CE methods for the determination of non-protein amino acids in foods

In addition to the 20 amino acids universally distributed as protein constituents in living organisms, there are other amino acids of non-protein origin that can be found in foods. The determination of these non-protein amino acids is interesting since they can be indicative of the quality and safety of foods. This work presents for the first time an updated and comprehensive review devoted to show the possibilities of capillary electrophoresis for the determination of non-protein amino acids in food samples. The results reported have been classified according to the chemical structure of the non-protein amino acid studied. Separation conditions as well as detection systems used have been detailed since most of these amino acidic compounds do not possess chromophore groups detectable by conventional UV-Vis detection, being in this case necessary a previous derivatization step. Finally, the application of microchip electrophoresis to the determination of non-protein amino acids in foodstuffs is also included in this review.     

Chromatographic methods for tetracycline analysis in foods.

The tetracyclines have served for decades as an important class of antibiotics in food animal health and production. As such, they have also been a source of concern for residue monitoring authorities around the world. In response to this concern a number of microbial inhibition, immunoassay and bacterial receptor methods have evolved for the detection of this class of compounds in various foods of animal origin. However, these methods often lack specificity and are subject to false positive and false negative results. For these reasons a number of chromatographic methods for the separation and determination of the tetracyclines isolated from foods have been developed that are capable of identifying and quantifying individual tetracycline drugs. We present here an overview of tetracycline analytical methods, including microbial inhibition, immunoassay and receptor technologies for detection, techniques for isolation from food matrices, and thin-layer chromatographic, high-performance liquid chromatographic, gas chromatographic and mass spectrometric procedures for determination of this class of compounds. A discussion of the variables involved in such methodology and a review of method criteria are offered.     

A review of multivariate calibration methods applied to biomedical analysis

The determination of the contents of therapeutic drugs, metabolites and other important biomedical analytes in biological samples is usually performed by using high-performance liquid chromatography (HPLC). Modern multivariate calibration methods constitute an attractive alternative, even when they are applied to intrinsically unselective spectroscopic or electrochemical signals. First-order (i.e., vectorized) data are conveniently analyzed with classical chemometric tools such as partial least-squares (PLS). Certain analytical problems require more sophisticated models, such as artificial neural networks (ANNs), which are especially able to cope with non-linearities in the data structure. Finally, models based on the acquisition and processing of second- or higher-order data (i.e., matrices or higher dimensional data arrays) present the phenomenon known as “second-order advantage”, which permits quantitation of calibrated analytes in the presence of interferents. The latter models show immense potentialities in the field of biomedical analysis. Pertinent literature examples are reviewed.     

Nuclear methods of analysis applied to quantitation in laser microprobe mass spectrometry

Laser microprobe mass spectrometry (LMMS) detection limits for mercury have been determined using mercury-doped Spurr's tissue embedding medium. Actual mercury concentrations were confirmed via INAA. Procedures have also been developed to measure lithium and indium concentrations in thin films of polymerized Spurr's samples via PIGE and PIXE. These elements are currently being investigated as laser power density internal standards in the analysis of human tissue for studies of trace element involvement in neurological diseases.     

Analytical methods applied to the determination of pesticide residues in foods of animal origin. A review of the past two decades

Pesticides are widely used in agriculture and can be transferred to animals in a number of ways. Consequently, reliable analytical methods are required to determine pesticide residues in foods of animal origin. The present review covers published methods and research articles (1990-2010) in which pesticide residues have been extracted from meat and meat products, milk and dairy products, fish and seafood, and eggs, then cleaned up, and isolated by chromatographic techniques to be identified and quantified by various detection methods. Recovery rates, quantification limits, the matrix effect and related parameters have all been considered. Lastly, future developments in this field are outlined.     

A review of sample preparation methods for the pesticide residue analysis in foods

The pesticide residues in foods have received increasing attention as one of the most important food safety issues. Therefore, more strict regulations on the maximum residue limits (MRLs) for pesticides in foods have been established in many countries and health organizations, based on the sensitive and reliable analysis methods of pesticide residues. However, the analysis of pesticide residues is a continuing challenge mainly because of the small quantities of analytes as well as the large amounts of interfering substances which can be co-extracted with them, often leading to experimental errors and damage to the analytical instruments. Thus, extensive sample preparation is often required for the pesticide residue analysis for the effective extraction of the analytes and removal of the interferences. This paper focuses on reviewing the recent development in the sample preparation methods for the pesticide residue analysis in foods since 2006. The methods include: liquid-liquid extraction (LLE), supercritical-fluid extraction (SFE), pressurized-liquid extraction (PLE), microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE), gel permeation chromatography (GPC), solid-phase extraction (SPE), molecularly imprinted polymers (MIPs), matrix solid-phase dispersion (MSPD), solid-phase micro-extraction (SPME), QuEChERS, cloud point extraction (CPE) and liquid phase micro-extraction (LPME), etc. Particularly their advantages, disadvantages and future perspectives will be discussed.     

Analytical methods used to measure acrylamide concentrations in foods

The state-of-the-art of analysis for acrylamide in food is reviewed. The majority of analytical methods adopts a similar approach: addition of internal standard to the specimen, extraction with water, purification of extract using a solid-phase extraction cartridge, and then determination using either gas chromatography coupled to mass spectroscopy (GC/MS) after bromination, or direct measurement with liquid chromatography coupled to mass spectroscopy (LC/MS). The available methods generally show good agreement and are likely to be accurate. However, improvements in precision (within-laboratory) and repeatability (between-laboratory) are needed by particular data users.     

HPLC analysis of metal chelating agents in micronutrients

The separation and quantitative determination of organic chelating agents such as DTPA, EDDHA, EDDHMA, EDTA and HEDTA as their copper chelates using HPLC and UV detection is described. Analysis is performed on a Spherogel^TM TSK column. The eluent consists of methanol/water (50: 50, v/v) and 0.25 mmol/L Cu(NO₃)₂. The pH value, the composition of the eluent, the temperature, the sample concentration, the flow rate of the eluent and the influence of the detection wavelength were optimized. The linearity of the UV detector was in the range of 0.5 mmol/L to 2.5 mmol/L.     

Ensemble methods and data augmentation by noise addition applied to the analysis of spectroscopic data

Near-infrared spectroscopy has gained great acceptance in the industry due to its multiple applications and versatility. Sometimes, however, the construction of accurate and robust calibration models involves the collection of a large number of samples with related reference analysis that can complicate and prolong the calibration stage.In this paper, ensemble methods and data augmentation by noise simulation have been applied to spectroscopic data in combination with PLSR to obtain robust models able to handle different types of perturbations likely to affect NIR data. Several types of noise have been investigated as well as different ensemble methods focused on obtaining robust PLS models able to predict both the original and the perturbed test data.The suitability of ensemble methods to perform robust calibration models has been investigated and compared to extended multiplicative signal correction (EMSC) and other calibration approaches in a real case of temperature compensation. Extended multiplicative signal correction (EMSC) and ensemble methods seem to be the most appropriate methods yielding the best results in terms of accuracy and prediction ability with a reduced calibration data set.     

Scientific methods applied to the study of art objects

Scientific methods applied to the study of works of art are varied (examination, analysis and dating) and must be chosen with care in accordance with the object of the research. This paper briefly sets out the state of the art highlighting the development and applications of non-destructive methods. Such methods come under either the use of electromagnetic or particle radiation for the formation of images based on shape, development technique, or, on the other hand, the quantitative determination of elements down to and including their traces, isotopes or microsurfaces for the purpose of identifying the matter, its date, origin and development.     

CE: a useful analytical tool for the characterization of Maillard reaction products in foods

The Maillard reaction (MR) is a complex series of nonenzymatic reactions between reducing compounds and amines, amino acids, peptides, or proteins that play an important role in the formation of flavors and colors in foods during processing and storage. Also, the antioxidant properties of some Maillard reaction products (MRP) was an additional benefit reported. On the other hand, these reactions decrease the nutritional quality of foods and may result in the formation of toxic MRP. Although, research to assess the risks and benefits associated with the consumption of MRP in the diet is still awaiting for new analytical methodologies to be developed. Structural characterization of MRP has been very challenging due to the chemical diversity of these compounds which present a wide range of polarities and molecular weights, making analyses difficult. CE is a technique that has gained popularity for the separation of complex mixtures that have otherwise proved difficult to analyze. Thus, the purpose of this overview is to give the reader an appreciation of some of the CE analytical developments on the analysis of MRP in model systems and foods, and to address the potential of CE on the characterization of this complex group of compounds.     

Depth-sensing indentation applied to polymers: A comparison between standard methods of analysis in relation to the nature of the materials

Mechanical data (hardness and elastic modulus) from instrumented indentation testing are often extracted assuming linear elasticity in the initial portion of the unloading. The method is nowadays widely accepted as a convenient tool to interpret depth-sensing data, however it is a matter of controversy when applied to polymer materials due to their time-dependent behavior. More recently, Loubet and co-workers applied continuous stiffness measurements (CSM), consisting of superimposing a small oscillation to the quasi-static component of loading, to the study of the mechanical properties of polymers and proposed a new model to account for the apparent increase in the contact area detected at the first stages of contact. The present work offers a comparative study between the Loubet’s model using CSM and the procedure yielding a single reading from the onset of unloading. A wide range of thermoplastic polymer materials including glassy and semicrystalline polymers have been investigated. The most important equations employed for each method are summarized and the advantages and disadvantages of employing one procedure or the other are discussed. The differences found between the results obtained from both approaches are discussed in relation to the nature of the polymer material. A comparison between mechanical data extracted from indentation measurements and from classical dynamic mechanical analysis is offered.     

Thin-layer chromatography applied to foods of animal origin: a tutorial review

The chromatography techniques are partially characterized by presence of two phases (stationary and mobile), which allows identification, semi-quantification or quantification of important compounds in different matrices. Among chromatography methods, the thin-layer chromatography (TLC) must be considered for using in routine laboratories due to a number of advantages such as practicality, fast results and effectiveness, low cost, and simultaneous determination of analytes. This review describes the application of this technique to foods of animal origin, as well as compares TLC with other chromatographic methods. TLC has a strong potential as a surrogate chromatographic model for qualitative and quantitative analysis. Therefore, several modifications have been carried out to the conventional TLC system. Nevertheless, further studies should be performed in order to contribute with the scientific community and propagate the TLC method, which has performance and economic advantages compared to other chromatographic techniques.     

Rapid methods to enumerate Escherichia coli in foods using 4-methylumbelliferyl-beta-D-glucuronide

Three methods to enumerate Escherichia coli in food were compared. They were based on AOAC methods using lauryl tryptose broth (LST) medium, LST-4-methylumbelliferyl-beta-D-glucuronide (MUG) medium, and a proposed method using regular LST in combination with E. coli (EC)-MUG medium. An efficacious and cost-effective method is needed that can detect E. coli and does not produce false presumptive positives. We tested 170 cheeses, 40 frozen processed seafood samples, 210 tree nuts, and 40 other samples. The method of choice for enumerating E. coli depends on the commodity itself. For a product, such as hard cheese or processed seafood, with a history of being negative for E. coli and other lactose-fermenting organisms, the proposed method using regular LST/EC-MUG is a good choice. These samples were seldom presumptive positive in the primary LST medium. If gas was produced, EC-MUG was an effective secondary medium. No false positives (fluorescence) or negatives were detected in EC-MUG medium. For a product with a history of being positive for E. coli and/or other lactose fermenting organisms, such as tree nutmeats or cheeses that are ripened by bacteria or mold, the method using LST-MUG is the method of choice. A presumptive positive in the LST-MUG medium was highly correlative with the biochemical tests that confirmed a sample contain E. coli. For samples spiked with E. coli, the results from each of these 3 methods were identical, and were consistent in enumerating E. coli.     

Calorimetric methods applied to the investigation of divided systems in colloid science

A new batch titration microcalorimeter has been used for estimation of thermodynamic properties in various investigated colloidal systems. As examples, we present enthalpic and kinetic data obtained from this calorimetric device for four different processes widely encountered in colloid science:

Thermal analysis and mechanical methods applied to studying properties of SBR compounds containing ionic liquids

The goal of this work was to study new systems for activating sulphur vulcanisation of butadiene-styrene elastomer (SBR) using thermal analysis techniques complementarily with rheological and mechanical properties measurements. New activating systems consist of nanosized zinc oxide and ionic liquids (ILs) – benzalkonium or alkylammonium salts. In this article, we discuss the effect of zinc oxide and ILs on the cure characteristics, vulcanisation kinetics, crosslink density, mechanical properties, damping behaviour and thermal stability as well as resistance to thermooxidative and UV ageing of SBR.Nanosized zinc oxide with ILs reduced the vulcanisation time and temperature of rubber compounds. Their application results in increased vulcanisate crosslink density as well as the improvement of mechanical properties such as tensile strength and vibration damping ability. The influence of ionic liquids on SBR properties depends mainly on the anion present in the molecule. The most active ILs seem to be those with the lactate anion.     

Chromatographic methods for the determination of pesticides in foods.

Chromatography is the most important technique available to the analyst dealing with the determination of pesticide residues in food, feed and environmental samples. Numerous methods for pesticide residues in foods have been developed in the past few years, and this paper reviews some of the most important procedures. A great variety of chromatographic methods, such as solid-phase extractions, column chromatographic clean-up methods, thin-layer, gas, high-performance liquid and supercritical fluid chromatography, and their coupling with sensitive and selective detection methods are surveyed.     

Computational methods applied to the discovery of stem cell factor ligands

A computational study of the stem cell factor (SCF) and potential ligands was carried out starting with a crystallographic model deposited in the protein data bank. The inhibition of the SCF dimerization equilibrium was considered as the rationale for the lead identification of specific ligands. A preliminary molecular dynamics characterization of the SCF dimer allowed to verify the most flexible loop involved in the dimeric area. Then a virtual screening, coupled with energy minimization in GB/SA water, scored the compounds implemented in the NCI diversity molecular database. Ten top ranked ligands were analyzed considering both the SCF loop perturbation in the dimerization area and the network of intermolecular hydrogen bonds. Among these ten compounds two natural agents were identified. The computational work revealed useful new insights for rational design of novel SCF dimerization inhibitors.