutritionals on March 17, 2015.

Reliability and measurement error of sagittal spinal motion parameters in 220 patients with chronic low back pain using a three-dimensional measurement device.

BACKGROUND CONTEXT: A basic premise for any instrument measuring spinal motion is that reliable outcomes can be obtained on a relevant sample under standardized conditions. PURPOSE: The purpose of this study was to assess the overall reliability and measurement error of regional spinal sagittal plane motion in patients with chronic low back pain (LBP), and then to evaluate the influence of body mass index, examiner, gender, stability of pain, and pain distribution on reliability and measurement error. STUDY DESIGN/SETTING: This study comprises a test-retest design separated by 7 to 14 days. PATIENT SAMPLE: The patient cohort consisted of 220 individuals with chronic LBP. OUTCOME MEASURES: Kinematics of the lumbar spine were sampled during standardized spinal extension-flexion testing using a 6-df instrumented spatial linkage system. METHODS: Test-retest reliability and measurement error were evaluated using interclass correlation coefficients (ICC(1,1)) and Bland-Altman limits of agreement (LOAs). RESULTS: The overall test-retest reliability (ICC(1,1)) for various motion parameters ranged from 0.51 to 0.70, and relatively wide LOAs were observed for all parameters. Reliability measures in patient subgroups (ICC(1,1)) ranged between 0.34 and 0.77. In general, greater (ICC(1,1)) coefficients and smaller LOAs were found in subgroups with patients examined by the same examiner, patients with a stable pain level, patients with a body mass index less than below 30 kg/m(2), patients who were men, and patients in the Quebec Task Force classifications Group 1. CONCLUSIONS: This study shows that sagittal plane kinematic data from patients with chronic LBP may be sufficiently reliable in measurements of groups of patients. However, because of the large LOAs, this test procedure appears unusable at the individual patient level. Furthermore, reliability and measurement error varies substantially among subgroups of patients.

Semi-automatic version of the potentiometric titration method for characterization of uranium compounds.

The potentiometric titration method was used for characterization of uranium compounds to be applied in intercomparison programs. The method is applied with traceability assured using a potassium dichromate primary standard. A semi-automatic version was developed to reduce the analysis time and the operator variation. The standard uncertainty in determining the total concentration of uranium was around 0.01%, which is suitable for uranium characterization and compatible with those obtained by manual techniques.

Novel screen-printed electrode for the determination of dodecyltrimethylammonium bromide in water samples.

The construction and electrochemical response characteristics of a screen-printed electrode (SPE) for the determination of dodecyltrimethylammonium bromide (DTAB) are described. The sensor was based on the use of DTA-tetraphenylborate ion association complex as an electroactive material in screen-printed electrode with dioctylsebacate (DOS) as a solvent mediator. In aqueous solution of pH 3, the sensor displayed a stable response for six months with reproducible potential and linear response for surfactant over the concentration range 1.20 × 10(-2) -5.6 × 10(-7) mol L(-1) at 25 °C with Nernstian slope of 55.95 ± 0.58 mV decade(-1) for detection limit of 6.8 x 10(-6) mol L(-1) . The response time was 6-10 s. The selectivity coefficients indicate excellent selectivity for DTAB over many common cations (e.g. Mg(2+), Na(+), K+, Co(2+), Ni(2+), Ca(2+), Cl(-), I(-), SO(4)(-2) and cetylpyridinium chloride (CPC). The sensor was used successfully for the determining of DTAB in pure form and water samples with average recoveries of 99.98, 98.78, and 99.99%.

Potentiometric sensor using sub-micron Cu2O-doped RuO2 sensing electrode with improved antifouling resistance.

A Cu(2)O-doped RuO(2) sensing electrode (SE) for potentiometric detection of dissolved oxygen (DO) was prepared and its structure and electrochemical properties were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron microscopy (XPS) and energy-dispersive spectroscopy (EDS) techniques. Cu(2)O-RuO(2)-SE displayed a linear DO response from 0.5 to 8.0 ppm (log[O(2)], -4.73 to -3.59) within a temperature range of 9-30 degrees C. The maximum sensitivity of -47.4 mV/decade at 7.27 pH was achieved at 10 mol% Cu(2)O. Experimental evaluation of the Cu(2)O-doped RuO(2)-SE demonstrated that the doping of RuO(2) not only improves its structure but also enhances both sensor's selectivity and antifouling properties. Selectivity measurements revealed that 10 mol% Cu(2)O-doped RuO(2)-SE is insensitive to the presence of Na(+), Mg(2+), K(+), Ca(2+), NO(3)(-), PO(4)(2-) and SO(4)(2-) ions in the solution in the concentration range of 10(-7)-10(-1) mol/l.

Two analyte calibrations from the transient response of a single potentiometric sensor employed with the SIA technique.

Simultaneous quantification of Cd(2+) and Pb(2+) in solution has been correctly targeted using the kinetic information from a single non-specific potentiometric sensor. Dual quantification was accomplished from the complex information in the transient response of an electrode used in a Sequential Injection Analysis (SIA) system and recorded after step injection of sample. Data was firstly preprocessed with the Discrete Wavelet Transform (DWT) to extract significant features and then fed into an Artificial Neural Network (ANN) for building the calibration model. DWT stage was optimized regarding the wavelet function and decomposition level, while the ANN stage was optimized on its structure. To simultaneously corroborate the effectiveness of the approach, two different potentiometric sensors were used as study case, one using a glass selective to Cd(2+) and another a PVC membrane selective to Pb(2+).

Simultaneous determination of zinc, cadmium and lead in environmental water samples by potentiometric stripping analysis (PSA) using multiwalled carbon nanotube electrode.

The present paper has focused on the potential application of multiwalled carbon nanotube for the development of a new, simple and highly selective electrochemical method for simultaneous Zn (II), Cd (II) and Pb (II) monitoring in water samples (lake and effluent waters), by using potentiometric stripping analysis (PSA). The electrochemical method is based on simultaneous preconcentration/reduction of metal ions onto a multiwall carbon nanotube electrode at -1.3V (versus Ag/AgCl(sat)) in 0.3 mol L(-1) acetate solution containing 15 mg L(-1) Hg (II) ions during 180s, followed by subsequent chemical stripping. The analytical curve for all analytes covered the linear range varying from 58.4 up to 646.2 microg L(-1) with correlation coefficients higher than 0.981. The limits of detection for Zn (II), Cd (II) and Pb (II) were found to be 28.0, 8.4 and 6.6 microg L(-1), while the relative standard deviation (RSD) at 352 microg L(-1) was 5.6, 7.1 and 5.6% (n=5), respectively. The behavior of the simultaneous determination in the presence of following ions Co (II), Cr (III) and Cu (II) was affected by using the analyte:interferent ratio 1:10. Therefore, by using standard addition method, Zn (II), Cd (II) and Pb (II) ions in lake and effluent water samples were determined after the spiking procedure and the results were successfully compared with those obtained by atomic absorption spectrometry (AAS). The obtained results suggest that the proposed method can be applied as a simple and efficient alternative for the simultaneous monitoring of heavy metals in water samples, according to those established requirements from environmental organizations. In addition, this method demonstrates the powerful application of carbon nanotubes in the field of potentiometric stripping analysis.

Urea enzymatic hydrolysis reaction: optimization by response surface methodology based on potentiometric measurements.

The enzymatic hydrolysis reaction of urea by urease is optimized in this work by the chemometric response surface methodology (RSM), based on an initial rate potentiometric measurement using an NH(4)(+) ion-selective electrode (ISE). In this investigation, the ranges of critical variables determined by a preliminary "one at a time" (OVAT) procedure were used as input for the subsequent RSM chemometric analysis. The RSM quadratic response was found to be quite appropriate for modeling and optimization of the hydrolysis reaction as illustrated by the relatively high value of the determination coefficient (R(2)=90.1%), along with the satisfactory results obtained by the analysis of variance (ANOVA). All the evaluated analytical characteristics of the optimized method such as: the linear calibration curve, the upper and lower detection limits, the within-day precisions at low and at high levels, the assay recovery in pool serum media, along with the activation kinetic parameters, were also reported. Further, in order to check the quality of the optimization and the validity of the model, the assay of urea, both in aqueous laboratory and human serum samples, were performed. It has to be noted that the kinetic initial rate measurement method used in this work, permitted to overcome the general problem of NH(4)(+) ISE low selectivity against Na(+) and K(+) interfering ions in real samples.

Chemometric determination of rabeprazole sodium in presence of its acid induced degradation products using spectrophotometry, polarography and anodic voltammetry at a glassy carbon electrode.

Chemometric stability indicating methods are presented for the determination of rabeprazole sodium in presence of its acid induced degradation products using spectrophotometry, differential pulse polarography and differential pulse anodic voltammetry at a glassy carbon electrode. The applied chemometric techniques are multivariate ones including classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS). A difference spectrophotometric (DeltaA) method has also been applied. To develop the multivariate calibrations, a training set was used, consisting of 20 mixture solutions of rabeprazole sodium and its degradation products. These mixtures show percentage degradation ranging from 0.5-65%, 0.5-95% and 0.6-75% for the spectrophotometric, polarographic and anodic voltammetric calibrations, respectively. The UV absorbances were recorded in 0.1 M NaOH within the wavelength range 220-340 nm at 2 nm intervals. The polarograms and anodic voltammograms were recorded in Britton-Robinson buffer (pH 8.0) within the potential range -500 to -1508 and 400 to 1192 mV at 6 mV intervals with a pulse amplitude of -100 and 50 mV, sweep rate of 15 and 10 mV s(-1) and pulse interval of 0.4 and 0.6 s for the polarographic and anodic voltammetric methods, respectively. All the studied methods have been validated and successfully applied to the determination of rabeprazole sodium in tablet dosage form. The results were statistically compared to those obtained using a published HPLC method. No significant difference has been found.

Determination of cationic surfactants in pharmaceutical disinfectants using a new sensitive potentiometric sensor.

A new sensitive potentiometric surfactant sensor was prepared based on a highly lipophilic 1,3-didecyl-2-methyl-imidazolium cation and a tetraphenylborate antagonist ion. This sensor was used as a sensing material and incorporated into the plasticized PVC-membrane. The sensor responded fast and showed a Nernstian response for investigated surfactant cations: cetylpyridinium chloride (CPC), hexadecyltrimethylammonium bromide (CTAB) and Hyamine with slope 59.8, 58.6 and 56.8 mV/decade, respectively. The sensor served as an end-point detector in ion-pair surfactant potentiometric titrations using sodium tetraphenylborate as titrant. Several technical grade cationic surfactants and a few commercial disinfectant products were also titrated, and the results were compared with those obtained from a two-phase standard titration method. The sensor showed satisfactory analytical performances within a pH range of 2-11, and exhibited excellent selectivity performance for CPC compared to all of the organic and inorganic cations investigated. The influence of the nonionic surfactants on the shape of titration curves was negligible if the mass ratio of ethoxylated nonionic surfactants and cationic surfactants (EONS:CS) was not greater than 5.

Determination of chloride in admixtures and aggregates for cement by a simple flow injection potentiometric system.

A simple flow injection system using three 3-way solenoid valves as an electric control injection valve and with a simple home-made chloride ion selective electrode based on Ag/AgCl wire as a sensor for determination of water soluble chloride in admixtures and aggregates for cement has been developed. A liquid sample or an extract was injected into a water carrier stream which was then merged with 0.1M KNO(3) stream and flowed through a flow cell where the solution will be in contact with the sensor, producing a potential change recorded as a peak. A calibration graph in range of 10-100 mg L(-1) was obtained with a detection limit of 2 mg L(-1). Relative standard deviations for 7 replicates injecting of 20, 60 and 90 mg L(-1) chloride solutions were 1.0, 1.2 and 0.6%, respectively. Sample throughput of 60 h(-1) was achieved with the consumption of 1 mL each of electrolyte solution and water carrier. The developed method was validated by the British Standard methods.

Azide-selective sensor based on tripodal iron complex for direct azide determination in aqueous samples.

A potentiometric azide-selective sensor based on the use of iron(III) hydrotris(3,5-dimethylpyrazolyl)borate acetylacetonate chloride [Tp(Me2)Fe(acac)Cl] as a neutral carrier for an azide-selective electrode is reported. Effect of various plasticizers, viz. o-nitrophenyloctyl ether (o-NPOE), dioctylphthalate (DOP), dibutylphthalate (DBP), and benzylacetate (BA), and an anion excluder, hexadecyltrimethylammonium bromide (HTAB), with [Tp(Me2)Fe(acac)Cl] complex in poly(vinyl chloride) (PVC) were studied. The best performance was obtained with a membrane composition of [Tp(Me2)Fe(acac)Cl]/HTAB/DOP/PVC in a ratio of 5:2:190:100 (w/w). The sensor exhibits significantly enhanced selectivity toward azide ions over the concentration range 6.3 x 10(-7) to 1.0 x 10(-2) M with a lower detection limit of 3.8 x 10(-7) M and a Nernstian slope of 59.4 +/- 1.1 mV decade(-1). Influences of the membrane composition, pH and possible interfering anions were investigated on the response properties of the electrode. Fast and stable response, good reproducibility, long-term stability and applicability over a wide pH range (3.5-9.0) are demonstrated. The sensor has a response time of 14 s and can be used for at least 45 days without any considerable divergence in the potential response. The proposed electrode shows fairly good discrimination of azide from several inorganic and organic anions. It was successfully applied to the direct determination of azide in orange juice, tea extracts and human urine samples.

Determination of potassium ions in biodiesel using a nickel(II) hexacyanoferrate-modified electrode.

In this work, nickel hexacyanoferrate-modified electrode was developed to determine potassium ions in biodiesel by potentiometry. The modified electrodes exhibit a linear response to potassium ions in the concentration range of 4.0 x 10(-5) to 1.0 x 10(-2) molL(-1), with a detection limit of 1.9 x 10(-5)mol L(-1), and a near-Nernstian slope (53-55 mV per decade) at 25 degrees C. The method developed in this work was compared with flame photometry and the potassium concentration found in biodiesel showed that the modified electrode method gives results similar to those obtained by flame photometry.

Good practices in single-cell amperometry.

Single-cell amperometry is a powerful tool for the study of the mechanisms underlying secretion from cells that release electrochemically active substances like catecholamines, histamine, or serotonin. Amperometry has changed our view of the secretory process and the quantal release phenomenon. Today, it is a relatively easy technique to set up and affordable for most laboratories. Amperometry can help solve many interesting problems in cell physiology or pharmacology. However, there are a number of issues about the experimental design, data analysis, and result interpretation that need to be considered. Here, we compile some recommendations and advice on how to conduct experiments with amperometry, covering tissue culture, electrode types and their construction, calibration, equipment, data acquisition, and strategies for electrical noise reduction. We concentrate on cultured chromaffin cells, although most of the information is equally applicable to other cell types.

Application of H-point standard addition method and partial least squares to the simultaneous kinetic-potentiometric determination of hydrazine and phenylhydrazine.

Simultaneous determination of hydrazine (HZ) and phenylhydrazine (PHZ) by H-point standard addition method (HPSAM) and partial least squares (PLS) regression was carried out based on kinetic data from novel potentiometry methods. The rate of chloride ion production in the reaction of HZ and PHZ with N-chlorosuccinimide (NCS) was monitored by a chloride ion-selective electrode. The experimental data show the good ability of ion-selective electrodes (ISEs) as detectors not only for the direct determination of chloride ion but also for simultaneous kinetic-potentiometric analysis using HPSAM and PLS methods. The methods are based on the differences observed in the production rate of chloride ions. The results show that simultaneous determination of HZ and PHZ can be performed in concentration ranges of 0.5 - 20.0 and 0.8 - 25.0 microg mL(-1), respectively. The total relative standard error for applying the PLS method to 8 synthetic samples in the concentration ranges of 1.0 - 16.0 microg mL(-1) for HZ and 2.0 - 16.0 microg mL(-1) for PHZ was 3.96. In order for the selectivity of the method to be assessed, we evaluated the effects of certain foreign ions upon the reaction rate and assessed the selectivity of the method. Both methods (PLS and HPSAM) were evaluated using a set of synthetic sample mixtures and then applied for simultaneous determination of HZ and PHZ in water samples.

Validación de una técnica potenciométrica para determinar el grado de desacetilación de la quitosana / Validation of potentiometric method to determine the degree of deacetylation of chitosan

Un método potenciométrico para la determinación del grado de desacetilación de muestras de quitosanas derivadas dequitina de langosta se validó según las exigencias internacionales actuales. Para garantizar que ocurriera la reaccióncompleta entre el analito y la disolución de HCl se aplicó calentamiento de las muestras a temperatura inferior a60ºC. Auxiliarmente a los cambios de pH, para la detección del primer punto de infl exión, se utilizó el anaranjadode metilo como indicador visual cuyo intervalo de transición está en un rango estrecho de pH ácido, entre 2 a 4. Nose registraron interferencias desde el punto de vista analítico en la zona de interés de la curva potenciométrica enausencia del analito, por lo que el método fue selectivo. Se demostró que el método fue lineal en el rango de 10.0a 15.0 mg/mL, además fue preciso y exacto para la determinación del porcentaje de grupos aminos libres

The purpose of this study was to validate, in accordance with international standards, a potentiometric method todetermine the degree of deacetylation of chitosan samples derived from lobster chitin. To ensure a complete reactionbetween the analyte and the HCl solution, the samples were heated to temperatures of up to 60ºC. The change in pHand the methyl orange method, as a visual indicator were used to detect the fi rst infl ection point. The transition intervalfell within the narrow pH acid range of 2 to 4. From an analytical point of view, no interference was observed onthe potentiometric curve in the absence of the analyte, thus showing that the method was suffi ciently selective. For thedetermination of the percentage of free amino groups, the method proved to be linear within the 10.0 to 15.0 mg/mL range, as well as precise and exact (AU)

Potentiometric batch and flow injection analysis of betaine hydrochloride.

Novel PVC membrane electrodes for the determination of betaine ion based on the formation of betaine-tetraphenylborate (Be-TPB) and betaine-phosphotungstate (Be-PT) ion-exchangers as electroactive materials are described. The sensors show a fast, stable, near Nernstian response for 6.92 x 10(-6) to 7.94 x 10(-3) M and 1.0 x 10(-4) to 1.0 x 10(-2) M betaine hydrochloride (Be.Cl) in case of Be-TPB electrode applying batch and flow injection analysis (FIA), respectively, and 2.95 x 10(-5) to 2.26 x 10(-3) M and 3.16 x 10(-5) to 1.0 x 10(-2) M in case of Be-PT electrode for batch and FIA electrodes, respectively, at 25 degrees C over the pH range of 3.5-10 with a cationic slope of 60.2 and 59.1 mV decade(-1) and a fast potential response of < or =15 s. The lower detection limits are 7.94 x 10(-6) and 3.18 x 10(-5) M Be.Cl for Be-TPB and Be-PT electrodes, respectively. Selectivity coefficient data for some common inorganic cations, sugars, amino acids and the components other than betaine, of the mixed drug investigated show negligible interference. The electrodes have been applied to the direct potentiometric determination of betaine hydrochloride in water and in a pharmaceutical preparation under batch and FIA conditions. Potentiometric titrations of Be.Cl with NaTPB and PTA as titrants were monitored with the developed betaine electrodes as an end point indicator electrode. The determination of Be.Cl shows an average recovery of 100.8% with mean relative standard deviation of 0.61%. The effect of temperature on the electrodes was also studied.

Development of a reference solution for the pH of seawater.

A method that uses a Harned cell to perform potentiometric pH measurements has been optimized and applied to an aqueous solution of simulated seawater that contains sodium perchlorate, sodium sulfate, sodium hydrogen carbonate and boric acid and has an ionic strength I of 0.57 mol kg(-1). The standard metrological approach developed for the measurement of pH in low ionic strength aqueous solutions was maintained, but a few modifications were necessary, and measurement procedures and calculations were modified ad hoc from those adopted in conventional protocols. When determining the standard potential of the cell, E degrees , NaClO4 salt was added to a 0.01 mol/kg HCl solution to attain the same ionic strength as the test solution and to investigate possible specific effects related to the high levels and the nature of the background electrolyte. An appropriate value of gamma (+/-HCl) (0.737) was then selected from the literature, based on a realistic value for I. Finally, in order to convert the acidity function at zero chloride molality into pH, a suitable value of gamma (Cl) (0.929) was calculated. As a result, we obtained pH=8.18 (T=25 degrees C) with an associated expanded uncertainty U=0.01 (coverage factor k=2). The aim was to establish a sound basis for the pH measurement of seawater by identifying the critical points of the experimental and theoretical procedure, and to discuss further possible developments that would be useful for achieving a reference solution.