Santiago A. Bortolato

Chemometrics-Assisted Excitation−Emission Fluorescence Spectroscopy on Nylon Membranes. Simultaneous Determination of Benzo[a]pyrene and Dibenz[a,h]anthracene at Parts-Per-Trillion Levels in the Presence of the Remaining EPA PAH Priority Pollutants As Interferences

This work presents a novel approach for the simultaneous ultratrace determination of benzo[ a]pyrene and dibenzo[ a,h]anthracene, the two most carcinogenic polycyclic aromatic hydrocarbons (PAHs), in a very interfering environment, combining the recently discovered ability of the nylon membrane to strongly retain and concentrate PAHs on its surface, the sensitivity of molecular fluorescence, and the selectivity of second-order chemometric algorithms. The fluorescence excitation-emission matrices, directly measured on a nylon-membrane surface, are processed by applying parallel factor analysis (PARAFAC) and unfolded partial least-squares coupled to residual bilinearization (U-PLS/RBL). The superiority of U-PLS/RBL to quantify BaP and DBA at concentrations below 10 ng L (-1) in the presence of the remaining 14 US EPA (United States Environmental Protection Agency) PAHs at total concentrations ranging from 1400 and 14,000 ng L (-1) is demonstrated. The present method successfully faces this complex challenge without using organic solvents, which are to known produce environmental contamination. Finally, the high sensitivity of the present method avoids preconcentration and elution steps, considerably decreasing the analysis time and the experimental errors. Because the instrumental involved in the determination is nonsophisticated, the experiments could be carried out in routine laboratories.

Non-Trilinear Chromatographic Time Retention−Fluorescence Emission Data Coupled to Chemometric Algorithms for the Simultaneous Determination of 10 Polycyclic Aromatic Hydrocarbons in the Presence of Interferences

Multivariate calibration coupled to high-performance liquid chromatography-fast scanning fluorescence spectroscopy (HPLC-FSFS) was employed for the analysis of 10 selected polycyclic aromatic hydrocarbons (PAHs), six of which correspond to heavy PAHs. The goal of the present study was the successful resolution of a system even in the presence of real interferences. Second-order HPLC-FSFS data matrices were obtained in a short time with a chromatographic system operating in isocratic mode. The difficulties in aligning chromatographic bands in complex systems, such as the ones presented here, are discussed. Two second-order calibration algorithms which do not require chromatographic alignment were selected for data processing, namely, multivariate curve resolution-alternating least-squares (MCR-ALS) and parallel factor analysis 2 (PARAFAC2). These algorithms did also achieve the second-order advantage, and therefore they were able to overcome the problem of the presence of unexpected interferences. The study was employed for the discussion of the scopes of the applied second-order chemometric tools, demonstrating the superiority of MCR-ALS to successfully resolve this complex system. The quality of the proposed techniques was assessed on the basis of the analytical recoveries from different types of water and olive oil samples after solid-phase extraction. The studied concentration ranges in water samples were 5.6 x 10(-3)-0.20 ng mL(-1) for heavy PAHs and 0.036-0.80 ng mL(-1) for light PAHs, while in oil samples the PAHs concentrations were 0.13-9.6 and 2.3-49.5 ng mL(-1) for heavy and light PAHS, respectively. All real samples were analyzed in the presence of the studied interferences.

Chemometric processing of second-order liquid chromatographic data with UV–vis and fluorescence detection. A comparison of multivariate curve resolution and parallel factor analysis 2

Second-order liquid chromatographic data with multivariate spectral (UV-vis or fluorescence) detection usually show changes in elution time profiles from sample to sample, causing a loss of trilinearity in the data. In order to analyze them with an appropriate model, the latter should permit a given component to have different time profiles in different samples. Two popular models in this regard are multivariate curve resolution-alternating least-squares (MCR-ALS) and parallel factor analysis 2 (PARAFAC2). The conditions to be fulfilled for successful application of the latter model are discussed on the basis of simple chromatographic concepts. An exhaustive analysis of the multivariate calibration models is carried out, employing both simulated and experimental chromatographic data sets. The latter involve the quantitation of benzimidazolic and carbamate pesticides in fruit and juice samples using liquid chromatography with diode array detection, and of polycyclic aromatic hydrocarbons in water samples, in both cases in the presence of potential interferents using liquid chromatography with fluorescence spectral detection, thereby achieving the second-order advantage. The overall results seem to favor MCR-ALS over PARAFAC2, especially in the presence of potential interferents.

A novel application of nylon membranes to the luminescent determination of benzo[a]pyrene at ultra trace levels in water samples

Very simple and highly sensitive methods are presented for the determination of benzo[a]pyrene, one of the most carcinogenic polycyclic aromatic hydrocarbons (PAHs). The approaches are based on solid-phase extraction of the analyte on a nylon membrane via a syringe procedure, and its fluorescent or phosphorescent determination on the solid surface. While the native fluorescence of benzo[a]pyrene retained on a nylon surface is measured directly, room-temperature phosphorescence is induced by spotting a few microlitres of thallium(I) nitrate solution on the surface (heavy-atom effect). An enhancement of the phosphorescence signal was corroborated when the measurements were carried under a nitrogen atmosphere. The analytical figures of merit obtained under the best experimental conditions demonstrate the capability of detecting benzo[a]pyrene at a sub-parts-per-trillion (sub-ng L(-1)) level. The potential interference from other common PAHs and also from different metal ions was studied. The feasibility of determining benzo[a]pyrene in real samples was successfully evaluated through the analysis of spiked tap, underground and mineral water samples of different origins. Recoveries obtained from spiked river waters were successfully compared with those provided by a reference method, through rigorous statistical analysis.

Chemometrics-assisted fluorimetry for the rapid and selective determination of heavy polycyclic aromatic hydrocarbons in contaminated river waters and activated sludges.

The most concerned polycyclic aromatic hydrocarbons (PAHs) benzo[a]pyrene, dibenz[a,h]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene and benz[a]anthracene were simultaneously determined in the presence of other 10 interfering PAHs, applying second-order multivariate calibration to the data obtained with a flow-through optosensor interfaced to a fast-scanning spectrofluorimeter. Using a sample volume of 2.5 mL, detection limits in the range 5-115 ng L(-1) were obtained in interfering samples, with a sample frequency of ca. 15 samples per hour, and with a minimum use of organic solvents, competing very favorably with chromatographic methods. The significance of this study lies in the solution of the quantitative analysis problem of six PAHs in real matrices of unknown composition. The unfolded partial least-squares/residual bilinearization (U-PLS/RBL) algorithm showed the best performance in resolving the complex studied system.

Second order multivariate curve resolution of Fourier transform infrared spectroscopic data of the photo-induced crosslinking of thymine functionalized polymers

A meaningful characterization of the photo-induced curing process of materials based on styrene monomers functionalized with thymine and charged ionic groups was accomplished using FT-IR spectroscopy in combination with second-order multivariate calibration algorithms. The polymer composition as well as the irradiation dose effects on the photo-crosslinking of copolymer films was experimentally determined. Each FT-IR absorption spectra was decomposed into the contribution of individual species by means of chemometric algorithms. A second-order strategy involving a three-way array for each sample and analyzing all arrays simultaneously was used. Temperature and solvent frequently have a strong influence on the FT-IR peak producing shifts and trilinearity lost. A new methodology to properly pre-align the spectroscopic matrix data is used based on the decomposition of a three-way array via a suitably initialized and constrained PARAFAC model. The chemical reaction mechanism describing the underlying process in terms of identifiable steps was determined. Associated key parameters and equilibrium rate constants that characterize the interconversion and stability of diverse species were predicted. Additionally, it was possible to quantify all the species even in the presence of a non-calibrated compound.

Optimization of Environmentally Benign Polymers Based on Thymine and Polyvinyl Sulfonate Using Plackett-Burman Design and Surface Response

Traditional approaches to the development of integrated circuits involve the use and/or manufacture of toxic materials that have a potential environmental impact. An extensive research has been done to design environmentally benign synthetic polymers containing nucleic acid bases, which can be used to enhance the photoresistor technologies. Water soluble, environmentally benign photopolymers of 1-(4-vinylbenzyl) thymine (VBT) and vinylphenyl sufonate (VPS) undergo a photodimerization reaction when exposed to low levels of ultraviolet irradiation leading to an immobilization of the copolymer on a variety of substrates. Plackett-Burman design (PBD) and central composite design (CCD) were applied to identify the significant factors influencing the polymer crosslinking and dye adsorption processes, which are relevant in the fabrication of copolymer films for potential photoresist use. The PBD results assigned a maximum absorption signal of 0.67, while optimal conditions obtained in this experiment following the CCD method predictions provided a response of 0.83 ± 0.03, being a solid foundation for further use of this methodology in the production of potential photoresistors. The pH effect was relevant for low concentrations but not significant for higher concentrations. To the best of our knowledge, this was the first report applying statistical experimental designs to optimize the crosslinking of thymine-based polymers.

Thymine based copolymers: feasible sensors for the detection of persistent organic pollutants in water

Polycyclic Aromatic Hydrocarbons (PAHs) are among the main persistent organic pollutants in water, because they can cause serious diseases in living organisms. The PAHs trace levels in environmental samples makes their detection particularly difficult. The development of new fluorescence spectroscopic sensors is a realistic alternative for the quantification of PAHs at very low concentrations. Bio-inspired copolymers based on thymine and charged groups showed high affinity for benzo[a]pyrene, the nastiest contaminant of the PAHs group, and can be used to enhance their native luminescence. In the present work we rationalized the observed experimental evidence using a theoretical model that studies the plausible non-covalent interactions (polar hydrogen–π, π–π “stacking”, etc.) between these compounds, in order to make a realistic design of new thymine-based copolymers sensors.

Multivariate analysis of organic acids in fermented food from reversed-phase high-performance liquid chromatography data

Multivariate calibration coupled to RP-HPLC with diode array detection (HPLC-DAD) was applied to the identification and the quantitative evaluation of the short chain organic acids (malic, oxalic, formic, lactic, acetic, citric, pyruvic, succinic, tartaric, propionic and α-cetoglutaric) in fermented food. The goal of the present study was to get the successful resolution of a system in the combined occurrence of strongly coeluting peaks, of distortions in the time sensors among chromatograms, and of the presence of unexpected compounds not included in the calibration step. Second-order HPLC-DAD data matrices were obtained in a short time (10min) on a C18 column with a chromatographic system operating in isocratic mode (mobile phase was 20mmolL-1 phosphate buffer at pH 2.20) and a flow-rate of 1.0mLmin-1 at room temperature. Parallel factor analysis (PARAFAC) and unfolded partial least-squares combined with residual bilinearization (U-PLS/RBL) were the second-order calibration algorithms select for data processing. The performance of the analytical parameters was good with an outstanding limit of detection (LODs) for acids ranging from 0.15 to 10.0mmolL-1 in the validation samples. The improved method was applied to the analysis of many dairy products (yoghurt, cultured milk and cheese) and wine. The method was shown as an effective means for determining and following acid contents in fermented food and was characterized by reducibility with simple, high resolution and rapid procedure without derivatization of analytes.

Fluorescence spectroscopy and multivariate analysis as a greener monitoring tool: characterization of the curing kinetics of bioinspired polymers

The photo-induced curing kinetics of bioinspired copolymers vinylbenzyl thymine (VBT) and vinylphenyl sulfonate was studied using fluorescence spectroscopy in combination with multivariate analysis. Fluorescence spectroscopy enables a detailed description of the curing process of VBT copolymers in real time, combining selectivity, simplicity and sensitivity, without the need of sample pre-treatments, being an advantage from the green analytical chemistry point of view. Two chemometric strategies were used to decompose the data matrix generated while monitoring the curing reaction, identifying the evolution of each species involved in the process in conjunction with the corresponding pure spectra. A comprehensive comparison between the developed approaches was made, clearly highlighting the advantages and disadvantages of both of them. The use of multivariate analysis applied to fluorescence spectroscopic data to study curing reactions have several advantages such as no sample pre-treatment, no sophisticated equipment requirement, reduced analysis time and use of non-toxic solvents, among others.