Paulo Henrique Gonçalves Dias Diniz

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.

Using UV-Vis spectroscopy for simultaneous geographical and varietal classification of tea infusions simulating a home-made tea cup.

In this work we proposed a method to verify the differentiating characteristics of simple tea infusions prepared in boiling water alone (simulating a home-made tea cup), which represents the final product as ingested by the consumers. For this purpose we used UV-Vis spectroscopy and variable selection through the Successive Projections Algorithm associated with Linear Discriminant Analysis (SPA-LDA) for simultaneous classification of the teas according to their variety and geographic origin. For comparison, KNN, CART, SIMCA, PLS-DA and PCA-LDA were also used. SPA-LDA and PCA-LDA provided significantly better results for tea classification of the five studied classes (Argentinean green tea; Brazilian green tea; Argentinean black tea; Brazilian black tea; and Sri Lankan black tea). The proposed methodology provides a simpler, faster and more affordable classification of simple tea infusions, and can be used as an alternative approach to traditional tea quality evaluation as made by skilful tasters, which is evidently partial and cannot assess geographic origins.

Using a simple digital camera and SPA-LDA modeling to screen teas

Classification or screening analysis of natural unprocessed teas using simple digital images and a variable selection algorithm is described. The proposed methodology uses color histograms generated on free downloadable software ImageJ 1.44p as a source of analytical information. Two chemometric methods were compared for classification of the resulting images, namely Soft Independent Modeling of Class Analogy (SIMCA), and Linear Discriminant Analysis (LDA) with variable selection by the Successive Projections Algorithm (SPA). The results were evaluated in terms of errors found in a sample set separate from the modeling process. The choice of more informative photometric color attributes (red-green-blue (RGB), hue (H), saturation (S), brightness (B), and grayscale) for screening the tea samples was made during the color modeling because SIMCA failed to give good results. Therefore the data treatment used SPA-LDA, which correctly classified all samples according to their geographical regions, whether from Brazilian, Argentinian or foreign soils.

Indirect determination of sodium diclofenac, sodium dipyrone and calcium gluconate in injection drugs using digital image-based (webcam) flame emission spectrometric method

This paper proposes a digital image-based flame emission spectrometric (DIB-FES) method for indirect determination of sodium diclofenac, sodium dipyrone and calcium gluconate in injectable forms. The proposed DIB-FES method uses digital images obtained from a webcam, based on the RGB (Red-Green-Blue) system. It offers a simple and inexpensive way to quantify these organic substances using the radiation emitted by the alkaline and earth-alkaline metals present in their formulae. Analytical curves were constructed on the basis of the relationship between RGB values and calibration solution concentrations. The results showed no statistical difference between the proposed and reference methods when applying the paired t-test at a 95% confidence level. The proposed DIB-FES method also performed well in terms of the figures of merit LOD, LOQ, linear range, precision, and the accuracy as revealed by recovery tests.

A flow-batch analyzer with piston propulsion applied to automatic preparation of calibration solutions for Mn determination in mineral waters by ET AAS

The increasing development of miniaturized flow systems and the continuous monitoring of chemical processes require dramatically simplified and cheap flow schemes and instrumentation with large potential for miniaturization and consequent portability. For these purposes, the development of systems based on flow and batch technologies may be a good alternative. Flow-batch analyzers (FBA) have been successfully applied to implement analytical procedures, such as: titrations, sample pre-treatment, analyte addition and screening analysis. In spite of its favourable characteristics, the previously proposed FBA uses peristaltic pumps to propel the fluids and this kind of propulsion presents high cost and large dimension, making unfeasible its miniaturization and portability. To overcome these drawbacks, a low cost, robust, compact and non-propelled by peristaltic pump FBA is proposed. It makes use of a lab-made piston coupled to a mixing chamber and a step motor controlled by a microcomputer. The piston-propelled FBA (PFBA) was applied for automatic preparation of calibration solutions for manganese determination in mineral waters by electrothermal atomic-absorption spectrometry (ET AAS). Comparing the results obtained with two sets of calibration curves (five by manual and five by PFBA preparations), no significant statistical differences at a 95% confidence level were observed by applying the paired t-test. The standard deviation of manual and PFBA procedures were always smaller than 0.2 and 0.1mugL(-1), respectively. By using PFBA it was possible to prepare about 80 calibration solutions per hour.

Digital image-based classification of biodiesel.

This work proposes a simple, rapid, inexpensive, and non-destructive methodology based on digital images and pattern recognition techniques for classification of biodiesel according to oil type (cottonseed, sunflower, corn, or soybean). For this, differing color histograms in RGB (extracted from digital images), HSI, Grayscale channels, and their combinations were used as analytical information, which was then statistically evaluated using Soft Independent Modeling by Class Analogy (SIMCA), Partial Least Squares Discriminant Analysis (PLS-DA), and variable selection using the Successive Projections Algorithm associated with Linear Discriminant Analysis (SPA-LDA). Despite good performances by the SIMCA and PLS-DA classification models, SPA-LDA provided better results (up to 95% for all approaches) in terms of accuracy, sensitivity, and specificity for both the training and test sets. The variables selected Successive Projections Algorithm clearly contained the information necessary for biodiesel type classification. This is important since a product may exhibit different properties, depending on the feedstock used. Such variations directly influence the quality, and consequently the price. Moreover, intrinsic advantages such as quick analysis, requiring no reagents, and a noteworthy reduction (the avoidance of chemical characterization) of waste generation, all contribute towards the primary objective of green chemistry.

Eco-friendly sonoluminescent determination of free glycerol in biodiesel samples

This paper proposes a flow-batch methodology for the determination of free glycerol in biodiesel that is notably eco-friendly, since non-chemical reagents are used. Deionized water (the solvent) was used alone for glycerol (sample) extractions from the biodiesel. The same water was used to generate water-cavitation sonoluminescence signals, which were modulated by the quenching effect associated with the amount of extracted glycerol. The necessarily reproducible signal generation was achieved by using a simple and inexpensive piezoelectric device. A linear response was observed for glycerol within the 0.001-100 mg/L range, equivalent to 0.004-400 mg/kg free glycerol in biodiesel. The lowest measurable concentration of free glycerol was estimated at 1.0 µg/L. The selectivity of the proposed method was confirmed by comparing the shape and retention of both real and calibration samples to standard solution chromatograms, presenting no peaks other than glycerol. All samples (after extraction) are greatly diluted; this minimizes (toward non-detectability) potential interference effects. The methodology was successfully applied to biodiesel analysis at a high sampling rate, with neither reagent nor solvent (other than water), and with minimum waste generation. The results agreed with the reference method (ASTM D6584-07), at a 95% confidence level.

Using iSPA-PLS and NIR spectroscopy for the determination of total polyphenols and moisture in commercial tea samples

In this work, a methodology is proposed for determining the content of total polyphenols and moisture in commercial tea samples by using near-infrared spectroscopy (NIRS) and Partial Least Squares (PLS) regression coupled with the Successive Projections Algorithm for interval selection (iSPA-PLS). For comparison, full-spectrum PLS and the Interval PLS (iPLS) were also used. Since the spectra are scattered and exhibit systematic variations on the baseline, standard normal variate transformation (SNV) and multiplicative scatter correction (MSC) were applied as data preprocessing methods. The number of PLS latent variables and the number of region intervals were optimized according to the root mean square error of cross-validation (RMSECV) and coefficient of determination (RCV2) in the calibration set. The predictive ability of the final model was evaluated in terms of the root mean square error of prediction (RMSEP), coefficient of determination (RPred2) and ratio performance deviation (RPDPred) in the external prediction set, which were not employed in the model-building process. For the determination of the total polyphenol content, 10-iSPA-PLS with MSC preprocessing presented the best results with the smallest RMSEP (0.599 mg kg−1), and the highest RPred2 (0.933) and RPDPred (3.863) values. For the determination of moisture content, 20-iSPA-PLS with MSC preprocessing achieved the best results with the smallest RMSEP (0.32 mg kg−1), and the highest RPred2 (0.94) and RPDPred (4.08) values. Thus, it can be concluded that the NIRS coupled with iSPA-PLS is a promising analytical tool for monitoring tea quality.

Determination of fat content in chicken hamburgers using NIR spectroscopy and the Successive Projections Algorithm for interval selection in PLS regression (iSPA-PLS)

Determining fat content in hamburgers is very important to minimize or control the negative effects of fat on human health, effects such as cardiovascular diseases and obesity, which are caused by the high consumption of saturated fatty acids and cholesterol. This study proposed an alternative analytical method based on Near Infrared Spectroscopy (NIR) and Successive Projections Algorithm for interval selection in Partial Least Squares regression (iSPA-PLS) for fat content determination in commercial chicken hamburgers. For this, 70 hamburger samples with a fat content ranging from 14.27 to 32.12mgkg-1 were prepared based on the upper limit recommended by the Argentinean Food Codex, which is 20% (ww-1). NIR spectra were then recorded and then preprocessed by applying different approaches: base line correction, SNV, MSC, and Savitzky-Golay smoothing. For comparison, full-spectrum PLS and the Interval PLS are also used. The best performance for the prediction set was obtained for the first derivative Savitzky-Golay smoothing with a second-order polynomial and window size of 19 points, achieving a coefficient of correlation of 0.94, RMSEP of 1.59mgkg-1, REP of 7.69% and RPD of 3.02. The proposed methodology represents an excellent alternative to the conventional Soxhlet extraction method, since waste generation is avoided, yet without the use of either chemical reagents or solvents, which follows the primary principles of Green Chemistry. The new method was successfully applied to chicken hamburger analysis, and the results agreed with those with reference values at a 95% confidence level, making it very attractive for routine analysis.

Identification of biodiesel feedstock in biodiesel/diesel blends using digital images and chemometric methods

This study aims to identify the biodiesel feedstock (cottonseed, sunflower, corn or soybean oil) in biodiesel/diesel blends using digital images and chemometric methods. For this purpose, colour histograms (extracted from digital images) coupled with supervised pattern recognition techniques: Soft Independent Modelling of Class Analogy (SIMCA), Partial Least Squares Discriminant Analysis (PLS-DA) and the Successive Projections Algorithm for variable selection associated with Linear Discriminant Analysis (SPA-LDA) were used. SPA-LDA coupled with intensity histograms provided better results by selecting 12 variables alone, achieving only one error of classification in the external validation (test) set. Thus, the proposed methodology presents a noteworthy eco-friendly approach for identifying the biodiesel feedstock in biodiesel/diesel blends using a simple, fast, inexpensive and non-destructive analytical tool.