An introductory review on the application of principal component analysis in the data exploration of the chemical analysis of food samples.

Principal component analysis (PCA) is currently one of the most used multivariate data analysis techniques for evaluating information from food analysis. In this review, a brief introduction to the theoretical principles that underlie PCA will be given, in addition to presenting the most commonly used computer programs. An example from the literature was discussed to illustrate the use of this chemometric tool and interpretation of graphs and parameters obtained. A list of recently published articles will also be presented, in order to show the applicability and potential of the technique in the food analysis field.

In-syringe dispersive liquid-liquid microextraction.

Dispersive liquid-liquid microextraction (DLLME) has recently been widely used in the separation and preconcentration of various chemical species. Among the various approaches using DLLME are systems that use a syringe as an extraction environment. In this review, details of some methods that use this approach are presented. The ways to promote dispersion, analytical characteristics, and the advantages and disadvantages of the methods, among other aspects, are discussed critically. Finally, some trends in the use of in-syringe microextraction systems are described.

Doehlert design in the optimization of procedures aiming food analysis - A review.

In the present paper is presented a review on the application of Doehlert design in the optimization of some of the steps of analytical procedures aimed the analysis of food samples. The theoretical principles and the main characteristics of this type of design are described. In addition, the main advantages and limitations of Doehlert design over other designs (Central Composite Design and Box-Behnken) and its application in the area of food analysis are discussed. Finally, to illustrate its potential, some examples of Doehlert design application in other areas of food chemistry without the purpose of analytical determination will be briefly presented.

Multivariate optimization of a dispersive liquid-liquid microextraction method for determination of copper and manganese in coconut water by FAAS.

In this study, multivariate methodologies were applied in the optimization of a dispersive liquid-liquid microextraction (DLLME) method, aiming at the determination of Cu and Mn in coconut water samples by flame atomic absorption spectrometry. Some extractors (chloroform and CCl4), dispersants (ethanol, methanol and acetonitrile) and complexing agents (5-Br-PADAP and Dithzone) were previously tested in the extraction. A mixture design was used to optimize the component proportions formed by chloroform (10%), acetonitrile (76%), and 0.020% 5-Br-PADAP solution (14%). Doehlert design optimized the variables pH, NaCl, and buffer amounts for the extraction of both metals. The following analytical characteristics, respectively for Cu and Mn, were accessed: limit of quantification (4.83 and 3.32 µg L-1), enrichment factors (11 and 8 fold), and precision (6.6 and 6.0% RSD, n = 10). Addition/recovery tests of the analytes allowed to find values in the range of 96.5-120% for Cu and 99-107% for Mn.

Multivariate optimization of a goat meat alkaline solubilization procedure using tetramethylammonium hydroxide for metals determination using FAAS.

In the present work, multivariate designs were used to optimize an alkaline dissolution, assisted by ultrasound energy, procedure of goat meat using tetramethylammonium hydroxide (TMAH) aiming to determine Ca, Cu, Fe, K, Mg, Na and Zn by flame atomic absorption (FAAS) and emission (FAES) spectrometry. The optimal conditions found for the dissolution were in the following ranges: 0.4-0.5 g for the sample mass, 12-15 min of sonication and using 700-1000 µL of 25% TMAH at a temperature of 50 °C. The obtained limits of quantification varied between 0.221 (Mg) and 7.60 (Ca) µg g-1. Accuracy was assessed by comparing the results obtained by applying the proposed method with the digestion in an acid medium using a digesting block and by analyzing bovine liver certified reference material. The application of a t-test revealed that, at a 95% confidence level, there were no significant differences between the values obtained.

An alkaline dissolution-based method using tetramethylammonium hydroxide for metals determination in cow milk samples.

This study approaches the development of a method for the determination of Ca, Mg, Zn, and Fe in liquid and powdered cow milk. The method is based on sample dissolution assisted by ultrasound energy in tetramethylammonium hydroxide (TMAH) media and determination by flame atomic absorption spectrometry (FAAS). Central composite design (CCD) associated with response surface methodology and desirability function allowed the fast and efficient optimization of the variables involved in the performance of the dissolution. The developed dissolution method allowed Ca, Fe, Zn, and Mg determination in milk samples with adequate analytical characteristics for these determinations. Addition/recovery tests and analysis of a certified reference material of skimmed powdered milk (ERM-BD150) have shown that this method presents enough accuracy to carry out these analyses.

Artificial neural network employment for element determination in Mugil cephalus by ICP OES in Pontal Bay, Brazil.

Fish are important sources of protein, making them very significant in the human diet. Although the consumption of this food is beneficial for health, it is essential that the product does not contain inorganic components above the limits recommended by the current legislation. Therefore, a method for determination of elements in fish (Mugil cephalus) samples was optimized. A simplex centroid mixture design with restriction was applied for optimization of the acid digestion of samples in an open system under reflux in order to evaluate the best ratio between the reagents HNO3, H2O2 and H2O. The results indicated that more intense analyte signals were obtained when a mixture containing 3.6 mL of HNO3 (65% v/v), 0.4 mL of H2O2 (30% v/v) and 6.0 mL of H2O was used. The accuracy of the method was assessed with a CRM of oyster tissue (NIST 1566b). The method presented relative standard deviations (RSDs) of 3.54%; 3.82%; 4.81% and 3.50% for Zn, Fe, Cu and S, respectively. The detection limits were 0.002 mg kg-1 for Cu and Zn and 0.02 mg kg-1 for Fe and S. The proposed method was applied for the determination of Zn, Fe, Cu and S in fish samples. A Kohonen Self-Organizing Map (KSOM) with K-means implementation was applied to better delimit the boundary between groups and the spatial and temporal influence on how concentrations of the chemical elements were perceived. To verify the separation, the Davies-Bouldin and Silhouette indices were used, obtaining 0.5374 and 0.8541, respectively, indicating satisfactory separation.

Mineral content of longissimus lumborum from growing lambs fed crude glycerin.

The objective of the study was to evaluate whether crude glycerin (CG), which was supplied as a dietary ingredient for growing lambs, affected the macro- and micromineral contents of the longissimus lumborum (LL). Twenty-four lambs were placed in two treatments: animals that received no CG and animals that received CG as part of their diet. The experiment lasted for 56 days. The phosphorus, potassium, magnesium, calcium and chromium contents in the LLs of the lambs were not significantly different between the groups. Cadmium, nickel and lead were not detected in the LLs of lambs fed CG. The zinc, iron and copper contents decreased in the LLs of lambs fed CG (approximately 10%, 14%, and 30%, respectively) (P ≤ .03). The sodium content in the LLs increased with the inclusion of CG in the diet (11%) (P = .029). We concluded that the zinc, iron and copper contents decreased in the LLs of the lambs fed CG and sodium content increased.

Simultaneous optimization of multiple responses and its application in Analytical Chemistry - A review.

This manuscript covers the application of the main techniques for simultaneous optimization of multiple responses generated by the application of multivariate designs (two-factor factorial, Central Composite, Doehlert, etc.) or by chromatographic runs in the development of analytical methods. Special attention will be given to the graphical method, desirability function, multiple response function and chromatographic response functions, since they are more frequently used in the analytical area. The advantages, disadvantages, limitations, and potentialities of these methods will also be addressed, as well as some of their applications, commenting on real examples from the literature. Some less usual methods in multiple response optimization in Analytical Chemistry will also be commented.

Doehlert design in the optimization of ultrasound assisted dissolution of fish fillet samples with tetramethyl ammonium hydroxide for metals determination using FAAS.

Doehlert design and desirability function were used in the optimization of an ultrasound assisted dissolution method of fish fillet samples with tetramethyl ammonium hydroxide (TMAH) for the determination of Ca, Fe, Zn and Mg by flame atomic absorption spectrometry. The variables values after optimization were 620 µL (volume of TMAH), 25 min (sonication time) and 46 °C (bath temperature). The quantification limits for Ca, Mg, Fe and Zn were 56, 107, 23 and 2.9 µg g-1, respectively. Accuracy was evaluated by comparing the results generated from the analysis of the samples treated by the proposed method and by wet digestion. Additionally, accuracy for Fe and Zn was assessed by the analysis of certified reference materials Tort-3 (Lobster hepatopancreas), ERM-CE 278 (mussel tissue) and Dolt-4 (Fish liver). There were no significant differences between the results obtained at a 95% confidence level when results were evaluated by t-test application.

Evaluation of macro and micronutrient elements content from soft drinks using principal component analysis and Kohonen self-organizing maps.

This study approaches the determination of nine elements from Brazilian carbonated soft drinks of several flavors and manufactures using inductively coupled plasma optical emission spectrometry (ICP OES). The concentrations of the elements varied as follows: (in µg L-1: Cu: 4.00-78.0; Fe: 74.0-506; Mn: 20.0-66.0; Zn: 104-584) and (in mg L-1: Ca: 4.81-16.2; K: 6.73-260; Na: 26.0-175; S: 1.43-5.41; P: 0.186-219). Principal component analysis has shown some tendencies to form two groups according to the drink flavor (orange and cola), but only cola presented a clear and complete separation. Using Kohonen maps, it was observed a tendency to form three flavor groups: (i) cola, (ii) orange and lemon, and (iii) guarana. However, this last tool proved to be more accurate in the groups' formation.

Screening of Passiflora L. mineral content using principal component analysis and Kohonen self-organizing maps.

A method using digestion with diluted nitric acid and inductively coupled plasma optical emission spectrometry was applied to determine metal ions in the peel, pulp, and seed of Passiflora edulis f. flavicarpa and Passiflora cincinnata cultivated in the Bahia state, Brazil. Plasma parameters (radio frequency power and argon flow rates) were optimized. The quantification limits (µg g-1) were: Ca (43.0); Co (1.3); Cu (10.0); Fe (10.0); K (20.0); Mg (26.6); Mn (0.33); Na (56.6) and Zn (10.0). The accuracy of the method was evaluated by the analysis of certified reference materials (NIST 1567a Wheat Flour and NIST 1577b Bovine Liver). Recovery studies were carried out and values found were between 89 and 120%. PCA and Kohonen self-organizing maps showed the formation of groups, corresponding to the fruit parts. Thus, passion fruit has great importance and biological potential, due to its high content of K and low Na.

Determination and Evaluation of Metallothionein and Metals in Mugil cephalus (Mullet) from Pontal Bay, Brazil.

To assess environmental contamination, studies have been increasingly carried out using biomarkers to diagnose the effects of toxic metal exposure, such as metallothionein (MT). In this context, the aims of the present study were to determine Cd, Cu, Ni and Pb concentrations, by ICP-MS, in liver samples from Mugil cephalus from the municipality of Ilhéus, located in North-Southeastern Brazil, in the state of Bahia, which has been increasingly suffering from anthropogenic pressure, and to quantify total MT in liver and gills. Among essential metals, copper (199.2 µg g-1) presented concentrations approximately 7 times higher than allowed by the World Health Organization (30 µg g-1). Liver samples showed higher concentrations than gills. Metallothionein concentrations indicate differential contamination along the study area. The first sampling showed higher induction of MT synthesis overall. Differences between liver and gill MT concentration trends were relatively minor, which may indicate the adequacy of analyzing gills in an environmental monitoring context.

Synthesis of a new solid-phase extractor and its application to preconcentration and determination of lead in water samples.

A procedure for preconcentration and determination of lead in water is described. The method is based on the sorption of Pb(II) in a minicolumn packed with a functionalized sorbent and subsequent elution with acidic solution. The determination of lead content in the eluate was carried out using flame atomic absorption spectrometry. The sorbent was prepared by immobilization of the ligand 4-(5'-bromo-2'-thiazolylazo)orcinol on polystyrene-divinylbenzene through an azo spacer. Diazotization and coupling reactions were used for synthesis of the sorbent. Some variables affecting the preconcentration were optimized using a full factorial design. Under optimized conditions, the method presented a detection limit of 0.5 microg/L and enrichment factor of 36 for a sample volume of 25 mL. The accuracy of the method was tested by the determination of lead in a standard reference material (National Institute of Standards and Technology 1643d Fresh Water). The proposed procedure was applied to the determination of lead in samples of natural and drinking waters.

Flow injection preconcentration system using a new functionalized resin for determination of cadmium and nickel in tobacco samples.

A solid-phase extraction method combined with flow injection (FI) on-line flame atomic absorption spectrometry (FAAS) for the determination of cadmium and nickel in tobacco samples is presented. The 2-aminothiophenol functionalized Amberlite XAD-4 (AT-XAD) resin was synthesized by covalent coupling of the ligand with the copolymer through a methylene group. A minicolumn packed with AT-XAD was connected into the automated on-line preconcentration system. Elution of metal ions from minicolumn can be made with 0.50 mol L(-1) hydrochloric acid solution. With a consumption of 21.0 mL of sample solution, detection limits (3 s) of 0.3 (Cd) and 0.8 microg L(-1) (Ni) were achieved at a sample throughput of 18 h(-1). Enrichment factors (EF) of 99 (cadmium) and 43 (nickel) were obtained compared with the slope of the linear portion of the calibration curves before and after preconcentration. The contents of Cd and Ni in a certified reference material (NIST 1570a, spinach leaves) determined by the present method was in good agreement with the certified value. The developed procedure was also successfully applied to the determination of Cd and Ni in local tobacco samples.