Flexible Learning and Assessment Package for Teaching Data Analysis and Chemometrics in Analytical Chemistry

Instrumentation for analytical chemistry has become enormously productive and convenient to use in recent times. However, despite successes in automation and computer software, the person driving the instrument is still of prime importance. In the wrong hands, even the very best computer controlled instrumentation will only produce more meaningless data faster. In analytical chemistry it is the quality of the data produced that is of the utmost importance. A related issue is the spread of chemometrics into the workplace for solving routine analytical chemistry problems in areas, which include everything from the petroleum industry to the environment to foodstuffs to forensic science. Students do learn about quality and data analysis principles in a statistics unit that they undertake but usually they are unable to make the connection between what they learn in statistics and what they learn in analytical chemistry. In any case, generalist statistics units don’t go far enough to prepare students for using chemometrics software packages in professional life

MicroNIR/chemometrics assessement of occupational exposure to hydroxyurea

Portable Near Infrared spectroscopy (NIRs) coupled to chemometrics was investigated for the first time as a novel entirely on-site approach for occupational exposure monitoring in pharmaceutical field. Due to a significant increase in the number of patients receiving chemotherapy, the development of reliable, fast, and on-site analytical methods to assess the occupational exposure of workers in the manufacture of pharmaceutical products, has become more and more required. In this work, a fast, accurate, and sensitive detection of hydroxyurea, a cytotoxic antineoplastic agent commonly used in chemotherapy, was developed. Occupational exposure to antineoplastic agents was evaluated by collecting hydroxyurea on a membrane filter during routine drug manufacturing process. Spectra were acquired in the NIR region in reflectance mode by the means of a miniaturized NIR spectrometer coupled with chemometrics. This MicroNIR instrument is a very ultra-compact portable device with a particular geometry and optical resolution designed in such a manner that the reduction in size does not compromise the performances of the spectrometer. The developed method could detect up to 50 ng of hydroxyurea directly measured on the sampling filter membrane, irrespective of complexity and variability of the matrix; thus extending the applicability of miniaturized NIR instruments in pharmaceutical and biomedical analysis

Effect of agro-climatic conditions on near infrared spectra of extra virgin olive oils

Authentication of extra virgin olive oil requires fast and cost-effective analytical procedures, such as near infrared spectroscopy. Multivariate analysis and chemometrics have been successfully applied in several papers to gather qualitative and quantitative information of extra virgin olive oils from near infrared spectra. Moreover, there are many examples in the literature analysing the effect of agro-climatic conditions on food content, in general, and in olive oil components, in particular. But the majority of these studies considered a factor, a non-numerical variable, containing this meteorological information. The present work uses all the agro-climatic data with the aim of highlighting the linear relationships between them and the near infrared spectra. The study begins with a graphical motivation, continues with a bivariate analysis and, finally, applies redundancy analysis to extend and confirm the previous conclusions.Peer Reviewe

Intra-regional classification of grape seeds produced in Mendoza province (Argentina) by multi-elemental analysis and chemometrics tools

The feasibility of the application of chemometric techniques associated with multi-element analysis for the classification of grape seeds according to their provenance vineyard soil was investigated. Grape seed samples from different localities of Mendoza province (Argentina) were evaluated. Inductively coupled plasma mass spectrometry (ICP-MS) was used for the determination of twenty-nine elements (Ag, As, Ce, Co, Cs, Cu, Eu, Fe, Ga, Gd, La, Lu, Mn, Mo, Nb, Nd, Ni, Pr, Rb, Sm, Te, Ti, Tl, Tm, U, V, Y, Zn and Zr). Once the analytical data were collected, supervised pattern recognition techniques such as linear discriminant analysis (LDA), partial least square discriminant analysis (PLS-DA), k-nearest neighbors (k-NN), support vector machine (SVM) and Random Forest (RF) were applied to construct classification/discrimination rules. The results indicated that nonlinear methods, RF and SVM, perform best with up to 98% and 93% accuracy rate, respectively, and therefore are excellent tools for classification of grapes.Fil: Canizo, Brenda Vanina. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales. Laboratorio de Química Analítica para Investigación y Desarrollo; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; ArgentinaFil: Escudero, Leticia Belén. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales. Laboratorio de Química Analítica para Investigación y Desarrollo; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; ArgentinaFil: Pérez, María Belén. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales. Laboratorio de Química Analítica para Investigación y Desarrollo; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; ArgentinaFil: Pellerano, Roberto Gerardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Wuilloud, Rodolfo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentin

Tracing the geographical origin of Argentinean lemon juices based on trace element profiles using advanced chemometric techniques

This study examines the application of chemometric techniques associated with trace element concentrations for origin evaluation of lemon juice samples. Seventy-four lemon juice samples from three different provinces of Argentina were evaluated according to their microelement contents to identify differences in patterns of elements in the three provinces. Inductively coupled plasma mass spectrometry (ICP-MS) was used for the determination of twenty-five elements (Ag, Al, As, Ba, Bi, Co, Cr, Cu, Fe, Ga, In, La, Li, Mn, Mo, Ni, Rb, Sb, Sc, Se, Sn, Sr, Tl, V, and Zn). Once the analytical data were collected, supervised pattern recognition techniques were applied to construct classification/discrimination rules to predict the origin of samples on the basis of their profiles of trace elements. Namely, linear discriminant analysis (LDA), partial least square discriminant analysis (PLS-DA), k-nearest neighbors (k-NN), random forest (RF), and support vector machine with radial basis function Kernel (SVM). The results indicated that it was feasible to attribute unknown lemon juice samples to its geographical origin. SVM had better performance compared to RF, k-NN, LDA and PLS-DA, listed in descending order. Eventually, this study verifies that trace element pattern is a powerful geographical indicator when identifying the origin of lemon juice samples by analyzing trace element data with the help of SVM technique. This level of accuracy provides an interesting foundation to propose the combination of trace element contents with SVM technique as a valuable tool to evaluate the geographical origin of lemon juice samples produced in Argentina.Fil: Gaiad, José Emilio. Universidad Nacional del Nordeste; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Hidalgo, Melisa Jazmin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina. Universidad Nacional del Nordeste; ArgentinaFil: Villafañe, Roxana Noelia. Universidad Nacional de San Luis; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; ArgentinaFil: Marchevsky, Eduardo Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Química de San Luis. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Química de San Luis; Argentina. Universidad Nacional de San Luis; ArgentinaFil: Pellerano, Roberto Gerardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina. Universidad Nacional del Nordeste; Argentin

Multivariate statistical analysis for the identification of potential seafood spoilage indicators

Volatile organic compounds (VOCs) characterize the spoilage of seafood packaged under modified atmospheres (MAs) and could thus be used for quality monitoring. However, the VOC profile typically contains numerous multicollinear compounds and depends on the product and storage conditions. Identification of potential spoilage indicators thus calls for multivariate statistics. The aim of the present study was to define suitable statistical methods for this purpose (exploratory analysis) and to consequently characterize the spoilage of brown shrimp (Crangon crangon) and Atlantic cod (Gadus morhua) stored under different conditions (selective analysis). Hierarchical cluster analysis (HCA), principal components analysis (PCA) and partial least squares regression analysis (PLS) were applied as exploratory techniques (brown shrimp, 4 °C, 50%CO2/50%N2) and PLS was further selected for spoilage marker identification. Evolution of acetic acid, 2,3-butanediol, isobutyl alcohol, 3-methyl-1-butanol, dimethyl sulfide, ethyl acetate and trimethylamine was frequently in correspondence with changes in the microbiological quality or sensory rejection. Analysis of these VOCs could thus enhance the detection of seafood spoilage and the development of intelligent packaging technologies.acceptedVersionPeer reviewe

Designing algorithms to aid discovery by chemical robots

Recently, automated robotic systems have become very efficient, thanks to improved coupling between sensor systems and algorithms, of which the latter have been gaining significance thanks to the increase in computing power over the past few decades. However, intelligent automated chemistry platforms for discovery orientated tasks need to be able to cope with the unknown, which is a profoundly hard problem. In this Outlook, we describe how recent advances in the design and application of algorithms, coupled with the increased amount of chemical data available, and automation and control systems may allow more productive chemical research and the development of chemical robots able to target discovery. This is shown through examples of workflow and data processing with automation and control, and through the use of both well-used and cutting-edge algorithms illustrated using recent studies in chemistry. Finally, several algorithms are presented in relation to chemical robots and chemical intelligence for knowledge discovery

Metabolomics : a tool for studying plant biology

In recent years new technologies have allowed gene expression, protein and metabolite profiles in different tissues and developmental stages to be monitored. This is an emerging field in plant science and is applied to diverse plant systems in order to elucidate the regulation of growth and development. The goal in plant metabolomics is to analyze, identify and quantify all low molecular weight molecules of plant organisms. The plant metabolites are extracted and analyzed using various sensitive analytical techniques, usually mass spectrometry (MS) in combination with chromatography. In order to compare the metabolome of different plants in a high through-put manner, a number of biological, analytical and data processing steps have to be performed. In the work underlying this thesis we developed a fast and robust method for routine analysis of plant metabolite patterns using Gas Chromatography-Mass Spectrometry (GC/MS). The method was performed according to Design of Experiment (DOE) to investigate factors affecting the extraction and derivatization of the metabolites from leaves of the plant Arabidopsis thaliana. The outcome of metabolic analysis by GC/MS is a complex mixture of approximately 400 overlapping peaks. Resolving (deconvoluting) overlapping peaks is time-consuming, difficult to automate and additional processing is needed in order to compare samples. To avoid deconvolution being a major bottleneck in high through-put analyses we developed a new semi-automated strategy using hierarchical methods for processing GC/MS data that can be applied to all samples simultaneously. The two methods include base-line correction of the non-processed MS-data files, alignment, time-window determinations, Alternating Regression and multivariate analysis in order to detect metabolites that differ in relative concentrations between samples. The developed methodology was applied to study the effects of the plant hormone GA on the metabolome, with specific emphasis on auxin levels in Arabidopsis thaliana mutants defective in GA biosynthesis and signalling. A large series of plant samples was analysed and the resulting data were processed in less than one week with minimal labour; similar to the time required for the GC/MS analyses of the samples