Agustín G. Asuero

By Julia Martín, Nieves Velázquez and Agustin G. Asuero

The results obtained when testing materials, equipment and procedures are not generally identical. Factors that influence the magnitude of the results are not fully controllable. As such, the interpretation and analysis of results must take into account the variations caused by numerous and random unavoidable causes. Intercomparison exercises are considered of being of importance, as they do allow the examination of the analytical process and their generated results. Youden plot is particularly aimed at interlaboratory comparisons. The raw results provided by the participating laboratories are treated by a statistical method applied by the centre performing the trial. In order to materialize this, two similar materials with small differences in the concentration of the characteristics are required. The advantage of Youden analysis is its ability to separate the random errors with a minimum effort by participants in the design from the point of view of the analytical requirement. This book chapter illustrates the method that has been applied to elaborate on data covering a diverse scientific field: polyunsaturated fatty acids in fat and oils, total blood cholesterol and aspirin in pharmaceutical preparations. Finally, liquid chromatography with tandem mass spectrometry detector has been applied to the determination of an emerging contaminant, methylparaben (MeP), in surface waters.

Part of the book: Quality Control and Assurance

By Julia Martín, María José Navas, Ana María Jiménez-Moreno and Agustín G. Asuero

Anthocyanins are naturally occuring pigments belonging to the group of flavonoids, a subclass of the polyphenol family. They are common components of the human diet, as they are present in many foods, fruits and vegetables, especially in berries and red wine. There were more studies conducted on effect of processing and storage on changes and stability of colors of anthocyanins in foods such as fruits and also for their use as natural colorants. Besides, the interest on anthocyanins is still growing also owing to their strong antioxidant activity against many chronic diseases, numerous studies about their medicinal, therapeutical and nutritional value were also conducted. There are pieces of evidence regarding the positive association of their intake with healthy biological effects. They act as antioxidants both in the foodstuffs in which they are found and in the organism that take in foods rich in anthocyanins. Many efforts have been carried out to develop new analytical techniques for identification and quantification of anthocyanins in plant materials, as well as their effects in vivo and in vitro. With this in mind, an overview to general considerations concerning (i) polyphenol and flavonoid history; (ii) chemical structure, color and intake of anthocyanins and (iii) sample preparation and extraction methods are presented in this chapter.

Part of the book: Phenolic Compounds

By Julia Martín, Eugenia Marta Kuskoski, María José Navas and Agustín G. Asuero

Anthocyanins are a family of natural pigments classified into the group of flavonoids, considered to be responsible for the color and taste of many fruits and vegetables, i.e. berries. Anthocyanins are common components of the human diet. Besides their interest as colorant because of their coloring properties, the study of anthocyanin compounds stems from their wide applicability in the prevention and even in the treatment of various human diseases. However, various aspects of the pharmacological roles of anthocyanins remain in the dark, having still several obstacles to the development of robust diets or prescribing lines on consumption of anthocyanins. The chemical structure of anthocyanins determines in large measure its capacity and efficacy as an antioxidant agent. In this study, the following aspects are reviewed: the antioxidant effect of anthocyanin pigments; the oxidative stress, the bioavailability after intake and biological aspects of anthocyanins, the method for measuring the antioxidant activity of anthocyanins, the relationship between structure and activity; and the influence of the anthocyanins in the antioxidant activity of wines. Finally an overview of some potential uses in food industry is attempted mainly focusing in the anthocyanin encapsulation topic. Attention has been paid to the more recent publications in the field.

Part of the book: Flavonoids

By Julia Martin, David Daffos Ruiz de Adana and Agustin G. Asuero

The aim of this chapter is to show checking the underlying assumptions (the errors are independent, have a zero mean, a constant variance and follows a normal distribution) in a regression analysis, mainly fitting a straight‐line model to experimental data, via the residual plots. Residuals play an essential role in regression diagnostics; no analysis is being complete without a thorough examination of residuals. The residuals should show a trend that tends to confirm the assumptions made in performing the regression analysis, or failing them should not show a tendency that denies them. Although there are numerical statistical means of verifying observed discrepancies, statisticians often prefer a visual examination of residual graphs as a more informative and certainly more convenient methodology. When dealing with small samples, the use of the graphic techniques can be very useful. Several examples taken from scientific journals and monographs are selected dealing with linearity, calibration, heteroscedastic data, errors in the model, transforming data, time‐order analysis and non‐linear calibration curves.

Part of the book: Uncertainty Quantification and Model Calibration

By Julia Martín, Lucía Fernández Sarria and Agustín G. Asuero

Kjeldahl method using concentrated boric acid is a common practice in many laboratories. A thorough study of the titration with hydrochloric acid of ammonia trapped in a solution of boric acid is made in an attempt to explain the fundamentals of a widely applied standard method. A new potentiometric method for the determination of the end point in the Kjeldahl titrimetric finish is proposed based on the linearization of the titration curve of the ammonia‐boric acid system. The method is strictly based on mole and charge balances, and no approximations are made in deriving the equations. The proposed method has proved very accurate when applied to synthetic titration curves and data. Some problems, however, are experienced in the practice, because the behavior of the experimental system studied is far from the expected one on the basis of the theoretical model. However, a slight modification of the devised method has been applied to the experimental titration of ammonia with hydrochloric acid, in boric acid as trapping solution, getting good results.

Part of the book: Advances in Titration Techniques

By Julia Martín, Laura Ortega Estévez and Agustín G. Asuero

An overview of the state of the art concerning with earlier approaches to titration in redox systems is given in this chapter, in which an overview on redox bibliography has also been undertaken. Titration error has been the subject of a variety of excellent papers, but the number of papers dealing with titration error in redox titrations is scarce. However, a single hyperbolic sine expression for the titration error in donor/acceptor titration of displacement and electronic transference reactions is derived in this chapter. The titration error expression is applicable to symmetrical redox reactions, that is to say, those in which no polynuclear species are involved in the equilibria. The donor versus acceptor particle notation is chosen to accentuate the analogy with that used in the description of acids and bases following the steps given by the French School and other recognized authors (Budevsky, Butler, Charlot, Gauguin, Inczedy, Monnier, Rosset). A diagram for the titration error in function of the difference between the end and equivalence point (pX) is drawn in order to facilitate the graphical calculation of titration error. A detailed error analysis concerning with the propagation of systematic and random error propagation in the titration error is given.

Part of the book: Redox

By Julia Martin, Gabriel Delgado Martin and Agustin G. Asuero

Plotting two straight line graphs from the experimental data and determining the point of their intersection solve a number of problems in analytical chemistry (i.e., potentiometric and conductometric titrations, the composition of metal-chelate complexes and binding interactions as ligand-protein). The relation between conductometric titration and the volume of titrant added lead to segmented linear titration curves, the endpoint being defined by the intersection of the two straight line segments. The estimation of the statistical uncertainty of the end point of intersecting straight lines is a topic scarcely treated in detail in a textbook or specialized analytical monographs. For this reason, a detailed treatment with that purpose in mind is addressed in this chapter. The theoretical basis of a variety of methods such as first-order propagation of variance (random error propagation law), Fieller’s theorem and two approaches based on intersecting confidence bands are explained in detail. Several experimental systems described in the literature are the subject of study, with the aim of gaining knowledge and experience in the application of the possible methods of uncertainty estimation. Finally, the developed theory has been applied to the conductivity measurements in triplicate in the titration of a mixture of hydrochloric acid and acetic acid with potassium hydroxide.

Part of the book: Advances in Titration Techniques

By Antonio Gustavo González, María Ángeles Herrador, Agustín García Asuero and Julia Martín

In this contribution, we outline the estimation of measurement uncertainty of analytical assays in a practical way, according to the so-called reconciliation paradigm, by considering the heritance of uncertainties according to the ISO Guide to the expression of uncertainty in measurement (ISO/GUM) approach and the accuracy (bias and precision) study coming from the in-house method validation. A cause and effect analysis is performed by using the Ishikawa diagram or fishbone plot, consisting of a hierarchical structure reaching a final outcome that is the analytical result. The procedure is illustrated with a case study. This procedure may be very suitable for processing data in accreditation of routine assays.

Part of the book: Quality Control in Laboratory

By Julia Martin, Enrique Jacobo Díaz-Montaña and Agustín G. Asuero

Cyclodextrins (CDs) are cyclic oligosaccharides produced by enzymatic degradation of starch. The most common CDs are the main natural ones, α, β and γ, which are constituted of 6, 7 and 8 glucopyranose units, respectively. The CD structure forms a torus or doughnut ring and the molecule actually exists as a truncated cone. The outer side of the toroid is hydrophilic in nature due to the hydroxyl groups of the glucopyranose units while the internal cavity is relatively apolar. Thus, CDs have a high potential to entrap entirely or partially a wide variety of compounds in a process known as complexation. This gives them new physico-chemical properties and characteristics. The main applications of CDs in drug formulation rely on CD complexation and include the protection of easily oxidizable molecules or the improvement of aqueous solubility. The use of CDs in analytical chemistry is based on his host-guest recognition property, known as supramolecular complex formation. Currently, CDs are successfully used in molecular recognition-based methods like chromatographic separations, spectroscopic and electroanalyses. Quiral analytical separations are a CD area of special relevance. In this work, attention is paid to more recent references, especially to selected reviews.

Part of the book: Cyclodextrin