Microfluidic Paper-Based Device Incorporated with Silica Nanoparticles for Iodide Quantification in Marine Source Dietary Supplements.

Iodine is an essential micronutrient for humans due to its fundamental role in the biosynthesis of thyroid hormones. As a key parameter to assess health conditions, iodine intake needs to be monitored to ascertain and prevent iodine deficiency. Iodine is available from various food sources (such as seaweed, fish, and seafood, among others) and dietary supplements (multivitamins or mineral supplements). In this work, a microfluidic paper-based analytical device (µPAD) to quantify iodide in seaweed and dietary supplements is described. The developed µPAD is a small microfluidic device that emerges as quite relevant in terms of its analytical capacity. The quantification of iodide is based on the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by hydrogen peroxide in the presence of iodine, which acts as the catalyst to produce the blue form of TMB. Additionally, powder silica was used to intensify and uniformize the colour of the obtained product. Following optimization, the developed µPAD enabled iodide quantification within the range of 10-100 µM, with a detection limit of 3 µM, and was successfully applied to seaweeds and dietary supplements. The device represents a valuable tool for point-of-care analysis, can be used by untrained personnel at home, and is easily disposable, low-cost, and user-friendly.

Construction of an electrochemical sensing platform for the sensitive determination of chlorogenic acid in locally consumed bitter coffee known as Mirra.

The demand for foods with high antioxidant capacity has increased and research on food analysis continues to increase. Chlorogenic acid is a potent antioxidant molecule and can exhibit various physiological activities. This study aims to analyze Mirra coffee for the determination of chlorogenic acid using an adsorptive voltammetric method. The method is based on the strong synergistic effect between carbon nanotubes and nanoparticles of gadolinium oxide and tungsten, providing sensitive determination of chlorogenic acid. The proposed method yielded a dynamic linear range of 2.5 × 10-9 âˆ¼ 1.6 × 10-6 M with a detection limit of 1.08 × 10-9 M for chlorogenic acid. The amount of chlorogenic acid in Mirra coffee was found to be 46.1 ± 0.69 mg/L by the proposed electrochemical platform.

Passion fruit-inspired dendritic mesoporous silica nanospheres-enriched quantum dots coupled with magnetism-controllable aptasensor enable sensitive detection of ochratoxin A in food products.

Ochratoxin A (OTA) is a powerful mycotoxin present in a variety of food products, and its detection is important for human health. Here, a fluorescent aptasensor is reported for sensitive OTA determination. Specifically, the surface of bio-inspired passion fruit-like dendritic mesoporous silica nanospheres-enriched quantum dots (MSNQs-apt) was first modified with the OTA aptamer as the recognition unit and fluorescence emitter, while the aptamer-complementary DNA (MNPs-cDNA) was linked with the magnetic nanoparticles (MNPs) as the separation element. In the range of 2.56 pg/mL to 8 ng/mL, the proposed aptasensor exhibited satisfactory linearity and a detection limit of 1.402 pg/mL. The developed aptasensor achieved recoveries of 90.98-103.20% and 94.33-107.57 % in red wine and wheat flour samples, respectively. By simply replacing the aptamer, this aptasensor can be easily extended to detection of other analytes, suggesting its potential as a universal detection platform for mycotoxins in food products.

Development of a responsive probe for colorimetric and fluorescent detection of bisulfite in food and animal serum samples in 100% aqueous solution.

Bisulfite (HSO3-) has the functions of bleaching, antiseptic, antioxidant, inhibiting bacterial growth, and controlling enzymatic reactions in food. However, long-term consumption of foods containing excessive amounts of bisulfite can be harmful to health. In addition, large doses of sulfur dioxide (SO2) can cause diarrhea, hypotension, allergic and asthmatic reactions in susceptible individuals. Therefore, it is urgent and essential to explore some rapid, reliable, and convenient tools to detect HSO3- in food and SO2 gas. Herein, we exploited a fluorescent probe, NPO, to detect HSO3- in 100 % aqueous solution. The probe has the advantages of easy synthesis, excellent water solubility, significant colorimetric change, good selectivity, high sensitivity, and fast response (within 1 min). Probe NPO was successfully applied for testing strips to visualize the behavior of HSO3- and SO2 gas. Moreover, the probe has been used to monitor the behavior of HSO3- in real food samples and animal serum samples.

Reliable Quantification of Ultratrace Selenium in Food, Beverages, and Water Samples by Cloud Point Extraction and Spectrometric Analysis.

Selenium is a trace element essential for the proper functioning of human body. Since it can only be obtained through our diet, knowing its concentrations in different food products is of particular importance. The measurement of selenium content in complex food matrices has traditionally been a challenge due to the very low concentrations involved. Some of the difficulties may arise from the abundance of various compounds, which are additionally present in examined material at different concentration levels. The solution to this problem is the efficient separation/preconcentration of selenium from the analyzed matrix, followed by its reliable quantification. This review offers an insight into cloud point extraction, a separation technique that is often used in conjunction with spectrometric analysis. The method allows for collecting information on selenium levels in waters of different complexity (drinking water, river and lake waters), beverages (wine, juices), and a broad range of food (cereals, legumes, fresh fruits and vegetables, tea, mushrooms, nuts, etc.).

Ultrasound-assisted deep eutectic solvent-based liquid-liquid microextraction for simultaneous determination of Ni (II) and Zn (II) in food samples.

A new approach was developed for the simultaneous pre-concentration and determination of Ni (II) and Zn (II) in food samples. This method is based on ultrasound-assisted liquid-liquid micro extraction using hydrophobic deep eutectic solvent (DES) and 1,10-phenanthroline as chelating agent. The effect of several parameters, such as pH, selection and volume of DES, amount of chelating agent, time of sonication and centrifugation, was studied. Under optimized conditions, the developed procedure offered exceptional sensitivity and linearity. The limit of detection was approximately 0.029 µg/Kg and 1.5 µg/Kg for Ni (II) and Zn (II), respectively. The proposed method was applied for the pre-concentration and determination of Ni (II) and Zn (II) in hydrogenated edible oils, fishes, and milk samples. The results of this study were compared with reported methods in the literature revealing its advantages.

Speciation and determination of inorganic selenium species in certain fish and food samples by gold-coated W-coil atom trap hydride generation atomic absorption spectrometry.

A very sensitive, selective, rapid and easy gas-phase preconcentration based method is presented for the determination and speciation of inorganic selenium in chicken meat, poultry eggs, mullet fish (Mugil Cephalus) and sea bass fish (Dicentrarchus Labrax) samples. Gold-coated W-coil atom trap was used to increase the sensitivity of conventional HG-AAS. LOD and LOQ values were calculated to be 0.021 µg/L and 0.070 µg/L, respectively. RSD% was found as 3.24. The sensitivity was increased 20 times more with the method used in the current study than the HG-AAS method. The interference effects of other metals on Se signal were significantly reduced by trap. SEM and EDX images of both bare and gold coated W-coil atom trap were screened. In order to check the accuracy of the method, "DOLT-5: Dogfish Liver" standard reference material was used and there was a good agreement between certified and found values at the 95% confidence level.

Magnetic dispersive micro-solid phase extraction coupled with dispersive liquid-liquid microextraction followed by graphite furnace atomic absorption spectrometry for quantification of Se(IV) and Se(VI) in food samples.

In this work, magnetic dispersive micro-solid phase extraction (MDMSPE) coupled with dispersive liquid-liquid microextraction (DLLME) was developed for Se(IV) and Se(VI) followed by graphite furnace atomic absorption spectrometry. MDMSPE involved the use of magnetic ZnFe2O4 nanotubes for adsorbing Se(VI). The sorbent was isolated from aqueous phase by using an external magnetic field instead of tedious centrifugation or filtration. In the following step, Se(IV) in the upper aqueous phase of MDMSPE was enriched by DLLME. Samples were prepared with artificial gastric juice to avoid the inter-conversion of target species. The main factors affecting the determination of the analytes were studied in detail. the detection limits of this method were 1.0 and 1.3 pg mL-1 for Se(IV) and Se(VI) with relative standard deviations of 4.6% and 5.1% (c = 1.0 ng mL-1, n = 9), respectively. An enrichment factor of 200 was obtained. This method was used for the detection of Se(IV) and Se(VI) in food samples without any pre-oxidation or pre-reduction operation. A certified reference material of milk powder was analysed by this method, and the determined values were in good agreement with the certified values. Recoveries of spike experiments were in the range of 91.0-107%.

A simple and green ultrasound liquid-liquid microextraction method based on low viscous hydrophobic deep eutectic solvent for the preconcentration and separation of selenium in water and food samples prior to HG-AAS detection.

A simple and green ultrasound liquid-liquid microextraction method based on low viscous hydrophobic deep eutectic solvent (ULLME-LV-HDES) was proposed for the preconcentration and separation of selenium prior to HG-AAS detection. Six different DESs were prepared for the extraction of selenium. Quercetin was used complexing agent for Se(IV) ions. Various analytical parameters such as pH, quercetin amount, DES type and its volume, sonication time, sample volume were optimized. Tolerance limits of anion, cation and transition metal ions were studied. Preconcentration and enhancement factor were found 62.5 and 121. Under the optimum conditions, limit of detection was found 0.25 ng L-1 with calibration range of 0.8-120 ng L-1. Relative standard deviation was found 3.2%. The accuracy of the method was confirmed with certified reference materials (NIST 1567a Wheat flour and NIST 1548a Typical diet). Finally, the developed method was successfully applied to food and water samples.

Rational Development of a New Reaction-Based Ratiometric Fluorescent Probe with a Large Stokes Shift for Selective Detection of Bisulfite in Tap Water, Real Food Samples, Onion Tissues, and Zebrafish.

Bisulfite (HSO3-) is usually widely added to tap water and food because it has antibacterial, bleaching, and antioxidant effects. However, its abnormal addition would cause a series of serious diseases related to it. Therefore, development of an effective method for HSO3- detection was of great significance to human health. In this work, a new reaction-based ratiometric fluorescent probe KQ-SO2 was rationally designed, which could be used for the highly selective detection of HSO3- in tap water, real food samples, onion tissues, and zebrafish. Specifically, a positively charged benzo[e]indolium moiety and a carbazole group through a condensation reaction resulted in KQ-SO2, which displayed two well-resolved emission bands separated by 225 nm, fast response (1 min), and high selectivity and sensitivity toward HSO3- upon undergoing the Michael addition reaction, as well as low cytotoxicity in vitro. In addition, KQ-SO2 has been successfully applied for the detection of HSO3- in tap water, real food samples, onion tissues, and zebrafish with satisfactory results. We predict that KQ-SO2 could be used as a powerful tool to reveal the relationship between HSO3- and the human health.

Development and validation of an UHPLC-qTOF-MS method for the quantification of cyclic polyesters oligomers in pasta by applying a modified QuEChERS clean-up.

An Ultra High-Performance Liquid chromatography method quadruple time-of-flight mass spectrometry has been developed for the analysis of 11 cyclic polyesters oligomers, following a modified QuEChERS clean-up with alumina/primary secondary amine, in pasta. Target analytes were polyethylene terephthalate (PET) 1st series cyclic dimer to heptamer, polybutylene terephthalate (PBT) dimer to pentamer and a polyurethane oligomer. Standard addition method was applied for the calibration, and the limits of quantification ranged from 3.2 to 17.2 ng g-1. Recoveries ranged from 86.4 to 109.8%, RSDs were lower than 12% for all analytes, and matrix effect never exceeded ± 2.5%. The method was successfully applied to real commercial pasta samples, where the PET 1st series cyclic trimer was the most abundant oligomer, being found in all tested samples. The 1st series PET cyclic dimer and tetramer, as well as 1,4,7-trioxacyclotridecane-8,13-dione, were found in considerable amounts. Traces of the 2nd and 3rd series PET cyclic dimers were also found.

Determination of trace levels of selenium in natural water, agriculture soil and food samples by vortex assisted liquid-liquid microextraction method: Multivariate techniques.

A green vortex assisted based liquid-liquid microextraction (VA-LLME) method was developed for preconcentration of selenium. Ammonium pyrrolidine dithiocarbamate (APDC) was used to form a hydrophobic complex with selenium in natural water, agricultural soil and food samples by GFAAS. Whereas Triton X-114, a nonionic surfactant and 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid were used for Se extraction as a dispersing medium. The conical flasks contents were shack on a vortex mixer to increase the extraction efficiency. Multivariate techniques were used to evaluate extraction parameters; pH, vortex time, APDC amount, volume of ionic liquid and Triton X-114 and centrifugation rate on the recovery of Se. The central composite design (CCD) was used for further optimization of the essential extraction parameters. The enhancement factor and limit of detection were obtained as 98.7 and 0.07 µg L-1. The certified reference materials was used for accuracy of method and the related standard deviation was found to be 3.51%. The resulted data indicated that concentrations of Se in all types of water samples were below the permissible limit recommended by WHO.

Multi-element determination in some foods and beverages using silica gel modified with 1-phenylthiosemicarbazide.

1-Phenylthiosemicarbazide bonded modified silica gel (PTC-SG) was synthesised and characterised by FTIR, SEM and elemental analysis for a novel separation/preconcentration of multiple elements based on solid phase extraction. The analytical parameters including pH of solutions, amounts of PTC-SG, flow rates of sample, eluent type and sample volume were optimised. The adsorption capacities of PTC-SG were found to be 7.9, 6.4, 6.3, 8.3, 7.2, 8.9 and 6.6 mg/g for Cu(II), Cd(II), Pb(II), Co(II), Cr(III), Ni(II) and Mn(II), respectively. The limit of detection (LOD) was calculated as 3x the standard deviation(s) of the reagent blank (k = 3, N = 21) and the LOD values were obtained to be 0.98 µg L-1 (Cu), 0.65 µg L-1 (Cd), 0.57 µg L-1 (Pb), 1.12 µg L-1 (Co), 1.82 µL-1 (Cr), 1.67 µg L-1 (Ni) and 0.55 µg L-1 (Mn). Certified reference materials were used to test the validation of the present method. The new solid phase extraction method was successfully applied to determination of the amount of multiple elements in food and beverage samples.

Nanomolar level sensing of glucose in food samples using glucose oxidase confined MWCNT-Inulin-TiO2 bio-nanocomposite.

Development of an effective sensor for sensing glucose in commercially available "sugar free" food products is important as people are becoming diabetic health conscious. Although multi-walled carbon nanotubes (MWCNTs) possess interesting electrical properties, their hydrophobic nature limits their applications. Their hydrophilicity can be improved through modification. In the present study, Inulin, that was isolated from Allium sativum L. using hot water diffusion and incorporated with titanium dioxide (TiO2), was used for the modification of MWCNTs. The as-synthesized MWCNT-Inulin-TiO2 bio-nanocomposite immobilized with glucose oxidase (GOx) was incorporated into the carbon paste matrix and was utilized for the sensing of glucose in food products. Differential pulse voltammetric studies revealed that the fabricated electrode demonstrated good linear range (1.6 nM to 1 µM) and was sensitive to nanomolar concentrations of glucose with a very low limit of detection up to 0.82 nM and exhibited a long term stability of 150 days.

A newly synthesized graft copolymer for magnetic solid phase microextraction of total selenium and its electrothermal atomic absorption spectrometric determination in food and water samples.

A newly synthesized polystyrene-g-polyoleic acid-g-polyethylene glycol graft copolymer (PoleS-PEG) was used as adsorbent in the solid phase microextraction of selenium ions by using electrothermal atomic absorption spectrometry (ETAAS). Neodymium magnet was used for separation of analyte ions. Various analytical parameters such as pH, adsorbent amount, mixing time, eluent solution, sample volume, etc. were optimized. The matrix effects of some cations and anions were also studied. The capacity of the adsorbent was found 11.5 mg g-1. The preconcentration factor was found to be 50. The detection limit (LOD) and quantification limit (LOQ) were found 6.06 ng L-1 and 20 ng L-1, respectively. The calibration curve was linear in the range of 0.02-4.0 µg L-1. Relative standard deviation was found 3.2%. The accuracy of the method was provided by using standard reference materials. The optimized method was successfully applied to natural water and food samples.

Nitrogen and phosphorus dual-doped carbon dots as a label-free sensor for Curcumin determination in real sample and cellular imaging.

A nitrogen and phosphorus dual-doped carbon dots (NP-Cdots) was fastly synthesized with glucose as the carbon source, 1,2-ethylenediamine as N-dopant and concentrated phosphoric acid as P-dopant. The as-synthesized NP-Cdots was utilized as a label-free sensor for determination of Curcumin (Cur). The proposed NP-Cdots-based fluorescence sensor was applied for sensitive detection of Cur in aqueous solution, achieving a linear range of 0.5-20 µmol/L and a detection limit of 58 nmol/L (21.37 ng/mL). The common amino acids and other drugs do not interfere with the detection of Cur, providing good selectivity. The constructed sensor was successfully applied to the determination of Cur in drinking water and the food samples with satisfactory results and the RSDs and recoveries were 0.08-5.39% and 95.2-105.2%, respectively. More importantly, the as-prepared NP-Cdots was used as effective fluorescent agent for cellular imaging without noticeable cytotoxicity. The proposed sensor is simple and practical, illustrating that the potential application of NP-Cdots for biosensing, food monitoring and cellular labeling and imaging.

Intellectual modifying a bare glassy carbon electrode to fabricate a novel and ultrasensitive electrochemical biosensor: Application to determination of acrylamide in food samples.

Acrylamide (AA) is a neurotoxin and carcinogen which is mainly formed in foods containing large quantities of starch processed at high temperatures and its determination is very important to control the quality of foods. In this work, a novel electrochemical biosensor based on hemoglobin-dimethyldioctadecylammonium bromide (HG-DDAB)/platinum-gold-palladium three metallic alloy nanoparticles (PtAuPd NPs)/chitosan-1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Ch-IL)/multiwalled carbon nanotubes-IL (MWCNTs-IL)/glassy carbon electrode (GCE) is proposed for ultrasensitive determination of AA in food samples. Development of the biosensor is based on forming an adduct by the reaction of AA with α-NH2 group of N-terminal valine of HG which decreases the peak current of HG-Fe+3 reduction. The modifications were characterized by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), energy dispersive X-ray spectroscopic (EDS) and scanning electron microscopy (SEM). Under optimized conditions, the biosensor detected AA by square wave voltammetry (SWV) in two linear concentration ranges of 0.03-39.0nM and 39.0-150.0nM with a limit of detection (LOD) of 0.01nM. The biosensor was able to selective detection of AA even in the presence of high concentrations of common interferents which confirmed that the biosensor is highly selective. Also, the results obtained from further studies confirmed that the proposed biosensor has a short response time (less than 8s), good sensitivity, long term stability, repeatability, and reproducibility. Finally, the proposed biosensor was successfully applied to determine AA in potato chips and its results were comparable to those obtained by gas chromatography-mass spectrometry (GC-MS) as reference method.

A simple and sensitive vortex-assisted ionic liquid-dispersive microextraction and spectrophotometric determination of selenium in food samples.

In the present study, a novel and eco-friendly vortex-assisted ionic liquid-based microextraction method was developed for the determination of selenium in food. The microextraction method is based on the liberation of iodine in the presence of selenium; the liberated iodine reacts with I- to form I3-. Anionic I3- reacts with cationic crystal violet dye, and the product is extracted into 1-hexyl-3-methylimidazolium hexafluorophosphate phase in the presence of Triton X-114. The proposed method is linear in the range of 2.0-70µgL-1 and has a detection limit of 9.8×10-2µgL-1. Relative standard deviations were 3.67% and 2.89% for the five replicate measurements of 14 and 35µgL-1 Se(IV), respectively. The proposed method was successfully applied to different food samples (NIST SRM 2976 mussel tissue, pepper, ginger, wheat flour, red lentil, traditional soup, cornflour, cornstarch, and garlic) after microwave digestion.

Method Development for the Determination of Total Fluorine in Foods by Tandem Inductively Coupled Plasma Mass Spectrometry with a Mass-Shift Strategy.

A method for total F determination in food and tea samples based on a mass-shift strategy using tandem inductively coupled plasma quadrupole mass spectrometry (ICP-MS-MS) was developed. This method consists of four steps: (1) conversion of the hardly ionized F atoms to BaF+ via ICP, (2) use of the first quadrupole (Q1, set at 157) to ensure only the m/z 157 ions (i.e., 138Ba19F+, 157Gd+, and 138Ba18OH+) enter the reaction cell (RC), (3) shifting 138Ba19F+ to a new mass 138Ba19F(14NH3)3+ by reacting with NH3 in RC to avoid the interfering ions (i.e., 157Gd+ and 138Ba18OH+), and (4) passing interference-free 138Ba19F(14NH3)3+ to the second quadrupole (Q2, set at 208) for detection by the MS detector. The mass-shift process of the target F (in ICP and RC) expected to follow the path: F + 138Ba+ → 157BaF+ + 3NH3 → 208BaF(NH3)3+, while the reaction pathway of dominant 157Gd+ in RC proposed to 157Gd+ + NH3 → 157Gd14N1H+ + nNH3 → 157Gd14N1H(14N1H3)n+ (n = 0-5). Under the optimized setting of tandem MS (Q1 → Q2 = 157 → 208) and RC reaction gas flow rate (NH3/He = 10:90, 8.0 mL min-1), the background equivalent concentrations (BECs) and limits of detection (LODs) were 0.021 and 0.022 µg mL-1, respectively. The calibration curve was linear in the range between 0.1 and 10 µg mL-1, with a correlation coefficient of R2 = 0.9999. The results obtained for 14 different food-related standard reference materials (SRMs) were in good agreement with the certified values on a 95% confidence level. The proposed method was then employed to evaluate the F contents of 13 branded tea samples. The total F concentrations ranged from 39.2 to 93.2 µg g-1. The tea infusions contained F between 23.5 and 85.4 µg g-1, with an extraction efficiency of 56.0-91.6%, and the water-soluble F contents of a Pu'er brick tea were 58.7, 21.4, 3.82, and 1.41 µg g-1 for filtrates 1, 2, 3, and 4, respectively.

Magnetic/non-magnetic argan press cake nanocellulose for the selective extraction of sudan dyes in food samples prior to the determination by capillary liquid chromatograpy.

Two methods for the determination of Sudan dyes (Sudan I, Sudan II, Sudan III and Sudan IV) in food samples, by solid phase extraction - capillary liquid chromatography, are proposed. Both methods use nanocellulose (NC) extracted from bleached argan press cake (APC), as a nano-adsorbent recycled from an agricultural waste material. One of the methods involves the dispersion of NC in food sample extracts, along with the waste and eluents being separated by centrifugation. In the other method, NC was modified by magnetic iron nanoparticles before using it in the extraction of Sudan dyes. The use of a magnetic component in the extraction process allows magnetic separation to replace the centrifugation step in a convenient and economical way. The two proposed methods allows the determination of Sudan dye amounts at the 0.25-2.00µgL-1 concentration range. The limit of detections, limit of quantifications and standard deviations achieved were lower than 0.1µgL-1, 0.20µgL-1 and 3.46% respectively, when using NC as a nano-adsorbent, and lower than 0.07µgL-1, 0.23µgL-1 and 2.62%, respectively, with the magnetic nanocellulose (MNC) was used. Both methods were applied to the determination of Sudan dyes in barbeque and ketchup sauce samples, obtaining recoveries between 93.4% and 109.6%.