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.).

Purity of Olive Oil Commercially Available in Poland.

The aim of this study was to examine olive oils purchased in Poland for their compliance with label declarations and EEC criteria. Statistical analysis was used to compare the olive oils in terms of their content and composition of essential constituents and color parameters. Fifty olive oils (extra virgin, bioextra virgin, cold-pressed, refined, and pomace) from different countries (Spain, Italy, Greece, Portugal, Germany, France, Israel, and the European Union), were purchased commercially in Poland. The contents of triacylglycerols, sterols, and tocopherols, the fatty acid composition, and the color parameters were determined using chromatographic and spectrophotometric methods. Statistical methods were used to divide the olive oils into clusters. Our results show that the composition and color parameters of olive oils available commercially in Poland, excluding pomace olive oils, are similar. It can thus be concluded that, irrespective of the type of olive oil stated on the label, their quality is the same or very similar.

An Exploratory Approach to Deriving Nutrition Information of Restaurant Food from Crowdsourced Food Images: Case of Hartford.

Deep learning models can recognize the food item in an image and derive their nutrition information, including calories, macronutrients (carbohydrates, fats, and proteins), and micronutrients (vitamins and minerals). This technology has yet to be implemented for the nutrition assessment of restaurant food. In this paper, we crowdsource 15,908 food images of 470 restaurants in the Greater Hartford region on Tripadvisor and Google Place. These food images are loaded into a proprietary deep learning model (Calorie Mama) for nutrition assessment. We employ manual coding to validate the model accuracy based on the Food and Nutrient Database for Dietary Studies. The derived nutrition information is visualized at both the restaurant level and the census tract level. The deep learning model achieves 75.1% accuracy when compared with manual coding. It has more accurate labels for ethnic foods but cannot identify portion sizes, certain food items (e.g., specialty burgers and salads), and multiple food items in an image. The restaurant nutrition (RN) index is further proposed based on the derived nutrition information. By identifying the nutrition information of restaurant food through crowdsourced food images and a deep learning model, the study provides a pilot approach for large-scale nutrition assessment of the community food environment.

Utilizing AgNPt-SALDI to Classify Edible Oils by Multivariate Statistics of Triacylglycerol Profile.

Edible oils are valuable sources of nutrients, and their classification is necessary to ensure high quality, which is essential to food safety. This study reports the establishment of a rapid and straightforward SALDI-TOF MS platform used to detect triacylglycerol (TAG) in various edible oils. Silver nanoplates (AgNPts) were used to optimize the SALDI samples for high sensitivity and reproducibility of TAG signals. TAG fingerprints were combined with multivariate statistics to identify the critical features of edible oil discrimination. Eleven various edible oils were discriminated using principal component analysis (PCA). The results suggested the creation of a robust platform that can examine food adulteration and food fraud, potentially ensuring high-quality foods and agricultural products.

Is the Magnesium Content in Food Supplements Consistent with the Manufacturers' Declarations?

Food supplements (FS) are gaining more and more popularity because they are a quick way to compensate for deficiencies in the diet. Due to their affordable price and easy-to-take form, they are eaten by all age groups and by healthy and sick people. There are many categories of this type of preparations on the market, and FS with magnesium (Mg) are some of the most commonly used. Therefore, the aim of the study was to determine the Mg content in FS and to compare the estimated value with that declared by the manufacturer. The study included 116 FS containing Mg. In order to determine the Mg content, the atomic absorption spectrometry (AAS) method was used. The tested FS were divided in terms of the declared content, pharmaceutical form, chemical form of Mg, composition complexity, and price. It was shown that in the case of 58.7% of the samples, the Mg content was different than the permissible tolerance limits set by the Polish chief sanitary inspectorate, which range from -20% to +45%. It has been estimated that as a result of the differences in the content, the patient may take up to 304% more Mg per day or 98% less than it is stated in the declaration. The above results indicate that the quality and safety of FS should be more closely monitored.

[Detection of Residual Solvents in Commercial Supplements Using Headspace (HS)-GC-MS].

In order to understand the actual state of residual solvents contained in commercial supplements, we performed a simultaneous analysis of residual solvents by headspace (HS)-GC-MS with reference to the Japanese Pharmacopoeia's "Residual Solvents", for 29 products selected from among commercial supplements (e.g., revitalizers, weight loss pills) that are deeply colored or contain coating agents and extract powder. As a result, benzene (class 1) was detected in eight black-colored supplements, and hexane (class 2B) was also detected in one of those products. On the other hand, methanol (class 2A) was detected in four products containing coating agents and extract powders, such as citrus peel extract. None of these residual solvents exceeded the concentration limits set by the Japanese Pharmacopoeia. Benzene was detected at 1.7 µg/g, which was near the concentration limit, in some products. As raw materials used for the manufacture of the black-colored supplements from which benzene was detected commonly included activated carbon, we analyzed the residual solvents contained in activated carbon commercially available for use as food additive and in food production and medicine. As a result, benzene was detected at high concentrations in activated carbon made from hemp (approximately 29 µg/g) and bamboo (approximately 140 µg/g).

Rapid Assessment of Quality Changes in French Fries during Deep-frying Based on FTIR Spectroscopy Combined with Artificial Neural Network.

Fourier transform infrared (FTIR) spectroscopy combined with backpropagation artificial neural network (BP-ANN) were utilized for rapid and simultaneous assessment of the lipid oxidation indices in French fries. The conventional indexes (i.e. total polar compounds, oxidized triacylglycerol polymerized products, oxidized triacylglycerol monomers, triacylglycerol hydrolysis products, and acid value), and FTIR absorbance intensity in French fries were determined during the deep-frying process, and the results showed the French fries had better quality in palm oil, followed by sunflower oil, rapeseed oil and soybean oil. The FTIR spectra of oil extracted from French fries were correlated to the reference oxidation indexes determined by AOCS standard methods. The results of BP-ANN prediction showed that the model based on FTIR fitted well (R2 > 0.926, RMSEC < 0.481) compared with partial least-squares model (R2 > 0.876). This facile strategy with excellent performance has great potential for rapid characterization quality of French fries during frying.

Edible Oils Adulteration: A Review on Regulatory Compliance and Its Detection Technologies.

Various events of edible oils adulteration with inferior ingredients were reported regularly in recent years. This review is aimed to provide an overview of edible oils adulteration practices, regulatory compliance and detection technologies. Many detection technologies for edible oils adulteration were developed in the past such as methods that are based on chromatography or spectroscopy. Electrochemical sensors like electric nose and tongue are also gaining popularity in the detection of adulterated virgin olive oil and virgin coconut oil. It can be concluded that these detection technologies are essential in the combat with food adulterers and can be improved.

A Graded Approach for Evaluating Health Claims about Plant-Based Food Supplements: Application of a Case Study Methodology.

The implementation of REGULATION (EC) No 1924/2006 has led to the formation of a list of health claims that can be used in food supplements (EU 432/2012). However, such supplements are often composed of plant preparations with claims omitted from this list. The peculiarity of plants is related to their long history of use, that could allow claims based on traditionally recognized health effects. In addition, the scientific literature has been enriched over the years through clinical studies that have assessed the bioavailability and efficacy of bioactive components, and investigated their mechanisms of action. Based on existing recognized models which aim to classify research according to the level of scientific evidence, Synadiet developed a three-grade model (A, B or C) for assessing plants health claims. In this paper, the applicability of the model is illustrated through an example for which a Grade B health claim attesting the possible contribution of red clover isoflavones to the improvement of blood lipid levels in postmenopausal women has been attributed. The model appears able to be easily extrapolated to claims pertaining to other plants. If adopted by consensus at European level, this model could initiate the implementation of a positive list of health claims on plant preparations.

Quality chemical analysis of crush-tear-curl (CTC) black tea from different geographical regions based on UHPLC-Orbitrap-MS.

Crush-tear-curl (CTC) black tea is a popular beverage, owing to its unique taste characteristics and health benefits. However, differences in the taste quality and chemical profiles of CTC black tea from different geographical regions remain unclear. In this study, 28 CTC black tea samples were collected from six geographical regions and analyzed using electronic tongue and ultrahigh performance liquid chromatography-Orbitrap-mass spectroscopy. The e-tongue analysis indicated that each region's CTC black tea has its own relatively prominent taste characteristics: Sri Lanka (more umami and astringent), North India (more umami), China (more sweetness and astringent), South India (moderate umami and sweetness), and Kenya (moderate umami and astringent). Based on multivariate statistical analysis, 78 metabolites were tentatively identified and used as potential markers for CTC black tea of different origins, mainly including amino acids, flavone/flavonol glycosides, and pigments. Different metabolites, which contributed to the taste characteristics of CTC black tea, were clarified by partial least squares regression correlation analysis. Our findings may serve as useful references for future studies on origin traceability and quality characteristic determination of CTC black teas. PRACTICAL APPLICATION: This study provides useful references for future studies on the origin traceability and taste characteristic determination of CTC black teas from different geographical regions.

[Determination of nine ginsenosides in health foods by solid extraction phase-ultra performance liquid chromatography-tandem mass spectrometry].

Ginsenosides are the main active compounds of ginseng, American ginseng and Panax notoginseng. They have certain pharmacological effects on the cardiovascular, immune and central nervous systems. Most ginsenosides are naturally classified as protopanaxatriol (PPT), protopanaxadiol (PPD), and oleanolic acid (OA) according to their aglycone skeletons. The nine main ginsenosides are Rb1, Rb2, Rb3, Rc, Rd, Re, Rf, Rg1 and Rg2. Accurate quantification of ginsenosides is imperative because they are the characteristic components and quality evaluation indicators of health foods. A new method based on solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry (SPE-UPLC-MS/MS) was developed for the determination of the nine ginsenosides in health foods. First, the pretreatment conditions were optimized. With the aim of purifying the samples and removing impurities, SPE cartridges with different packing materials, such as Alumina-N/XAD-2 SPE Cartridge, C18 and HLB were investigated. Based on the purification efficiencies, recoveries and other factors, the Alumina-N/XAD-2 SPE cartridge composite SPE column was selected as the pretreatment purification column. The eluents were then optimized. When water was used as the eluent, the ginsenosides could remain adsorbed on the SPE column, and could not be eluted down with other water-soluble substances. By increasing the proportion of ethanol in the eluent, the ginsenoside adsorbed on the filler of the SPE column could be gradually eluted. When the proportion of ethanol in the eluent reached 70%, the ginsenosides could be completely eluted. The effects of different volumes of 70% ethanol elution solvent (5-30 mL) on the extraction efficiencies of ginsenosides were also investigated. The results showed that when the volume of the elution solvent reached 20 mL, the ginsenosides were completely eluted. Then, the chromatographic conditions and MS parameters were optimized. By examining the ionization cracking of ginsenosides, the quasi-molecular ions and corresponding fragment ions in ginsenoside primary MS were determined. After optimizing the chromatographic conditions and MS parameters, not only the sensitivity of the method was improved, but also the isomers Rb2, Rb3 and Rc with the same quasi-molecular ions and the corresponding fragment ions were completely separated. Good separation was achieved for the nine ginsenosides, thus meeting the requirements for accurate quantification. Finally, chromatographic separation was achieved on a Hypersil Gold C18 column (100 mm×2.1 mm, 1.9 µm) under linear gradient elution using a 5 mmol/L ammonium acetate solution (with 0.1% formic acid) and acetonitrile as the mobile phases. The nine ginsenosides were detected using a triple quadrupole MS detector under ESI - and multiple reaction monitoring (MRM) modes, and quantified by the external standard method. The nine ginsenosides showed a strong positive linear correlation (r 2>0.9950) in the range of 0.005-0.5 µg/mL. The sample recoveries and the corresponding relative standard deviations (RSDs) were 81.1%-114.2% and 0.4%-8.0% (n=6), respectively. Eleven batches of health foods on the market, among which six batches contained ginseng, American ginseng or Panax notoginseng ingredients, were analyzed by the developed method, and the ginsenosides were detected. The total ginsenosides contents were close to those mentioned on the label. However, the nine ginsenosides were detected in one batch of health food, whose label did not indicated ginseng, American ginseng or Panax notoginseng. The nine ginsenosides were not detected in the remaining batches of health foods.The health food extract was directly loaded and purified without any complex pretreatment. The UPLC⁃MS/MS method, not only helped shorten the analysis time, but also accurate quantification of low ginsenoside contents in complex matrix samples. The developed method is simple and rapid, with high throughput, thus being suitable for the quantitative analysis of the nine ginsenosides in health foods.

Pyrrolizidine alkaloids in tea, herbal tea and iced tea beverages- survey and transfer rates.

The transfer rate of 37 pyrrolizidine alkaloids (PA) found in ten naturally contaminated teas and herbal teas to their brews was studied in detail. Mixed herbal, peppermint, red bush, senna, black tea and green tea infusions were prepared according to the ISO guide and vendor's instructions, respectively, and parameters like herb-to-water ratio, steeping time and multiple extractions studied. In general, a transfer rate of 38-100% (median 95%) for brews following vendor's instructions was determined. The total concentration range of PA in these ten samples was 154-2412 ng/g (median 422 ng/g) in the herb and for single analytes 0.1-170 ng/g. Seven of the 37 PA occurred unexpectedly; these were tentatively identified and quantified by liquid chromatography-high resolution mass spectrometry (LC-HR-MS), since their contributions to total PA-content matter. Additionally, 46 iced tea beverages were analysed for their PA-load, determined to be in the range 0-631 ng/L (median 40 ng/L). The applied solid-phase extraction (SPE) clean-up turned out to be capable of separating PA in the free base pyrrolizidine alkaloids (PAFB) and their N-oxides (PANO) in a two-step elution, which was a valuable tool to support identification of unexpected PA. Further, atropine was found in 50% of the ten tea herb samples (range: 1-4 ng/g) and in 13% of the iced tea beverage samples (range: 2-65 ng/L).

Characterization of Glucuronosyl-diacyl/monoacylglycerols and Discovery of Their Acylated Derivatives in Tomato Lipid Extracts by Reversed-Phase Liquid Chromatography with Electrospray Ionization and Tandem Mass Spectrometry.

Glucuronic acid containing diacylglycerols (3-(O-α-d-glucuronopyranosyl)-1,2-diacyl-sn-glycerols, GlcA-DAG) are glycolipids of plant membranes especially formed under phosphate-depletion conditions. An analytical approach for the structural characterization of GlcA-DAG in red ripe tomato (Solanum lycopersicum L.) extracts, based on reversed-phase liquid chromatography (RPLC) coupled with electrospray ionization (ESI) and tandem mass spectrometry (MS/MS) using a linear ion trap, is described in this paper. At least 14 GlcA-DAG (R1/R2) species, including four regioisomers, containing three predominant fatty acyl chains C16:0, C18:2, and C18:3, were identified for the first time. Moreover, 29 GlcA-DAG acylated on the glucuronosyl ring (acyl-R3 GlcA-DAG) were discovered, alongside 15 acylated lyso-forms, i.e., acylated 3-(O-α-d-glucuronosyl)monoacylglycerols, abbreviated as acyl-R3 GlcA-MAG (R1/0) or (0/R2). Although many of these acylated lyso-forms were isomeric with GlcA-DAG (i.e., acyl chains with equivalent sum composition), they were successfully separated by reversed-phase liquid chromatography (RPLC) using a solid-core C18 column packed with 2.6 µm particle size. Tandem MS (and eventually MS3) data obtained from sodium adducts ([M + Na]+) and deprotonated molecules ([M - H]-) were fundamental to detect diagnostic product ions related to the glucuronosyl ring and then determine the identity of all investigated glycolipids, especially to recognize the acyl chain linked to the ring. A classification of GlcA-MAG, GlcA-DAG, and acylated GlcA-DAG and GlcA-MAG was generated by an in house-built database. The discovery of acylated derivatives emphasized the already surprising heterogeneity of glucuronic acid-containing mono- and diacylglycerols in tomato plants, stimulating interesting questions on the role played by these glycolipids.

Special Issue: NMR-Based Metabolomics.

Nuclear magnetic resonance (NMR) spectroscopy remains one of the core analytical platforms for metabolomics, providing complementary chemical information to others, such as mass spectrometry, and offering particular advantages in some areas of research on account of its inherent robustness, reproducibility, and phenomenal dynamic range [...].

Rapid detection of Chinese-specific peony seed oil by using confocal Raman spectroscopy and chemometrics.

Peony seed oil (PSO) is a new woody nut oil which is unique to China. Its unsaturated fatty acids are over 90% and are rich in α - linolenic acid. Although the PSO industry is in its infancy, it is bound to become a top vegetable oil food material because of its own advantages. The potential high commercial profit of its adulteration with cheap vegetable oil will be an important factor hindering the healthy development of PSO industry. It is of great significance to study the adulteration of PSO for preventing large-scale adulteration. In this study, the qualitative and quantitative analysis of PSO was realised based on Raman spectroscopy combined with chemometrics analysis, and the fatty acid composition of PSO was analysed according to Raman characteristic peaks. The technology can be applied to routine analysis and quality control of PSO.

Comparative evaluation of different methods for determining phytochemicals and antioxidant activity in products containing betalains - Verification of beetroot samples.

This study presents methods that can be used to assess the health quality of products containing betalains. The paper compares and verifies data on the phytochemical composition of three different pigmented beetroot cultivars using spectrophotometric, HPLC-DAD, HPTLC and LC-Q-Orbitrap-HRMS techniques. Additionally, we compared the total antioxidant activity in both the cell-free and cellular systems. Betalain contribution to antioxidant activity was also determined using post-column derivatization and it was found that in the case of red beetroot it is about 50%. Photometric measurements are recommended for a simple and inexpensive analysis of the total betacyanin and betaxanthin content. Liquid chromatography techniques produced more precise information on phytochemical composition in the tested samples. The combination of liquid chromatography with high-resolution mass spectrometry produced the largest amount of quantitative and qualitative data; in beetroot samples sixty-four phytochemicals have been identified therefore, this approach is recommended for more detailed metabolomics studies.

Combined Effect of Impregnation with an Origanum vulgare Infusion and Osmotic Treatment on the Shelf Life and Quality of Chilled Chicken Fillets.

The scope of this work is the study of a combined process including a dipping step into an oregano (Origanum vulgare ssp. hirtum) infusion (OV) followed by osmotic treatment of chicken fillets at 15 °C. Chicken fillets were immersed in an osmotic solution consisting of 40% glycerol and 5% NaCl with (OV/OD) and without (OD) prior antioxidant enrichment in a hypotonic oregano solution. A comparative shelf life study of all the samples (untreated, OD and OV/OD treated) was then conducted at 4 °C in order to assess the impact of this process on the quality and shelf life of chilled chicken fillets. Microbial growth, lipid oxidation and color/texture changes were measured throughout the chilled storage period. Rates of microbial growth of pretreated fillets were significantly reduced, mainly as a result of water activity decrease (OD step). Rancidity development closely related to off odors and sensory rejection was greatly inhibited in treated fillets owing to both inhibitory factors (OD and OV), with water-soluble phenols (OV step) exhibiting the main antioxidant effect. Shelf life of treated chicken fillets exhibited a more than three-fold increase as compared to the untreated samples based on both chemical and microbial spoilage indices, maintaining a positive and pleasant sensory profile throughout the storage period examined.

Determination of selenite and selenomethionine in kefir grains by reversed-phase high-performance liquid chromatography-inductively coupled plasma-optical emission spectrometry.

A new and efficient reversed-phase high-performance liquid chromatography-inductively coupled plasma-optical emission spectrometry method was developed for the simultaneous separation and determination of SeO3 2- and seleno-dl-methionine in kefir grains. For the system, limits of detection and quantitation values for SeO3 2- and seleno-dl-methionine were calculated as 0.52/1.73 mg/kg (as Se) and 0.26/0.87 mg/kg (as Se), respectively. After performing the system analytical performance, recovery experiment was done for kefir grains and percent recovery results for SeO3 2- and seleno-dl-methionine were calculated as 98.4 ± 0.8% and 93.6 ± 1.0%, respectively. It followed by the feeding studies that the kefir grains were exposed to three different concentrations of SeO3 2- (20, 30, and 50 mg/kg) for approximately 4 days at room temperature to investigate the conversion/non-conversion of SeO3 2- to seleno-dl-methionine. Next, the fed grains were extracted with tetramethylammonium hydroxide pentahydrate solution (20%, w/w) and then sent to the developed system. There was no detectable seleno-dl-methionine found in fed kefir grains at different concentrations of SeO3 2- while inorganic or elemental selenium in the fed kefir grains was determined between 1579.5 - 3116.0 mg/kg (as Se). Selenium species in the kefir grains samples was found in the form of SeO3 2- proved by using an anion exchange column.

Improved quantification method of crocins in saffron extract using HPLC-DAD after qualification by HPLC-DAD-MS.

Crocins in commercial liquid saffron extracts (Saffr'activ®) were identified using high-performance liquid chromatography (HPLC) with a diode array detector (DAD) and mass spectrometry (MS). The impact of storage on the qualities of the saffron extract were studied with HPLC-DAD-MS by exposing trans-4-GG crocin to environmental factors. Light and temperature induced degradation after only one week. Trans-4-GG crocin was totally hydrolyzed when stored at 60 °C and exposed to light. A quick and reliable method using HPLC-DAD was then developed to improve quantification of crocins in commercial liquid saffron extracts. An internal standard quantification method that uses a response factor, corrected with the molecular weight of each crocin, improved results for old saffron extracts.

Biofortification quality in bananas monitored by energy-dispersive X-ray fluorescence and chemometrics.

Biofortification is a nutritional strategy used to enhance nutrients in a variety of staple foods. As bananas and plantains (Musa spp.) are considered staple food in many developing countries, monitoring zinc (Zn) content in biofortified bananas is crucial to ensure this mineral intake. Bananas were biofortified by injecting Zn sulfate heptahydrate (ZnSO4·7H2O) solutions into banana trees' pseudostem (1%, 2%, and 4%) compared with the control treatment. Zinc content was estimated using energy-dispersive X-ray fluorescence (EDXRF) and multivariate calibration using partial least squares (PLS). The impressive result is the possibility of high throughput analysis of Zn in bananas after biofortification to guarantee the quality when eaten as a central portion of the diet.