Simultaneous Determination of Cyclamate,Acesulfame, and Aspartame in Beverages by Titania-Based RP-HPLC

This paper aims at establishing a rapid method for simultaneous separation and determination of the sweeteners including cyclamate, acesulfame, and aspartame in beverages by titania-based reversed-phase high-performance liquid chromatography. The chromatographic conditions were as follows: a titania Sachtopore-RP C18 column (250?×?4.6 mm; 5 μm) as a separation column, a mixture of water and methanol at a volume ratio of 95:5 containing 1.0 % phosphate acid used as mobile phase, flow rate of 1.0 mL min^?1, and the detection wavelength was 205 nm. The linear ranges of cyclamate and aspartame were 0.02–8.0 mg mL^?1 with limits of detection (LODs) of 16.35 and 19.56 μg mL^?1, respectively, and their limits of quantitation (LOQs) were 55.50 and 68.50 μg mL^?1, respectively. The recoveries of cyclamate were between 93.52 and 103.54 %. The recoveries of aspartame were between 93.31 and 102.63 %. The linear range of acesulfame was 0.125–50 μg mL^?1 with LOD of 0.08 μg mL^?1 and LOQ of 0.25 μg mL^?1. The recoveries of acesulfame were between 94.34 and 103.21 %. Relative standard deviation (n?=?8) for all determinations was less than 0.72 %.     

Tocopherols and Tocotrienols: an Adapted Methodology by UHPLC/MS Without Sample Pretreatment Steps

Ultra high-performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC/ESI/MS) methodology was adapted for identification and quantification of tocopherols and tocotrienols in vegetable oils with no derivatization or sample preparation steps. The UHPLC analysis was performed using a C18 column and mobile phase composed of methanol: water: ammonium hydroxide (99:1:0.1 v/v/v) and isopropanol. A single mass spectrometer with electrospray on negative mode was used as a detector for tocopherols and tocotrienols. The samples were diluted in isopropanol. The limit of quantification for tocopherols was 0.006 μg mL^?1, and the linear range was 0.006 to 0.01 μg mL^?1; for tocotrienols, the limit of quantification was 0.002 μg mL^?1, and the linear range of analysis was 0.002 to 0.003 μg mL^?1. The correlation coefficients were higher than 0.99, indicating that the method has suitable linearity. The methodology has proven to be precise, reproducible, and robust for the parameters studied.     

Validation of a LC–MS Method for the Determination of Urea Contamination in Market Teas

Tea is one of the most widely consumed beverages in the world preceded only by water. In some culture style of tea plant, urea fertilizer is sprayed on tea leaf in order to increase crop output; besides, in some processing method of green tea, urea is illegally added to maintain tea’s vivid color. The above-mentioned process may unavoidably cause urea residue, and prolonged or repeated exposure of body to urea may cause adverse effects. In this work, an easy and reliable hydrophilic interaction liquid chromatography/mass spectrometry analytical method for determination of urea in tea was firstly validated; the method exhibited a linear response from 4 to 60 μg mL^?1 (R ²?>?0.9996), the limit of quantitation for urea is 4 μg mL^?1, the mean recoveries of urea spiked at levels of 10 and 20 μg mL^?1 were 95–110 %, and the relative standard deviations of intra- and inter-day measurements were less than 7.8 %. The method was later successfully applied to the analysis of urea residue in some market tea samples. The result showed that there is obvious urea contamination in some market teas, and the contamination percentage is especially high in green tea samples. Among the samples investigated, urea was detected at concentration ranges of 24.02–46.02 mg/kg. Some attention should be paid on the health effect resulting from such urea contamination in tea.     

Development of a Headspace-Solid Phase Microextraction-Gas Chromatography/Mass Spectrometry (HS-SPME-GC/MS) Method for the Determination of Benzene in Soft Drinks

A method based on headspace-solid phase microextraction and gas chromatography with mass spectrometry has been developed and validated for the determination of benzene in soft drinks. The extraction step was optimized using a rotatable central composite design including the following experimental variables: extraction temperature, extraction time, sample weight, and salt concentration. The optimized procedure, which was carried out at 30 °C during 30 min by using a 75 μm carboxen-polydimethylsiloxane fiber, showed good linearity within the concentration range 0–25 μg?kg^?1 (r ² ?>?0.999), mean recoveries from 97.5 to 103.1 %, and coefficients of variation from 1.5 to 13.4 % for repeatability and from 1.5 to 15.7 % for within-laboratory reproducibility. Limits of detection and quantification were calculated at 0.02 and 0.08 μg?kg^?1, respectively. The method was applied to determine the concentrations of benzene in 77 samples of beverages from the Brazilian market. Levels from <0.08 to 10.84 μg?kg^?1 were obtained, which are comparable to those verified in other countries. Most of the samples (72.2 %) contained benzene up to 1 μg?kg^?1.     

3-Monochloro-1,2-propandiol (3-MCPD) in soy sauce from the Bulgarian market

The 3-monochloro-1,2-propandiol (3-MCPD) levels in soy sauces which contained hydrolysed vegetable protein were evaluated for the Bulgarian market. For analysis of 3-MCPD, a gas chromatography–mass spectrometry (GC-MS) method was applied with a linear range of 0.03–2.00 μg mL^?1 and a limit of detection (LOD) of 2.3 μg kg^?1 and a limit of quantification (LOQ) of 3.4 μg kg^?1. At these levels, the standard deviation was 5.1%, with recoveries between 81% and 102%. The method was applied to the analysis of 21 samples of soy sauce from the Bulgarian market. Results ranged from 3.7 to 185.6 μg kg^?1. Soy sauces produced from hydrolysed soy protein contained higher levels of 3-MCPD than naturally fermented sauces. In 38.4% of samples of Bulgarian origin, the 3-MCPD content was above the EU limit of 20 μg kg^?1. In all analysed samples, 33.3% had a 3-MCPD content above the EU limit.     

Development of a Competitive Indirect Enzyme-Linked Immunosorbent Assay for Screening Phenylethanolamine A Residues in Pork Samples

Phenylethanolamine A (PEA), a new alternative β-agonist, has been illegally used in farming to promote the muscle growth in food-producing animals. In this study, a sensitive and convenient competitive indirect enzyme-linked immunosorbent assay (ciELISA) was developed for determination of PEA residues in pork samples. The produced antibody was highly specific to PEA and exhibited a negligible cross-reactivity toward some other β-agonists. The developed technique was characterized by the limit of detection below 0.08 μg kg^?1 and the IC₅₀ value of 0.93 pmol mL^?1 (0.32 ng mL^?1). Validation of the technique was done using artificially spiked and naturally contaminated pork samples. The recoveries ranged from 79.6 to 112.6 % for the samples spiked at levels of 0.1–5 μg kg^?1 with the variation coefficients below 15 %. The analysis of naturally contaminated samples showed that the obtained data corresponded with the data obtained by the LC-MS/MS. The developed ciELISA was shown to be a feasible highly sensitive and specific screening tool for PEA residue analysis.     

Comparison of HPLC Separation of Phenylalanine Enantiomers on Different Types of Chiral Stationary Phases

HPLC separation of phenylalanine by using chiral stationary phases (CSPs) with chiral selectors β-cyclodextrin, isopropylcarbamate cyclofructan 6, teicoplanin, and ristocetin were studied. The effects of mobile phase composition and column temperature from 0 to 30 °C on the retention and resolution of enantiomers were investigated. β-cyclodextrin and isopropylcarbamate cyclofructan 6 CSPs showed chiral recognition in normal phase separation mode. The sufficient enantioseparations (resolution values 1.59 and 2.75) were reached using teicoplanin and ristocetin-based stationary phases at 23 °C in reversed-phase mode with mobile phases consist of acetonitrile and water at ratios 75/25 and 60/40 (v/v), respectively. Chiral HPLC system coupled with circular dichroism and polarimetry detector could be used to determine enantiomeric elution order. The optimized and validated HPLC-UV method with teicoplanin-based chiral stationary phase was applied for determination of phenylalanine in real samples. Both of the enantiomeric forms were detected in samples of dietary supplements and L-phenylalanine in samples of energy drinks. Obtained recoveries were higher than 82% with an RSD less than 10%. The HPLC method showed good linearity (correlation coefficients >?0.998) in concentration range 0.1–500 μg mL^?1. The limit of detection was 0.1 μg mL^?1 for both enantiomers.     

A deep eutectic solvent based liquid phase microextraction for the determination of caffeine in Turkish coffee samples by HPLC-UV

ABSTRACT

A novel liquid-phase microextraction procedure for the determination and extraction of caffeine using a deep eutectic solvent based liquid-phase microextraction method (DES-LPME) was developed. A deep eutectic solvent consisting of choline chloride-phenol (1:3) and tetrahydrofuran as a dilution solvent were used for the extraction of caffeine from Turkish coffee samples. The quantitative recoveries were obtained when the DES volume was 400 µL, and the volume of tetrahydrofuran that was used as an emulsifier solvent was 800 µL. The limit of detection and the limit of quantification were found to be 0.12 and 0.40 µg mL^?1, respectively. Linear dynamic range was 0.5–100 µg mL^?1, and coefficient of determination (R²) was 0.9998. The relative standard deviation (RSD) was 2.20% when the standard solution concentration was 1.0 µg mL^?1. The fact that the determination coefficient obtained from the calibration curve was greater than 0.9998 gives information about the accuracy of the method. Also, in order to determine the accuracy of the developed method, selected coffee samples were spiked with 25 and 50 µg mL^?1 caffeine.     

A Novel Method for Bisphenol A Analysis in Dairy Products Using Graphene as an Adsorbent for Solid Phase Extraction Followed by Ion Chromatography

A novel and reliable ion chromatography (IC) method using graphene (G) as a solid phase extraction (SPE) adsorbent for the rapid analysis of bisphenol A (BPA) in dairy products was developed. The performances of graphene (G) and commercial C18 for BPA extraction from dairy samples were evaluated; results showed that G had higher adsorption efficiency. IC coupled with an electrochemical detector (ED) is eco-friendly, labor and time saving compared to liquid chromatography mass spectrometry (LC-MS) and gas chromatography mass spectrometry (GC-MS). The effects of the experimental parameters of the IC-ED system were assessed, and the parameters were optimized to provide maximum sensitivity. The linear range is 5–20,000 ng?mL^?1 with an R value of 0.999. The limit of the detection is 0.8 ng?mL^?1 for a 25-μL injection loop. The mean relative recoveries ranged between 83.3 % and 104.6 %, the corresponding inter-day precision was below 5.3 % for 20, 200, 2,000, and 15,000 ng?mL^?1. This method was successfully employed to analyze BPA in dairy samples.     

Simultaneous Determination of Multiclass Pesticides and Antibiotics in Honey Samples Based on Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

A simple, fast, and efficient method was developed for simultaneous determination of 79 pesticides and 13 antibiotics compounds of different chemical classes of pesticides and antibiotics in honey samples by ultra-high performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS). The sample preparation procedure includes homogenization with McIlvaine buffer 0.1 mol L^?1 (pH 4), followed by extraction with acetonitrile and cleanup with florisil, using dispersive solid phase extraction (d-SPE). The proposed method was validated with good results, such as linearity (r ²?>?0.9901), normality, and independence of the evaluated data, as well as recoveries between 70 and 120 % with relative standard deviation (RSD) <20 % for most of the compounds spiked from 0.1 to 200 μg kg^?1. The experimental method limits of detection and quantification were from 0.03 to 1.51 μg kg^?1 and from 0.1 to 5 μg kg^?1, respectively, for the pesticides. For the antibiotics, the decision limits (0.1 to 2 μg g^?1) and the detection capacity (0.12 to 2.81 μg g^?1) were below the maximum residue limits (MRLs) established for honey by the Brazilian and European legislation. The method was successfully applied to real samples from different botanical and geographic origins. From them, 44 % presented residues from 0.12 to 10 μg kg^?1 of one or more analytes. The proposed method combines the advantages of a quick sample preparation step with the selectivity and sensitivity of the UHPLC-MS/MS and proved to be suitable for routine analyses.     

Application of High-Performance Liquid Chromatography with Diode Array Detector for Simultaneous Determination of 11 Synthetic Dyes in Selected Beverages and Foodstuffs

A simple, inexpensive and robust high-performance liquid chromatography diode array detector (HPC-DAD) procedures are proposed to analyse food dyes in beverages, hard candy and fish roe samples. An ether-linked phenyl stationary phase provides sufficient selectivity and chromatographic performance for separation of 11 sulfonated azo dyes. Beverage samples were only diluted (and degassed when needed) before analysis. Solid-phase extraction (SPE) or matrix solid-phase dispersion (MSPD) procedures are proposed for efficient extraction of the analytes from candies or fish roe samples, respectively. Limits of detection (LODs) were from 0.005 to 0.013 μg mL^?1 and limits of quantification (LOQs) between 0.014 and 0.038 μg mL^?1. HPLC-DAD method was validated in terms of intra- and inter-day accuracy and precision at three concentration levels 2, 1, and 0.1 μg mL^?1. Validation was also performed for SPE and MSPD extraction procedures including intra- and inter-day accuracy (Recovery %) and precision (RSD%), as well as intra-laboratory reproducibility. Application to analysis of beverages and food samples available to consumers proved that described methods are suitable for the routine analysis of dyes in food products.     

Simultaneous Determination of TBH<Subscript>2</Subscript>Q and BHA Antioxidants in Food Samples Using Eosin Y Film Modified Electrode

A glassy carbon electrode (GCE) was modified with eosin Y that was electrodeposited on GCE via continuous cycling between ??1.6 and 1.5 V (vs Ag/AgCl). This electrode was characterized by scanning electron microscopy and electrochemical impedance spectra. The resulting electrode exhibited excellent electrocatalytic activity toward the oxidation of butylated hydroxyanisole (BHA) and tert-butyl hydroquinone (TBH₂Q); in addition, the oxidation products of BHA and TBH₂Q were found to be the same, which was studied by CV and in situ FT-IR spectroelectrochemistry. Under the optimized condition, the oxidation peak currents were linear to BHA/TBH₂Q in the range from 0.10 to 7.00 μg mL^?1 with the detection limits of 0.01 μg mL^?1 (S/N?=?3) for BHA and 0.015 μg mL^?1 (S/N?=?3) for TBH₂Q, respectively. Moreover, the reproducibility and repeatability of the electrode were determined. The proposed method was successfully applied in the simultaneous determination of BHA and TBH₂Q in several edible oil samples, and satisfactory results when compared with those obtained using high-performance liquid chromatography.     

A Highly Sensitive Resonance Rayleigh Scattering Method for the Determination of Vitamin C Based on the Formation of Zirconium Hexacyanoferrate (II) Nanoparticles

In pH 2.55 HCl solution, vitamin C (VC) could deoxidize [Fe(CN)₆]^3? producing [Fe(CN)₆]^4?, which reacted with Zr (IV) to form Zr[Fe(CN)₆] complex, then aggregated to produce {Zr[Fe(CN)6]}_n nanoparticles by virtue of hydrophobic force and van der Waals force. The intensity of RRS at 340 nm is directly proportional to the concentration of VC in the range of 0.1–1.45 μg mL^?1, and the detection limit (3 s/k) is 0.128 ng mL^?1. In this work, the spectral characteristics of RRS, the optimum condition, the reaction mechanism of the reaction, and their influencing factors especially the effect of organic solvent have been studied. The sensitive, rapid, and simple method based on resonance Rayleigh scattering was successfully applied to determine trace amount VC in VC injection and tablet.     

Preconcentration and Simultaneous Analysis of Benzimidazole Anthelmintics in Milk Samples by Ultrasound-Assisted Surfactant-Enhanced Emulsification Microextraction and High-Performance Liquid Chromatography

The proposed ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) coupled with high-performance liquid chromatography-photodiode array detection (HPLC-PDA) has been developed for the preconcentration and simultaneous analysis of five benzimidazole anthelmintics. Dichloromethane (extraction solvent) and Triton X-114 (emulsifier) was used for extraction of the target analytes. The parameters affecting the extraction efficiency were investigated and optimized. Under the optimum conditions, linearity was in the range from 10 to 150 μg?L^?1 with good coefficients of determination (R ²) higher than 0.994. Preconcentration factors were obtained up to 60, corresponding to limits of detection range of 1.8???3.6 μg?L^?1. Intra-day (n?=?5) and inter-day (n?=?4?×?3) precisions were obtained with relative standard deviation of retention time and peak area below 0.8 and 9.2 %, respectively. Good recoveries for the spiked target anthelmintics at different concentrations (e.g., 20, 50, and 100 μg?L^?1) of milk samples were obtained in 72.5–113.5 %. The results demonstrated that the proposed UASEME-HPLC-PDA can be used as an alternative powerful method for the simultaneous determination of the target analytes in milk samples.     

Determination of Chloramphenicol in Honey, Shrimp, and Poultry Meat with Liquid Chromatography–Mass Spectrometry: Validation of the Method According to Commission Decision 2002/657/EC

Chloramphenicol (CAP) is an antibiotic used for the treatment of bacterial infections in human and veterinary medicine. The use of CAP was prohibited in the European Union in 1994. Control laboratories are required to use suitably validated analytical methods to check sample compliance with the regulation. A quantitative method based on liquid chromatography coupled to isotopic dilution tandem mass spectrometry was developed for the determination of chloramphenicol in honey, shrimp, and poultry meat. The experimental protocol consisted of a liquid–liquid extraction with ethyl acetate. Separation and detection were realized, respectively, by a 2690 Waters HPLC (Milford, MA, USA) and a Micromass Triple Quadrupole mass spectrometer (Micromass, Manchester, UK), equipped with an electrospray source. The effects of mobile-phase additives on the response of LC/ESI/MS were examined. Two different HPLC columns were tested: the X-Terra from Waters and the Alltima HP C18 HL from Alltech (Deerfield, IL, USA). A validation of the method was conducted according to the EU criteria for the analysis of chloramphenicol in foods. The decision limits (CCα) were 0.04, 0.03, 0.07 μg?kg^?1, and the detection capabilities (CCβ) were 0.05, 0.04, 0.08 μg?kg^?1 for honey, shrimp, and poultry meat, respectively. Those values are below the minimum required performance limit set at 0.3 μg?kg^?1 by the EU and 0.1 μg?kg^?1 by Belgium. Our protocol has the advantage to propose a unique extraction method working as well for honey, shrimp, and poultry meat, contrary to similar published methods in which a different extraction method is used for each type of matrix.     

Purification of Purple Sweet Potato Extract by Dead-End Filtration and Investigation of Membrane Fouling Mechanism

Pulsed ultrasound-assisted extraction with water was carried out to extract valuable compounds from purple sweet potato (PSP). Quality properties and dead-end filtration of PSP extract were investigated. Solutes concentration in PSP extract were 118.60?±?2.83, 599.8?±?8.28, and 0.72?±?0.03 μg mL^?1 for total protein, total polyphenol, and total anthocyanin, respectively. Filtration with PES 50 kDa membrane-augmented polyphenol purity from 83.4 % in extract to 99.6 %. A protein removal coefficient of 99 % was achieved. Resistance in series model and Hermia’s model was applied to quantify filtration resistance and investigate fouling mechanism during filtration. Gel layer resistance was the most important for all three used membranes (PES 0.1 μm, PES 100 kDa, and PES 50 kDa). Fitting of experimental data by Hermia’s model revealed that the most suitable fouling mechanism varied, cake layer model for PES 0.1 μm and PES 100 kDa membrane and intermediate blocking model for PES 50 kDa membrane. For the purpose of more efficient polyphenol production, advanced filtration modules, such as cross-flow and rotating disk filtration module, are expected.     

Simple Voltammetric Determination of Rhodamine B by Using the Glassy Carbon Electrode in Fruit Juice and Preserved Fruit

This paper reported an innovative simple voltammetric approach for determination of rhodamine B based on a glassy carbon electrode. Cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical behavior of rhodamine B. After optimizing the experimental conditions, the anodic peak current of rhodamine B was linear to its concentration in the range of 4.78–956.1 μg?L^?1, and the limit of detection was 2.93 μg?L^?1 in pH 4.0 buffer solution. The electrode showed good repeatability and acceptable selectivity. This method was successfully applied to the detection of rhodamine B in preserved fruit and fruit juice samples, which has shown good reliability.     

Development of vapor generation combined with potentiometric detection for determination of sulfite in beverages

This paper describes a simple, sensitive and cost effective method developed for determination of sulfite in beverages. The procedure is based on chemical vapor generation of hydrogen sulfide, collection of the vapor in an alkaline solution, and then potentiometric determination of the sulfide using a commercial sulfide selective electrode. The influential parameters on analytical performance such as concentration of reagents, flow rate of carrier gas, reaction temperature and gas collection time are evaluated and discussed. In the optimum conditions, the method was linear in the range of 2–25 μg mL^?1 of sulfite with a detection limit of 0.7 μg mL^?1. The relative standard deviation of the method was 1.2 % for five replicate experiments at 10 μg mL^?1 concentration level. The method was successfully applied for determination of sulfite in different beverages with the relative recoveries between 92.2 and 96.2 %. The proposed method can be applied for quality control and consumer safety in food and beverages industrial plants.     

Triple Quadrupole Mass Spectrometry with Liquid Chromatography and Dispersive Liquid-Liquid Microextraction for the Determination of Monoterpenes in Alcoholic Drinks

Five monoterpenes (linalool, geraniol, eugenol, carvacrol, and thymol) were directly preconcentrated from alcoholic drinks with no previous sample treatment step using a miniaturized technique based on dispersive liquid-liquid microextraction. Chloroform (300 μL) was rapidly injected into 8 mL of sample, while the addition of a disperser solvent was obviated because of the ethanol content of the alcoholic beverages. The enriched phase was evaporated, reconstituted in 50 μL water, and analyzed by reversed phase liquid chromatography with a mobile phase consisting of 25% acetonitrile (0.1% formic acid) and 75% water (0.1% formic acid) and tandem mass spectrometry with a triple quadrupole in the selected reaction monitoring mode. The matrix effect was evaluated, and quantification by the standard additions method is recommended. Limits of detection ranged from 0.003 to 1.5 ng mL^?1, depending on the compound and the matrix. Enrichment factors of between 12 and 88 were obtained. The method was validated through recovery tests, finding values in the 76–128% range. The intraday precision was lower than 20% in terms of relative standard deviation. Different types of alcoholic drinks were analyzed, monoterpenes being detected at concentrations from 0.4 to 627 ng mL^?1.     

Rapid Screening of Quinoxaline Antimicrobial Growth Promoters and Their Metabolites in Swine Liver by Indirect Competitive Enzyme-Linked Immunosorbent Assay

Quinoxaline feed additives are antimicrobial growth promoters (AGPs); use three of them is permitted, and two of them are illegally used. It results in residue of quinoxaline AGPs and their metabolites in edible animal tissues, which are potentially harmful to human health. In order to effectively monitor the multiple residues of them in swine liver, an indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) was developed based on polyclone antibody preparation. Protein conjugates were synthesized and immune to New Zealand white rabbit according to designed schemes. The effective antiserum with 50 % inhibiting concentration (IC₅₀) value of 1.34 μg?L^?1 was obtained. A new synthesized quinoxaline with similar chemical structure to olaquindox but longer spacer arm was used as coating antigen. Cross-reactivity of other four quinoxaline AGPs and their eight metabolites was tested; seven of them have cross-reactivity over 10 %, with IC₅₀ of 0.10–2.50 μg?L^?1. At the spike level of 1 to 100 μg?kg^?1 in swine liver, the recoveries of all compounds ranged from 80.14 % to 96.90 %, with the inter-day variation coefficient (CV) of 5.67–13.82 % and the intra-assay CV of 6.22–14.19 %. The limit of detection ranged from 0.03?±?0.002 to 0.79?±?0.05 μg?L^?1. Positive samples were determined by the ic-ELISA method and successfully confirmed by liquid chromatography-tandem mass spectrometry. The proposed ELISA is feasible for screening quinoxaline AGPs and their metabolites in swine liver.