Quantification of Se-Methylselenocysteine and Its γ-Glutamyl Derivative from Naturally Se-Enriched Green Bean (Phaseolus vulgaris vulgaris) After HPLC-ESI-TOF-MS and Orbitrap MS n -Based Identification

Orthogonal liquid chromatographic (ion exchange, reversed phase, and ion pairing) and mass spectrometric [electrospray ionization (ESI)-TOF-MS, ESI-Orbitrap MS, and inductively coupled plasma mass spectrometry (ICP-MS)] methods were addressed to identify and quantify selenium species from a naturally Se-enriched green bean (Phaseolus vulgaris vulgaris) sample after proteolytic digestion. While selenomethionine (10.1 mg/kg as Se) and selenate (9.5 mg/kg as Se) could be quantified in a straightforward way by anion exchange LC-ICP-MS technique, a multistep purification protocol was required to identify Se-methylselenocysteine and γ-glutamyl-Se-methylselenocysteine in an unambiguous way prior to quantification by using either in-source fragmentation (LC-ESI-TOF-MS) or collision-induced dissociation (LC-ESI-Orbitrap MS). Finally, Se-methylselenocysteine (2.6 mg/kg as Se) and γ-glutamyl-Se-methylselenocysteine (1.2 mg/kg as Se) could contribute to the overall selenium recovery of 72 %. This sample is the first of the Faboideae subfamily and Phaseolus ssp. to be speciated to such an extent for selenium including γ-glutamyl-Se-methylselenocysteine, a highly potential selenium species, which makes this bean material an ideal candidate for functional food purposes.     

Analysis of Fourteen β-Agonists in Weight-Reducing Dietary Supplements Using QuEChERS-Based Extraction Followed by High Resolution UHPLC-MS

In the present study, a method for analysis of 14 β-agonists in weight-reducing dietary supplements using the QuEChERS procedure followed by UHPLC-ESI/MS-MS based on two scan events (full scan FTMS and HCD data dependent MS/MS) in positive ionization mode has been developed. Sample extraction and purification were carried out using a modified QuEChERS method. Rapid analysis was carried out by ultra-high performance liquid chromatography coupled with high resolution Fourier transform mass spectrometer. Fourteen β-agonists were separated within 15 min with limit of detection in the range of 1.8–23.1 μg kg^?1. The average recoveries in spiked dietary supplements varied from 67.1 to 107.3 %, which were carried out with spiked samples at three concentration levels. Validation parameters including linearity and repeatability were satisfactory. Finally, based on the results, it is concluded that the proposed method is an appropriate procedure for β-agonists analysis in weight-reducing dietary supplements.     

UV-Visible Spectroscopy and Multivariate Classification as a Screening Tool to Identify Adulteration of Culinary Spices with Sudan I and Blends of Sudan I + IV Dyes

This work propose a feasible, rapid, and simple method for detecting culinary spices adulterated either with Sudan I dye or blends of Sudan I + IV dyes at three concentration levels. The method is based on the use of UV-visible spectroscopy with multivariate analysis. Four types of spices were studied: three paprika varieties (mild, hot, and smoked) and a spice commonly consumed in Argentina called aji molido. Principal components analysis was firstly applied as an exploratory analysis and then, two classification techniques were used: K-nearest neighbors (KNN) and partial least squares-discriminant analysis (PLS-DA). Three classes were defined: unadulterated samples and adulterated samples with Sudan I or blends of Sudan I + IV dyes at 1, 2.5, and 5 ppm (mg L^?1). Classification techniques gave satisfactory results: between 89 and 100 % for PLS-DA and between 83 and 92 % for KNN. The sensitivity and specificity of the models were above 83 %. It has to be highlighted that none of the adulterated samples were assigned as unadulterated, which is very positive because of the implication that these results have on consumer health. The capability of detecting mixtures of Sudan dyes is a very important advantage because each Sudan dye generates different hazardous metabolites in human body so their toxicity may be enhanced by the simultaneous presence of such dyes.     

Aluminium and Its Complexes in Teas and Fruity Brew Samples,Speciation and Ions Determination by Ion Chromatography and High-Performance Liquid Chromatography–Fluorescence Analytical Methods

The paper presents results of aluminium determination in samples of black and fruit teas. Total aluminium concentration was determined along with the concentration of aluminium in a cup of tea in tea samples in two price groups (>1€ and <1€). Based on the conducted study, no differences were found in aluminium concentration in black and fruit teas depending on the price group. Developed ion chromatography method was applied to determine inorganic and organic ions in tea samples, especially those which may form complexes with aluminium: fluoride, sulphate, oxalate and citrate ions. Analysis by this method using ion chromatography allowed for the determination of 12 anions: F^?, HCOO^?, CH₃COO^?, NO₂ ^?, Br^?, NO₃ ^?; Cl^?, CH₂(COO)₂ ^2?, SO₄ ^2?, C₂O₄ ^2?, PO₄ ^3? and C₃H₅O(COO)₃ ^3? in the time of 40 min. Speciation analysis of aluminium was performed in optimised HPLC-fluorescence analytical system (with Lumogallion as a post-column reagent). It was observed that organic aluminium complexes are quickly degraded to form Al³⁺ which is the reason why speciation analysis in tea samples does not provide the full image of speciation distribution. Nevertheless, this developed method was successfully used in the determination of aluminium complexes with fluorides in tea samples.     

Characterization of Volatile Organic Compounds of Vinegars with Novel Electronic Nose System Combined with Multivariate Analysis

A novel electronic nose system (also called artificial olfaction system) based on colorimetric sensor array was developed for characterization and identification of the volatile organic compounds (VOCs) of vinegars fermented from different raw materials. Fifteen chemo-responsive dyes including nine metalloporphyrins and six pH indicators were selected according to their sensitivity to volatile compounds from vinegar samples. The colorimetric sensor array was made by printing selected chemo-responsive dyes on a silica gel plate. A color change profile for each sample was obtained by differentiating the images of the colorimetric sensor array before and after exposure to the odorant of vinegar sample. The digital data (i.e., red, green, and blue components of the image) representing the color change profiles for the vinegar samples were analyzed. Genetic algorithm partial least squares was employed to select sensitive image digital variable to build a calibration model. Several methods (i.e., linear discrimination analysis, LDA; partial least square discrimination analysis; artificial neural network) were also used comparatively for classification, the result was evaluated by the % correct identification of samples. The optimal model was achieved by LDA model with 14 image digital variables used, and all the vinegar samples were correctly identified both in training and testing sets. This research suggests that the system shows significant potential in vinegar VOCs characterization and discrimination.     

Optimisation of Glucose Biosensors Based on Sol–Gel Entrapment and Prussian Blue-Modified Screen-Printed Electrodes for Real Food Analysis

In this study, we report the construction of amperometric screen-printed glucose biosensors for food analysis by using two procedures for Prussian Blue (PB) deposition and different membranes for enzymatic immobilisation. The comparison between the screen-printed electrodes modified with PB by electrochemical and chemical deposition showed higher analytical performance (detection limit of 1 μM, linear range from 0.5 to 500 μM and a sensitivity of 823 μA mM^?1 cm^?2) when the latter was employed. Then, the immobilisation of glucose oxidase (GOD) by silica sol–gel and polyvinyl alcohol (PVA) hydrogel was performed on electrochemically modified PB electrodes. The electrochemical response of two glucose biosensors was evaluated by flow injection analysis. Biosensors constructed by silica sol–gel entrapment showed a wider linear range (0.005–1 mM) and a detection limit (0.02 mM) that was 10-fold lower than using entrapped GOD in PVA. The selected glucose biosensor showed negligible interference from ascorbic acid when the Nafion membrane was used to cover the PB-modified electrode surface. Additionally, it exhibited an operating lifetime of 8 h under continuous glucose injections ranging from 0.01 to 2 mM. Finally, the biosensor was applied for specific determination of glucose in red and white wines, juices and dried fruit.     

Application of Box–Behnken Design in the Optimization of In Situ Surfactant-Based Solid Phase Extraction Method for Spectrophotometric Determination of Quinoline Yellow in Food and Water Samples

In this work, a simple, rapid and sensitive method using in situ surfactant-based solid phase extraction (ISS-SPE) combined with UV–vis spectrophotometry has been developed for the preconcentration and determination of trace amounts of quinoline yellow in food and water samples. The Box–Behnken design was employed to optimize the extraction efficiency. The variables of interest were pH, surfactant volume, extraction time and NaI volume. In the optimal conditions, the calibration graph was linear in the range of 10.0–750 μg L^?1 with a correlation coefficient of 0.9982. The limit of detection (LOD) was 2.1 μg L^?1, and the preconcentration factor was calculated to be 51.8.     

An LC-IT-MS/MS-Based Method to Determine Trichothecenes in Grain Products

The aim of this work was to evaluate the usefulness of the ion trap mass spectrometry coupled to high-performance liquid chromatography for simultaneous determination of selected trichothecenes (nivalenol, deoxynivalenol, fusarenon-X, neosolaniol, 3-acetyl-deoxynivalenol, diacetoxyscirpenol, HT-2 and T-2 toxins) in grain products. These compounds were extracted from the grain products and then cleaned up with the developed, simple and robust procedure using some mixture of neutral alumina, charcoal and diatomaceous earth. Method recovery was 88–125 % depending on combination of the analysed mycotoxins, sample matrix and the fortification level. Method precision expressed by relative standard deviation ranged from 2.6 to 27.4 %. The concentrations of the selected trichothecenes have been determined in 94 samples of cereal-based products. Maize-based next to wheat-based products were the most contaminated with deoxynivalenol, neosolaniol, 3-acetyl-deoxynivalenol, diacetoxyscirpenol and HT-2 toxin. In 83 % of wheat-based products, deoxynivalenol was determined at the average level of 249 μg kg^?1. The highest concentration of deoxynivalenol—2,026 μg kg^?1 (476?±?471 μg kg^?1 on the average)—was found in the maize-based product. Other mycotoxins were found much less frequently: 3-acetyl-deoxynivalenol in only one sample at the concentration of 59 μg kg^?1, neosolaniol, HT-2 toxin and diacetoxyscirpenol in a few samples on average concentrations close to respective limits of quantification.     

Determination of Deoxynivalenol-3-Glucoside in Cereals by Hydrophilic Interaction Chromatography with Ultraviolet Detection

A new hydrophilic interaction liquid chromatography (HILIC) method was developed for the determination of deoxynivalenol-3-glucoside (D3G) in cereals. D3G was extracted with water and cleaned with an immunoaffinity (IA) column, followed by chromatographic separation on a Syncronis HILIC column with acetonitrile-water (90:10, v/v) as the mobile phase, and detected at 220 nm by UV detection. The calibration curve was found to be linear in the range of 0.1–2.0 μg/ml. Limit of detection and limit of quantification were 8 and 25 μg/kg, respectively. The method was applied to the determination of D3G in 14 cereal samples, which were analyzed as well as by LC-MS/MS. The results indicate that the method can be considered as an alternative to LC-MS/MS and could be adopted by nonprofessional analytical labs.     

A New Gas Chromatography Method for Quality Control of Methylsulfonylmethane Content in Multicomponent Dietary Supplements

This paper reports the first gas chromatography method with flame ionization detection (GC–FID) for rapid assay of the quality control of methylsulfonylmethane (MSM) content in multicomponent dietary supplements. The proposed method was completely validated and used for quality control of multicomponent dietary supplements available in the local market. The study showed that the content of MSM varied in different commercial samples (77.7–112.3 % of the declared amount) and was dependent on different qualities of the dietary supplement producer. The developed method was based on the rapid extraction of MSM into acetone using ultrasound bath (5 min) and on the subsequent quantification of the MSM by gas chromatography. The used GC conditions were as follows: fused silica cyanopropylphenylmethylpolysiloxane capillary column Alltech AT^TM-624 (30 m?×?0.32 mm i.d., 1.8-μm film thickness), injection mode split of 1:10, sample volume of 1.0 μL, injector temperature of 190 °C, detector temperature of 190 °C, column temperature held at 190 °C for whole analysis time, and helium carrier gas flow rate of 0.7 mL min^?1. Nitrobenzene was chosen as internal standard for precise and accurate quantification of MSM in dietary supplements. Method precision evaluated as relative standard deviation was 1.7 %, and method accuracy evaluated as recovery was in the range of 102.5–106.2 %. The method required no special sample pretreatment, so it showed to be simple, robust, rapid (short analysis time of less than 4 min), and suitable for routine analysis of MSM in food quality control laboratories.     

Development of an Efficient Acid Digestion Procedure Utilizing High-Pressure Asher Technique for the Determination of Iodine and Metallic Elements in Milk Powder

An effective wet digestion procedure for the determination of total iodine contents in milk powder samples was developed utilizing a high-pressure asher technique. The optimized method based on a two-stage digestion procedure. In the first stage, 500 mg samples were digested at 300 °C for 2 h using 15.2 mol L^?1 HNO₃ (5 mL) and 30 % H₂O₂ (3 mL). After the first digestion stage, digestion vessels were allowed to cool down and 1.2 mL of 20 % (w/v) Na₂S₂O₈ solution was added as an additional oxidizing agent to the samples. After that, the vessels were closed, and they were heated at 100 °C for 30 min, resulting in clear and colorless sample solutions. Iodine concentrations in the digested samples were measured with inductively coupled plasma mass spectrometry. The accuracy of the optimized method was confirmed by analyzing milk powder reference material (BCR-151, milk powder). The obtained value for iodine (5.29?±?0.37 mg kg^?1, n?=?6) was in good agreement with the certified value (5.35?±?0.14 mg kg^?1). Furthermore, the results obtained for reference material showed that the developed method can be applied also for the determination of other elements, e.g., copper, iron, and lead in the digested milk powder samples.     

Rapid Quantification of Soyasaponins I and βg in Italian Lentils by High-Performance Liquid Chromatography (HPLC)–Tandem Mass Spectrometry (MS/MS)

In this work, an innovative and fast analytical method for the quantification of soyasaponins I and βg in lentils has been developed. Samples were extracted using 70 % aqueous ethanol at room temperature and then injected into a high-performance liquid chromatography–tandem mass spectrometry system. The correlation coefficients of calibration curves of the analyzed compounds were ≥0.9997. The recoveries obtained by spiking the lentil samples with a standard mixture of soyasaponins I and βg at 50 and 100 mg l^?1 were in the range of 96–101 and 98–103 %, respectively. The validated method was applied to the analysis of 30 lentil samples from central Italy. Soyasaponins I and βg were present in these lentils in concentrations that ranged from 54 to 226 mg kg^?1 and from 436 to 1,272 mg kg^?1, respectively. Our data indicated that lentils cultivated in fields at intermediate altitudes (1,142–1,387 m) showed the highest levels of soyasaponins, a finding confirmed by principal component analysis.     

Improvement of Determination of Trace Amounts of Arsenic and Selenium in Slim Coffee Products by HG-ICP-OES

A method for the determination of total inorganic arsenic and selenium in slim instant coffees using hydride generation inductively coupled plasma optical emission spectrometry (HG-ICP-OES) was proposed. Various sample preparation procedures, including the traditional total decomposition by the hot-plate or microwave heating in a HNO₃/H₂O₂ mixture and alternative procedures based on the solubilisation in aqua regia or tetramethyl ammonium hydroxide (TMAH) and the dilution only with water or a low concentrated HNO₃ solution were examined and compared. Corresponding As and Se hydrides were generated in the reaction of an acidified sample solution with the NaBH₄ reductant in the presence of antifoam A. A small sample preparation with aqua regia in an ultrasonic bath followed by the pre-reduction with KI–ascorbic acid in the HCl medium for total As and the boiling with HCl for total Se were found to be optimal. The external calibration using standards treated and measured as the same as samples were applied for the analysis. Limits of detection (LODs) of 0.96 and 0.55 ng ml^?1 were assessed for As and Se, respectively. The precision (as the relative standard deviation [RSD]) was within 1.6–7.1 %. The accuracy of the method was confirmed by the recovery test and the analysis of a standard reference material (non-fat milk powder, SRM 1459). The developed procedure was applied for the analysis of six commercial instant slim coffee products available in the Polish market and it was found that these products contain traces of As (0.114–0.247 μg g^?1) and Se (0.089–0.137 μg g^?1).     

Ridgetail White Prawns,Exopalaemon carinicauda,Storage Time Rapid Determination Using Electronic Nose

Ridgetail white prawns, Exopalaemon carinicauda, storage time rapid determination method based on electronic nose was investigated in this paper. Prawns were stored at 4 °C for 9 days. Each day, electronic nose responses, and total volatile basic nitrogen index were measured during the storage period. Total volatile basic nitrogen index provided a freshness standard according to China standard protocols. Signal-to-noise ratio spectrum calculated by stochastic resonance discriminates prawn samples under different storage days successfully. Prawns' storage time determination model was developed based on signal-to-noise ratio eigenvalues. Validating experiments demonstrated that this model predicted prawn storage time with an accuracy of 90 %. Prawn freshness critical value ?82.77066 was also obtained by referring to total volatile basic nitrogen index and the developed model. This method is promising in seafood freshness evaluation.     

A Fast and Accurate UPLC Method for Analysis of Proteinogenic Amino Acids

A reliable and inexpensive method for the measurement of proteinogenic amino acids was developed. It allows the screening of large sample volumes that is important for current food and feed applications, but also for future biobased applications. The method is based on acid hydrolysis and automated pre-column derivatision in the injection needle of the autosampler using o-phthalaldehyde/ethanethiol reagent in combination with 9-fluorenylmethyl chloroformate. The calculated mean limit of detection and limit of quantification of pure amino acids were 2.3 and 4.6 μM, respectively. With this method, it was possible to accurately analyse the amino acid composition of bovine serum albumin, soy meal, Jatropha press cake, and cyanophycin. Mean reproducibility of all amino acids from bovine serum albumin was 6.8 %, with a mean recovery of 95 %. The sample run time is 16 min with a total cycle time from injection to injection of an acid hydrolyzed sample of 22 min, resulting in a greener method due to a reduction in solvent consumption.     

Graphene Reinforced Hollow Fiber Liquid Phase Microextraction for the Enrichment of some Phenylurea Residues in Milk Sample

Graphene, as a kind of novel and interesting carbon material, has gained much attention in recent years. In this paper, a new sample preparation technique, graphene reinforced hollow fiber liquid phase microextraction (G-HF-LPME), was developed and used to pre-concentrate some phenylurea herbicides (chlortoluron, isoproturon, diuron, monolinuron, and buturon) in milk sample prior to high-performance liquid chromatography–ultraviolet detection. Different parameters influencing the extraction efficiency of the G-HF-LPME were investigated and optimized. Under the optimized conditions, a good linearity was observed in the range between 10.0 and 400.0 μg L^?1 with the correlation coefficients ranging from 0.9911 to 0.9987. The limit of detection (S/N?=?3) of the method was lower than 2.0 μg L^?1. The developed method is simple, efficient, and has been successfully applied to the determination of the phenylureas in milk samples.     

Optimization of Sample Preparation in the Determination of Minerals and Trace Elements in Honey by ICP-MS

In this paper, analytical procedures are proposed for determination of inorganic constituents in honey samples from different regions of Brazil. Inductively coupled plasma with mass spectrometry detection (ICP-MS) was used to determine the analytes, using two different sample preparation methods: acid mineralization in block digester and microwave-assisted acid digestion. The methods were optimized in order to minimize the final acidity and the residual carbon content after the sample preparation. It was observed that mineralization using microwave radiation with 2 mol L^?1 HNO₃ was the most suitable method for determination of minerals and trace elements by ICP-MS. Besides, Se, Mg, Ca, Al, P, Mn, Fe, Cu, Zn, Ba, and Pb were determined in 60 honey samples by ICP-MS. The appropriate instrumental conditions were also evaluated for this determination, as the need of the use of collision–reaction interface and internal standards. The accuracies were evaluated using two certified reference materials, and the recoveries ranged from 82 to 115 %. The results showed no evidence of contamination in the honey samples analyzed.     

Silica Gel Chemically Modified with Ionic Liquid as Novel Sorbent for Solid-Phase Extraction and Preconcentration of Lead from Beer and Tea Drink Samples Followed by Flame Atomic Absorption Spectrometric Determination

Lead is a harmful metal element that has aroused considerable concern; therefore, it is of great importance to develop sensitive and reliable analytical techniques for the precise monitoring of lead in various foodstuffs. In the present study, an enrichment and separation procedure for lead via its solid-phase extraction as dithizone chelate on an ionic liquid 1,3-di(n-butyl) imidazolium hexafluorophosphate [DnBIM][PF₆]-chemically modified silica gel has been established prior to its flame atomic absorption spectrometric determination. The parameters that affect the extraction recovery of lead was investigated, including sample pH, dithizone concentration, eluent type and volume, and flow rate of sample and eluent. The analytical performance of the method was evaluated. Under the optimized conditions (sample pH, 8.0; dithizone concentration, 0.0005 % (w/v); eluent, 2 mL of 1.0 mol/L HNO₃; sample flow rate, 3 mL/min; eluent flow rate, 0.5 mL/min), the limit of detection was 0.36 μg/L (3σ, n?=?7), and the relative standard deviation was 3.5 % (c?=?5.0 μg/L, n?=?7). The proposed method was successfully applied to the determination of trace lead in beer and tea drink, and the recoveries for the spiked samples were in the range of 97.3–102.5 %.     

Development of a Nanobody-Based Competitive Dot ELISA for Visual Screening of Ochratoxin A in Cereals

A polyvinylidene fluoride membrane-based dot immunoassay using nanobody (Nb) for rapid, qualitative, and visual detection of ochratoxin A (OTA) in cereals was developed. On the basis of optimal assay conditions, the cut-off level of this method assessed visually was 5 μg/kg for OTA, and the final results were obtained within 20 min. This method was simple with no time-consuming cleanup procedure. Good accuracy and reproducibility were obtained in recovery experiments. Results of the Nb-based dot ELISA are in agreement with the ELISA kit, except for samples that were negative for OTA presence assessed through Nb-based dot ELISA but found positive through the ELISA kit. These results indicated that the developed method could be a useful on-site screening tool for rapid detection of OTA in cereals without special instrument.

Open image in new window

Graphic Abstract Flow chart of nanobody-based dot ELISA for OTA visual screening

     

Reduced Graphene Oxide-Modified Screen-Printed Carbon (rGO-SPCE)-Based Disposable Electrochemical Sensor for Sensitive and Selective Determination of Ethyl Carbamate

Ethyl carbamate (EC), a multi-site genotoxic carcinogen, exists in fermented food and beverages. However, the existing analytical methods need precise instrument, complex sample pretreatment, time-consuming, and high cost. Therefore, a disposable electrochemical biomimetic sensor was developed for fast and selective detection of EC based on reduced graphene oxide/screen-printed carbon composite electrode (rGO/SPCE). Firstly, the SPCE is modified with rGO by electrodeposition process that increased current signal and decreased the impedance of contact interface. Secondly, the OAP/rGO/SPCE biomimetic sensor was synthesized through electropolymerization by cyclic voltammograms in mixed solution of template of EC and monomer of O-aminophenol (OAP). The sensor specifically bound to EC quickly without sample pretreatment. A linear range was from 100 to 1300 nM, and a detection limit of 37 nM was achieved. The detection time is less than 5 min. The sensor possesses advantages include good chemical and mechanical stability, simplicity, low cost of preparation, and sensitive and label-free determination.

Open image in new window

Graphical abstract Schematic diagram of preparation of rGO-SPCE based sensor