A 3D-printed robotic system for fully automated multiparameter analysis of drinkable water samples.

This work describes a 3D-printed robotic system named RSAWA (robotic system for automatic water analysis) for fully automated water analysis. RSAWA consists of a robotic arm coupled to a syringe pump, temperature and conductivity sensors, a low-cost webcam as colorimetric detector, and a 96-well microplate placed on a 3D-printed platform. The robotic system is controlled by software and it performs all analytical procedures. RSAWA was applied to measure conductivity (CDT), pH, total alkalinity (TA), total hardness (TH), chloride (Cl-), nitrite (NO2-), total dissolved phosphorus (TP), and total iron (TI) in drinkable water samples. A simple circuit was designed for conductivity determinations, while colorimetric pH determinations were carried out using Hue values extracted from digital images and a pH universal indicator. HSV histograms were used to calculate Pearson's correlation coefficients, allowing the construction of accurate titration curves. In addition to achieving sample throughputs of 112 h-1 for TA and TH determinations and 92 h-1 for Cl- determinations, RSAWA produced 99.5% less waste than the corresponding reference methods during titrations. Colorimetric measurements were performed through RGB vector norms calculated from digital images were used as analytical signals. Limits of quantification (µg L-1) were 6.83, 13.0 and 1.5 mg L-1 for NO2-, TP, and TI determinations, respectively. Sample throughputs (samples h-1) were 83 for NO2- and TP and 72 for TI with a 98.5% reduction in waste generation. Thus, RSAWA is a low-cost, feasible, and environmentally friendly alternative to quickly and accurately determine several chemical and physicochemical parameters in aqueous samples.

Quantum chemical DFT study of the interaction between molecular oxygen and FeN4 complexes, and effect of the macrocyclic ligand.

Density functional theory (DFT) was used to examine the interaction between molecular oxygen (O2) and macrocyclic iron complexes of the type FeN4 during the formation of FeN4--O2 adducts. In order to understand how this interaction is affected by different macrocyclic ligands, O2 was bonded to iron-tetraaza[14]annulene (FeTAA), iron-tetramethyl-tetraaza[14]annulene (FeTMTAA), iron-hexamethyl-tetraaza[14]annulene (FeHMTAA), iron dibenzotetraaza[14]annulene (FeDBTAA), and two iron-tetramethyl-dibenzotetraaza[14]annulene complexes (FeTMDBTAA1, FeTMDBTAA2). The ground state for FeN4-O2 adducts was the open-shell singlet. Analysis of the factors influencing the O2 bonding process showed that different macrocyclic ligands yielded adducts with differences in O--O and Fe--O2 bond lengths, total charge over the O2 fragment, O--O vibrational frequency, and spin density in the O2 fragment. A smaller energy gap between the α-HOMO of the FeN4 complexes and the ß-LUMO of O2 increased the interaction between the complex and the O2 molecule. The order of activity was FeDBTAA < FeTMDBTAA2 < FeTMDBTAA1 < FeTAA < FeTMTAA < FeHMTAA.

Flow injection photometric determination of NaCl, KCl and glucose in injectable drugs exploiting Schlieren signals.

A flow injection photometric system that exploits Schlieren signals for analytical measurement is described. The system was designed to be used as a new strategy for determining the contents of sodium chloride, potassium chloride and glucose, each respectively in injectable drugs. The proposed methodology was based on the difference between the refractive indices of the sample zone and of the carrier stream. With this perspective, a lab-made photometer based on LED-phototransistor technology was employed as a detection system to investigate the different analytical profiles related to the Schlieren effect in low flow rate conditions. The parameters of the flow system, such as flow-rate, optical path length, and sampling loop, were adjusted in order to obtain suitable Schlieren profiles for the measurements. Data evaluation was performed with the application of partial least squares regression (PLS-1). The obtained results demonstrated the predictive ability of the constructed PLS models, and the predicted concentration values were in agreement with the reference values, with a 95% confidence level.

Digital image-based flame emission spectrometry.

A digital image-based flame emission spectrometric (DIB-FES) method for the quantitative chemical analysis is proposed here for the first time. The DIB-FES method employs a webcam to capture the digital images which are associated to a radiation emitted by the analyte into an air-butane flame. Since the detection by webcam is based on the RGB (red-green-blue) colour system, a novel mathematical model was developed in order to build DIB-FES analytical curves and estimate figures of merit for the proposed method. In this approach, each image is retrieved in the three R, G and B individual components and their values were used to define a position vector in RGB three-dimensional space. The norm of this vector is then adopted as the RGB-based value (analytical response) and it has revealed to be linearly related to the analyte concentration. The feasibility of the DIB-FES method is illustrated in three applications involving the determination of lithium, sodium and calcium in anti-depressive drug, physiological serum and water, respectively. In comparison with the traditional flame emission spectrometry (trad-FES), no statistic difference has been observed between the results by applying the paired t-test at the 95% confidence level. However, the DIB-FES method has offered the largest sensitivities and precision, as well as the smallest limits of detection and quantification for the three analytes. These advantageous characteristics are attributed to the trivariate nature of the detection by webcam.

Digital image-based titrations.

The exploitation of digital images obtained from a CCD camera (WebCam) as a novel instrumental detection technique for titration is proposed for the first time. Named of digital image-based (DIB) titration, it also requires, as a traditional titration (for example, spectrophotometric, potentiometric, conductimetric), a discontinuity in titration curves where there is an end point, which is associated to the chemical equivalence condition. The monitored signal in the DIB titration is a RGB-based value that is calculated, for each digital image, by using a proposed procedure based on the red, green, and blue colour system. The DIB titration was applied to determine HCl and H3PO4 in aqueous solutions and total alkalinity in mineral and tap waters. Its results were compared to the spectrophotometric (SPEC) titration and, by applying the paired t-test, no statistic difference between the results of both methods was verified at the 95% confidence level. Identical standard deviations were obtained by both titrations in the determinations of HCl and H3PO4, with a slightly better precision for DIB titration in the determinations of total alkalinity. The DIB titration shows to be an efficient and promising tool for quantitative chemical analysis and, as it employs an inexpensive device (WebCam) as analytical detector, it offers an economically viable alternative to titrations that need instrumental detection.

A multiscale wavelet data treatment for reliable localization of inflection points for analytical purposes.

Instrumental analysis techniques that employ measurements based on inflection points may have their accuracy compromised due to the need for signal differentiation, which is very sensitive to instrumental noise. This paper presents a strategy for localizing inflection points that exploits the multiscale processing capability of the Wavelet Transform and avoids the need for explicit signal differentiation. The strategy is illustrated in simulated examples and also in a real analytical problem involving the determination of Pb and Cd by potentiometric stripping analysis. In this application, the results were in good agreement with the expected values and were slightly better than those obtained from the first derivative of the curves after smoothing by a Windowed Fourier Transform.