Experimental Investigation of the Tensile Behavior of Selected Tire Cords Using Novel Testing Equipment.

Aramid and polyamide cords are used in a wide range of applications, particularly in the automotive industry (tire reinforcement) and textile industry for military and fireguard purposes. The problem of the reliable experimental study of tensile behavior of synthetic cords is considered in this paper. In the available standards for synthetic cord testing, particularly ASTM D 885-03, the tensile test must result with the cord damage in the middle of gauge length, and the cords should be fixed in the machine clamps. The trial test gave damage near the clamps. We propose a novel testing stage mounted in the testing machine clamps to achieve the uniform tensile stress distribution in the gauge length of the measured cords. The results of the deformations were measured in two ways: using testing machine head displacement and a videoextensometer. Stress curves of four distinguished cords were evaluated and compared. The second method allowed to acquire results differing from the manufacturers' data from 0.7% to 21.5%, which allowed for the conclusion that the designed test stand allows for obtaining reliable results for stretched cords.

The Use of an Acylhydrazone-Based Metal-Organic Framework in Solid-Contact Potassium-Selective Electrode for Water Analysis.

A solid-contact ion-selective electrode was developed for detecting potassium in environmental water. Two versions of a stable cadmium acylhydrazone-based metal organic framework, i.e., JUK-13 and JUK-13_H2O, were used for the construction of the mediation layer. The potentiometric and electrochemical characterizations of the proposed electrodes were carried out. The implementation of the JUK-13_H2O interlayer is shown to improve the potentiometric response and stability of measured potential. The electrode exhibits a good Nernstian slope (56.30 mV/decade) in the concentration range from 10-5 to 10-1 mol L-1 with a detection limit of 2.1 µmol L-1. The long-term potential stability shows a small drift of 0.32 mV h-1 over 67 h. The electrode displays a good selectivity comparable to ion-selective electrodes with the same membrane. The K-JUK-13_H2O-ISE was successfully applied for the determination of potassium in three certified reference materials of environmental water with great precision (RSD < 3.00%) and accuracy (RE < 3.00%).

Novel Integrated Flow-Based Steam Distillation and Titration System for Determination of Volatile Acidity in Wines.

Novel integrated flow-based steam distillation and titration system with spectrophotometric detection was developed for determination of volatile acidity in wines. Using the system, the distillation procedure was carried out in an automatic manner, starting with introducing into a heated steam distillation module a sample and subjecting it to steam distillation. Under selected conditions, all the analyte was transferred to the distillate; therefore, the system did not require calibration. The collected distillate and titrant were introduced into the next monosegments in varying proportions, in accordance with the developed titration procedure, and directed to the detection system to record the titration curve. The titration was stopped after reaching the end point of titration. Procedures for distillation and titration were developed and verified separately by distillation of acetic acid, acetic acid in the presence of tartaric acid as well as acetic acid, tartaric acid, and titratable acidity, with precision (relative standard deviation) and accuracy (relative error) for both procedures lower than 6.9 and 5.6%, respectively. The developed steam distillation and titration systems were used to determine volatile acidity in samples of white and rosé wines separately and as the integrated steam distillation and titration system, both with precision lower than 9.4% and accuracy better than 6.7%.

A Perspective of the Comprehensive and Objective Assessment of Analytical Methods Including the Greenness and Functionality Criteria: Application to the Determination of Zinc in Aqueous Samples.

The recently proposed concept of White Analytical Chemistry (WAC), referring to the Red-Green-Blue color model, combines ecological aspects (green) with functionality (red and blue criteria), presenting the complete method as "white". However, it is not easy to carry out an overall quantitative evaluation of the analytical method in line with the WAC idea in an objective manner. This paper outlines the perspective of the future development of such a possibility by attempting to answer selected questions about the evaluation process. Based on the study consisting in the evaluation of selected model methods by a group of 12 independent analysts, it was shown how well individual criteria are assessed, whether the variability of assessments by different people is comparable for each criterion, how large it is, and whether averaging the scores from different researchers can help to choose the best method more objectively.

Comprehensive Assessment of Flow and Other Analytical Methods Dedicated to the Determination of Zinc in Water.

An original strategy to evaluate analytical procedures is proposed and applied to verify if the flow-based methods, generally favorable in terms of green chemistry, are competitive when their evaluation also relies on other criteria. To this end, eight methods for the determination of zinc in waters, including four flow-based ones, were compared and the Red-Green-Blue (RGB) model was exploited. This model takes into account several features related to the general quality of an analytical method, namely, its analytical efficiency, compliance with the green analytical chemistry, as well as practical and economic usefulness. Amongst the investigated methods, the best was the flow-based spectrofluorimetric one, and a negative example was that one involving a flow module, ICP ionization and MS detection, which was very good in analytical terms, but worse in relation to other aspects, which significantly limits its overall potential. Good assessments were also noted for non-flow electrochemical methods, which attract attention with a high degree of balance of features and, therefore, high versatility. The original attempt to confront several worldwide accepted analytical strategies, although to some extent subjective and with limitations, provides interesting information and indications, establishing a novel direction towards the development and evaluation of analytical methods.

3D-printed manifold integrating solid contact ion-selective electrodes for multiplexed ion concentration measurements in urine.

Urinalysis is a simple and non-invasive approach for the diagnosis and monitoring of various health disorders. While urinalysis is predominantly confined to clinical laboratories the non-invasive sample collection makes it applicable in wide range of settings outside of central laboratory confinements. In this respect, 3D printed devices integrating sensors for measuring multiple parameters may be one of the most viable approaches to ensure cost-effectiveness for widespread use. Here we evaluated such a system for the multiplexed determination of sodium, potassium and calcium ions in urine samples with ion-selective electrodes based on state of the art octadecylamine-functionalized multi-walled carbon nanotube (OD-MWCNT) solid contacts. The electrodes were tested in the clinically relevant concentration range, i.e. ca. 10-4 - 10-1 mol L-1 and were proven to have Nernstian responses under flow injection conditions. The applicability of the 3D printed flow manifold was investigated through the analysis of synthetic samples and two certified reference materials. The obtained results confirm the suitability of the proposed system for multiplexed ion analysis in urine.

3D-printed flow manifold based on potentiometric measurements with solid-state ion-selective electrodes and dedicated to multicomponent water analysis.

A 3D-printed flow manifold dedicated to potentiometric simultaneous determination of potassium, sodium, calcium and chloride in water is presented. The method is based on application of miniature solid-contact ion selective electrodes with a special design obtained with the use of 3D printing. The electrodes offer many attractive advantages including short response time and miniaturization feasibility. The use of the proposed novel electrodes enables performance of rapid potentiometric measurements in flow-injection technique and registration of many injection peaks in a short time. One of the advantages of using a special 3D-printed flow vessel for potentiometric measurements was miniaturization of electrodes and the possibility of integrating several (from three up to six) ion selective electrodes in one module enabling realization of multi-component analyses in the same time. Thanks to that the volume of each solution and measurement time were significantly reduced during multi-component analysis. In order to find out if the proposed manifold works properly, three multi-component synthetic samples and four certified reference materials were analyzed. The presented study shows that the proposed 3D-printed flow manifold with solid-state ion-selective electrodes could be an effective tool in a modern multi-component analysis meeting the requirements of green analytical chemistry.

Novel Approach to Automated Flow Titration for the Determination of Fe(III).

A novel approach to automated flow titration with spectrophotometric detection for the determination of Fe(III) is presented. The approach is based on the possibility of strict and simultaneous control of the flow rates of sample and titrant streams over time. It consists of creating different but precisely defined concentration gradients of titrant and analyte in each successively formed monosegments, and is based on using the calculated titrant dilution factor. The procedure was verified by complexometric titration of Fe(III) in the form of a complex with sulfosalicylic acid, using EDTA as a titrant. Fe(III) and Fe(II) (after oxidation to Fe(III) with the use of H2O2) were determined with good precision (CV lower than 1.7%, n = 6) and accuracy ( | RE | lower than 3.3%). The approach was applied to determine Fe(III) and Fe(II) in artesian water samples. Results of determinations were consistent with values obtained using the ICP-OES reference method. Using the procedure, it was possible to perform titration in 6 min for a wide range of analyte concentrations, using 2.4 mL of both sample and titrant.

Novel Approach to Sample Preconcentration by Solvent Evaporation in Flow Analysis.

A preconcentration module operated in flow mode and integrated with a sequential injection system with spectrophotometric detection was developed. Using the system, preconcentration was performed in continuous mode and was based on a membraneless evaporation process under diminished pressure. The parameters of the proposed system were optimized and the system was tested on the example of the spectrophotometric determination of Cr(III). The preconcentration effectiveness was determined using the signal enhancement factor. In the optimized conditions for Cr(III), it was possible to obtain the signal enhancement factors of around 10 (SD: 0.9, n = 4) and determine Cr(III) with precision and intermediate precision of 8.4 and 5.1% (CV), respectively. Depending on the initial sample volume, signal enhancement factor values of about 20 were achieved. Applicability of the developed preconcentration system was verified in combination with the capillary electrophoresis method with spectrophotometric detection on the example of determination of Zn in certified reference materials of drinking water and wastewater. Taking into account the enhancement factor of 10, a detection limit of 0.025 mg L-1 was obtained for Zn determination. Zn was determined with precision less than 6% (CV) and the results were consistent with the certified values.

Employment of electrostriction phenomenon for label-free electrochemical immunosensing of tetracycline.

The presented work describes a simple label-free electrochemical immunosensor for the determination of tetracycline (TC). The functioning of the sensor was based on the electrostriction of a antibody-terminated thiol layer self-assembled on a gold electrode surface, serving as a dielectric membrane. The intensity of electrostriction was correlated with the amount of TC captured through an affinity reaction with its specific antibody, and was followed in the form of capacitance-potential curves. The process of the immunosensor construction was optimized using electrochemical impedance spectroscopy (EIS). The chemisorption time of the thiol, the duration of the TCAb immobilization and its concentration were optimized. The developed immunosensor exhibited a linear response in two concentration ranges: from 0.95 to 10 µmol L-1 and from 10 to 140 µmol L-1, with the mean sensitivity of 6.27 nF µmol-1 L (88.67 nF µmol-1 L cm-2) and 0.56 nF µmol-1 L (7.84 nF µmol-1 L cm-2), respectively. The limit of detection was evaluated as 28 nmol L-1. The specificity of the proposed sensor toward other antibiotics, amoxicillin and ciprofloxacin, was examined. The immunosensor was successfully employed to quantify TC in a tablet form and in a matrix of river water.

Reliable calibration by nonlinear standard addition method in the presence of additive interference effects.

ABSTRACT: The possibility of adapting the Standard Addition Method (SAM) to calibration in very difficult analytical conditions, namely when there is a need to determine an analyte with the use of nonlinear calibration graph and in the presence of matrix components causing additive interference effect, is investigated. To this aim the SAM in the common version and the Chemical H-point Standard Addition Method (C-HPSAM) realized by the flow injection technique were applied. Specifically, a flow manifold was used for construction of a set of nonlinear calibration graphs in different chemical conditions. As the graphs were intersected indicating both the additive interference effect and the analytical result free of this effect, the analyte concentration in the sample was able to be obtained with improved accuracy. The applicability of this approach was verified on the example of spectrophotometric determination of paracetamol in pharmaceuticals and of total acidity in wines. The C-HPSAM method enabled complete compensation of the additive effect and obtaining analytical results at a relative error not exceeding 6.0%.

Sequential injection system with in-line solid phase extraction and soil mini-column for determination of zinc and copper in soil leachates.

A sequential injection (SI) system equipped with in-line solid phase extraction column and in-line soil mini-column is proposed for determination of zinc and copper in soil leachates. The spectrophotometric determination (560 nm) is based on the reaction of both analytes with 1-(2-Pyridylazo)-2-naphthol (PAN). Zinc is determined after retaining copper on a cationic resin (Chelex100) whereas copper is determined from the difference of the absorbance measured for both analytes, introduced into the system with the use of a different channel, and zinc absorbance. The influence of several potential interferences was studied. Using the developed method, zinc and copper were determined within the concentration ranges of 0.005-0.300 and 0.011-0.200 mg L-1, and with a relative standard deviation lower than 6.0% and 5.1%, respectively. The detection limits are 1.4 and 3.0 µg/L for determination of zinc and copper, respectively. The developed SI method was verified by the determination of both analytes in synthetic and certified reference materials of water samples, and applied to the determination of the analytes in rain water and soil leachates from laboratory scale soil core column and in-line soil mini-column.

Flow manifold for chemical H-point standard addition method implemented to electrochemical analysis based on the capacitance measurements.

The paper presents a novel analytical method for electrochemical potassium determination using gold electrodes with self-assembled thiol monolayers (SATMs) deposited on its surface. The whole analytical procedure was carried out in a dedicated flow manifold using capacitance detection mode. The terminal functional groups on the surface of the dielectric monolayer interacts selectively with the analyte, changing the thickness of the layer depending on the amount of the analyte and the applied voltage, resulting in a change in the registered dielectric capacitance. New calibration approach based on the Chemical H-point Standard Addition Method (C-HPSAM), allowing both specific (proportional) and unspecific (constant) interference effects caused by sodium ions to be corrected, was applied. The calibration method is based on the registration of the calibration graphs by the standard addition method (SAM) three times in such different chemical conditions, which are able to differentiate the slope of each graph. The C-HPSAM was applied for the first time in electrochemical analysis. As a chemical parameter differentiating the sensitivity of the calibration graphs, the concentration of ionic strength stabilizer (ethylenediamine) was used. In order to improve the analytical procedure, to make it faster and automated, the dedicated flow system was applied. The constructed flow system was composed of several modules individually dedicated to the appropriate step of the whole analytical procedure: electrochemical cleaning of work electrode surface, adsorption of SATMs and analytical calibration. The calibration curves were obtained in the range of 0.1-0.9 mmol L-1 with good linearity (R2 = 0.996 ±â€¯0.001) and the LOD and LOQ of 28.6 and 85.8 µmol L-1, respectively. The proposed method was employed for potassium determination in highly mineralized water, juice and pharmaceutical samples without any special pretreatment.

Application of gradient ratio flow-injection technique to implementation of the Chemical H-point Standard Addition Method.

A new gradient ratio approach to Chemical H-point Standard Addition Method (C-HPSAM) was developed in flow injection analysis with spectrophotometric detection. C-HPSAM is based on an idea to use SAM for calibration in several different chemical conditions in order to correct unspecific (additive) interferences in samples with unknown matrix. The approach proposed in this paper employs the gradient ratio flow-injection technique to generate a continuous change of chemical conditions. By doing so a set of two-point SAM calibration curves with different slopes are possible of registering that are intersected in a common point indicating the values of both unspecific interferences and analyte concentration in a sample. The applicability of the approach was verified on the examples of spectrophotometric determinations of ascorbic acid and paracetamol. Ascorbic acid was determined in soft drinks and juices basing on reduction of Fe(III) to Fe(II) and reaction of the latter ion with o-phenantroline to form the ferroin complex absorbing at 512 nm. Paracetamol determined in pharmaceuticals was nitrificated in reaction with sodium nitrite in acidic medium and then the formed derivative species was converted into a more stable compound in reaction with sodium hydroxide, for which absorbance was recorded at 430 nm. All analytical results were obtained within the confidence interval of the values obtained by capillary electrophoresis and the relative errors were below 6%. It was proved that the developed method is readily applicable to analysis of real samples of complex unknown matrices. As it is additionally effective, low-cost and green, it can be considered as a helpful analytical tool.

An automated continuous homogeneous microextraction for the determination of selenium and arsenic by hydride generation atomic fluorescence spectrometry.

An automated continuous homogeneous microextraction approach based on a flow system has been developed and coupled with a hydride generation atomic fluorescence spectrometry system (HG-AFS). The developed approach was applied for the determination of trace arsenic and selenium in environmental water and liver samples. The nonanoic acid was investigated as a switchable hydrophilicity solvent (SHS) for homogeneous microextraction of As(III) and Se(IV) complexes with pyrrolidinedithiocarbamate (PDC). The procedure involved on-line mixing ammonium PDC (aqueous phase), sodium nonanoate (aqueous phase) and acid sample solution resulting in the formation of SHS (nonanoic acid) dispersed into the acid aqueous phase. By this continuous process, analytes complexes with PDC were formed and extracted into the fine SHS droplets followed by retention into a monolithic column packed with block of porous PTFE. Finally, the retained complexes were eluted with NaOH solution and delivered to the HG-AFS system. The limits of detection, calculated from a blank test based on 3σ, were 0.01µgL-1 for both analytes.

New approach to H-point standard addition method for detection and elimination of unspecific interferences in samples with unknown matrix.

A novel method for correction of unknown unspecific (additive) interferences was developed in sequential injection analysis (SIA) using a Lab on Valve module (LOV) with spectrophotometric detection. The method implements a novel idea to calibrate by the standard addition method in several different chemical conditions created in such a way to measure different signal for an analyte and unchanged signal for interferents causing additive effect. This approach, being an enhancement of the H-point standard addition method (HPSAM), enables to quantify unbiased concentration of an analyte in the presence of unknown interferences. The method was tested on the example of the determination of ascorbic acid in soft drinks and juices basing on reduction of Fe(III) to Fe(II) and reaction of the latter with o-phenanthroline to the ferroin complex absorbing at 512.0nm. The analytical utility of the method has been verified and confirmed by the spectrophotometric determination of total acidity in rose and red wines in the presence of bromothymol blue absorbing at 616.0nm. Calibration solutions were prepared automatically in the designed flow system. Ascorbic acid was determined with LOD of 1.4mgL-1 and LOQ of 4.2mgL-1 within linear working range up to 80mgL-1, while in case of the determination of total acidity the values of 4.2, 11.8 and 100, respectively, were obtained. A sample was consumed in volumes of 400 and 1000µL in both cases. The analyses are simple, "green", and non-expensive. The developed method is readily applicable to analysis of real samples of complex unknown matrices and adaptable to different analytical methods.

Novel electroanalytical method based on the electrostriction phenomenon and its application to determination of Cr(VI) by the flow injection technique.

The electrostriction phenomenon is observed in membranes of thickness in the nanometer range, e.g. bilayer lipid membranes or self-assembled monolayers. Strong electrical field of 105-106V/cm in intensity appears when applying the potential lower than 1V to these membranes. Electrostatic forces change the dimensions of a dielectric, hence the membrane compression and decrease in thickness are observed. As a result, increase in the membrane capacitance is recorded. The presented work covers development and application of a new analytical method based on the innovative capacitance-to-frequency conversion method and flow technique. Construction of the novel flow manifold designed for realization of the whole analytical procedure of chromium(VI) determination with the use of capacitance measurements and its operating rules are shown. The main element of the system is a specially designed measurement cell for realization of chromium determination using a three-electrode system. Au electrode with a self-assembled monolayer of thiols grafted with functional groups selectively interacting with the analyte is employed as a dielectric layer. Ag/AgCl electrode and Pt one are used as a reference and auxiliary electrode, respectively. Accuracy, repeatability and reproducibility of the proposed analytical procedure were tested in determination of Cr(VI) in synthetic solutions and environmental water matrices spiked with the analyte. Benefits and drawbacks of the developed manifold were critically discussed.

Univariate analytical calibration methods and procedures. A review.

An original focus on univariate calibration as an experimental process of quantitative analysis is presented. A novel classification system is introduced against the background of the present situation concerning nomenclature of calibration methods. Namely, it has been revealed that four methods well-known in analytical chemistry: the conventional method, the internal standard method, the indirect method and the dilution method, can be split into those carried out in both the interpolative and the extrapolative mode. It is then shown that the basic procedures of all these methods can be modified including different approaches, such as matrix-matched technique, spiking the sample with a reactant, bracketing calibration, and others. For the first time (as compared to monographies dealing with univariate calibration) it is reviewed how the methods are mixed and integrated with one another thereby creating new calibration strategies of extended capabilities in terms of enhanced resistance to the interference and non-linear effects - as the main sources of systematic calibration errors. As additional novelty, rationally possible combinations of the calibration methods - not met hitherto in the literature - have been predicted. Finally, some general rules relating to calibration are formulated and the main calibration problems that still need to be solved are displayed.

Solenoid micropump-based flow system for generalized calibration strategy.

Generalized calibration strategy (GCS) is one of the innovative approaches aimed at verification and improvement of accuracy of analytical determinations. It combines in a single procedure the interpolative and the extrapolative calibration approaches along with stepwise dilution of a sample with the use of a dedicated flow system. In the paper a simple solenoid micropump-based flow system designed for implementation of GCS has been described. The manifold consists of several modules fully operated by a computer and connected with each other in a properly designed network. Its performance and usefulness were tested on determination of calcium by FAAS in synthetic and natural samples containing strong interferents. It was shown how GCS can serve for detection, examination and elimination of the interference effects. It was demonstrated that the designed manifold enabled to perform GCS procedure with very good precision, in short time and with very low standard, sample and reagent consumption.

An automatic, vigorous-injection assisted dispersive liquid-liquid microextraction technique for stopped-flow spectrophotometric detection of boron.

A novel automatic vigorous-injection assisted dispersive liquid-liquid microextraction procedure based on the use of a modified single-valve sequential injection manifold (SV-SIA) was developed and applied for determination of boron in water samples. The major novelties in the procedure are the achieving of efficient dispersive liquid-liquid microextraction by means of single vigorous-injection (250 µL, 900 µL s(-1)) of the extraction solvent (n-amylacetate) into aqueous phase resulting in the effective dispersive mixing without using dispersive solvent and after self-separation of the phases, as well as forwarding of the extraction phase directly to a Z-flow cell (10 mm) without the use of a holding coil for stopped-flow spectrophotometric detection. The calibration working range was linear up to 2.43 mg L(-1) of boron at 426nm wavelength. The limit of detection, calculated as 3s of a blank test (n=10), was found to be 0.003 mg L(-1), and the relative standard deviation, measured as ten replicable concentrations at 0.41 mg L(-1) of boron was determined to be 5.6%. The validation of the method was tested using certified reference material.