Separations

Mycotoxins are a type of toxins harmful for not only animal but also human health. Cooccurrence of multi-mycotoxins could occur for food infected by several molds, producing multi-mycotoxins. It is necessary to develop corresponding determination methods, among which current mass spectrometry (MS) dominates. Currently, the accurate identification and quantitation of mycotoxins in complex matrices by MS with low resolution is still a challenge since false-positive results are typically obtained. Here, a method for the simultaneous determination of 23 mycotoxins in broiler tissues using ultra-high performance liquid chromatography-quadrupole/orbitrap HRMS was established. After the extraction by acetonitrile-water-formic acid (80:18:2, v/v/v), the purification by multifunctional purification solid phase extraction cartridges and the chromatographic separation on a C18 column, representative mycotoxins were determined by HRMS in full scan/data-dependent MS/MS acquisition mode. The quantitation was based on the external standard method. An MS/MS database of 23 mycotoxins was established to achieve qualitative screening and simultaneous quantification. Mycotoxins had a good linear relationship within a certain concentration range with correlation coefficients (r²) larger than 0.991 as well as the limit of quantitation of 1.80–300 μg/kg. The average recoveries at three different levels of low, medium and high fortification were 61–111% with relative standard deviations less than 13.5%. The method was fast, accurate, and suitable for the precise qualification of multiple mycotoxins in broiler tissues. 15 μg/kg zearalenone (ZEN) was detected in one liver sample among 30 samples from markets including chicken breast meat, liver, and gizzards. The result illustrated that the pollution of ZEN should not be neglected considering its harmful effect on the target organ of liver. Full article

Due to the increasing environmental awareness of the public, green chemistry has become an important element of environmental protection. In laboratories around the world, millions of analyses of inorganic and organic anions and cations in water and wastewater samples, and solid and gaseous samples are performed daily. Unfortunately, these activities still generate large costs, including environmental costs, which are related to the scale of the studies, the use of toxic chemical reagents, the waste generated, and the energy consumed. The methods used so far for inorganic ion analysis, including classical methods, are increasingly being replaced by instrumental methods, primarily based on ion chromatography. This paper presents the most important advantages and limitations of ion chromatography, and compares them with the costs of classical analyses for the analytes and sample types. Both the financial and environmental costs associated with the determination of common inorganic ions, such as Cl⁻, NO₂⁻, NO₃⁻, and NH₄⁺, in 1000 environmental samples, were compared using selected reference wet classical methods and ion chromatography. The advantages and limitations of ion chromatography that allow this separation technique to be classified as a green analytical chemistry method have been described herein. Full article

Sweat chloride analysis is one of the important approaches in cystic fibrosis diagnosis. The commonly used Macroduct method to acquire sweat samples is semi-invasive, time consuming and expensive. Furthermore, this method often fails to collect a sufficient amount of sweat in newborns due to the insufficient sweating rate. In this work, we present a novel, simple, 3D-printed sampling device that is used to collect sweat specimens completely noninvasively in less than one minute. The device has a flow-through channel adjacent to the skin surface, through which 500 µL of deionized water is flushed and the spontaneously formed sweat on the skin in the channel area is washed into a plastic vial. The developed skin-wash procedure is a single step operation, is completely noninvasive and it always produces a sweat specimen. The ions from the skin-wash are subsequently analyzed by capillary electrophoresis with contactless conductivity detection and selected ion ratio (Cl⁻/K⁺) or ((Cl⁻ + Na⁺)/K⁺) is used as a cut-off value to diagnose cystic fibrosis patients with sensitivity and specificity comparable to the conventional Macroduct method. Full article

This study investigated the potential of using the changes in polyphenol composition of red wine to enable a more comprehensive chemometric differentiation and suitable identification of authentication markers. Based on high performance liquid chromatography-mass spectrometry (HPLC-MS) data collected from Feteasca Neagra, Merlot, and Cabernet Sauvignon finished wines, phenolic profiles of relevant classes were investigated immediately after vinification (Stage 1), after three months (Stage 2) and six months (Stage 3) of storage, respectively. The data were subjected to multivariate analysis, and resulted in an initial vintage differentiation by principal component analysis (PCA), and variety grouping by canonical discriminant analysis (CDA). Based on polyphenol common biosynthesis route and on the PCA correlation matrix, additional descriptors were investigated. We observed that the inclusion of specific compositional ratios into the data matrix allowed for improved sample differentiation. We obtained simultaneous discrimination according to the considered oenological factors (variety, vintage, and geographical origin) as well as the respective clustering applied during the storage period. Subsequently, further discriminatory investigations to assign wine samples to their corresponding classes relied on partial least squares-discriminant analysis (PLS-DA); the classification models confirmed the clustering initially obtained by PCA. The benefits of the presented fingerprinting approach might justify its selection and warrant its potential as an applicable tool with improved authentication capabilities in red wines. Full article

Every human body is a source of a unique scent, which can be used for medical or forensic purposes. Human skin scent is a complex mixture of more or less volatile compounds with different chemical and physical properties, which often differ significantly in their concentrations. The most efficient technique for separating such complex samples is comprehensive two-dimensional gas chromatography (GC × GC). This work aimed to find the optimal arrangement of a two-dimensional chromatographic system and define a suitable chromatographic method for non-targeted analysis of human scent samples. Four different chromatographic columns (non-polar Rxi-5MS and TG-5HT, medium polar Rxi-17Sil MS and Rtx-200MS) and their different configurations were tested. The best system was the 30 m primary column Rtx-200MS (with the 2 m pre-column Rtx-200MS) and the 1 m secondary column TG-5HT in a reverse configuration. This system achieved the highest theoretical and conditional peak capacities, optimal resolution, and the lowest number of coelutions. Full article

Cannabis sativa L. seeds are rich in essential polyunsaturated fatty acids and highly digestible proteins, with a good nutritional value. Proteomics studies on hempseed reported so far have mainly been conducted on processed seeds and, to our knowledge, no optimization of protein extraction from hemp seeds has been performed. This study investigates the SDS-PAGE profile of hempseed proteins comparing different methods of extraction, (Osborne sequential extraction, TCA/acetone, MTBE/methanol, direct protein solubilization of defatted hempseed flour), two conditions to keep low temperature during seed grinding (liquid nitrogen or ice) and two solubilization buffers (urea-based or Laemmli buffer). Among the tested conditions, the combination of liquid nitrogen + TCA/acetone + Laemmli buffer was not compatible with SDS-PAGE of proteins. On the other hand, urea-based buffer achieved more reproducible results if combined with all the other conditions. TCA/acetone, MTBE/methanol, and direct protein solubilization of defatted hempseed flour demonstrated a good overview of protein content, but less abundant proteins were poorly represented. The Osborne sequential separation was helpful in diluting abundant proteins thus enhancing the method sensitivity. Full article

The traceability of typical foodstuffs is necessary to protect high quality of traditional products. It is well-known that several factors could influence metabolites content in certified foods, but soil composition, altitude, latitude and coded production protocols constitute the territorial conditions responsible for the peculiar organoleptic and nutritional properties of labelled foods. Instead, regardless of origin, seasonality, cultivar, collection year can affect all agricultural products, so it is appropriate to include them in data analysis in order to obtain a correct interpretation of the differences linked to growing areas alone. Therefore, it is useful to use a flexible all-round technique, and NMR spectroscopy coupled with multivariate statistical analysis is considered a powerful means of assessing food authenticity. The purpose of this review is to investigate the relevance of year, cultivar, and seasonal period in the determination of food geographical origin using NMR spectroscopy. The strategy for testing these three factors may differ from author to author, but a preliminary study of cultivar or collection year effects on NMR spectra is the most popular method before starting the geographical characterization of samples. In summary, based on the available literature, the most significant influence is due to cultivar, followed by harvesting year, however seasonality is not considered a source of variability in data analysis. Full article

A high percentage of the agricultural wells in the state of Sonora are overexploited, thus generating a significant degree of saline intrusion and abandonment by nearby communities. In this paper, the effect of temperature on the final concentration of diluted water was evaluated with variations in voltage and input concentration in a batch electrodialysis reversal (EDR) process in order to find the optimal operating conditions, with an emphasis on reducing the energy consumption and cost of desalinated water. Thirty-six samples were prepared: eighteen samples of 2000 mg/L total dissolved solids (TDS) and eighteen samples of 5000 mg/L TDS; brackish well water of 639 mg/L TDS and synthetic salt were mixed to obtain these concentrations. Three different temperatures (25, 30, and 35 °C) and two different voltages (10 and 20 V) were tested for each sample after evaluating the limiting current density. The best salt removal occurred in the 20 V sets, with 18.34% higher removal for the 2000 mg/L TDS experiments and 25.05% for the 5000 mg/L experiments (average between the 25 to 35 °C tests). The temperature positively affected the EDR, especially in the experiments at 10 V, where increasing by 10 °C increased the efficiency by 10.83% and 24.69% for 2000 and 5000 mg/L TDS, respectively. The energy consumption was lower with increasing temperature (35 °C), as it decreased by 1.405% and 1.613% for the 2000 and 5000 mg/L TDS concentrations, respectively (average between the 10 and 20 V tests), thus decreasing the cost per m³ of water. Full article

We report the first fabrication of sputtered carbon, solid-phase microextraction (SPME) fibers. These fibers have competitive extraction capabilities compared with the commercial carbon wide range (CWR) SPME fiber. This report also includes a demonstration of a newly developed SPME test mix that includes 15 different compounds with a wide range of functional groups and chemical properties. The fiber fabrication process involves sputtering carbon onto fused silica fibers, and the effects of throw distance on the morphology of the carbon coatings were studied. Four different carbon coating thicknesses were evaluated, with PDMS added as a stationary phase. These fibers were characterized with multiple analytical techniques, including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), water contact angle (WCA) goniometry, as well as headspace (HS) and direct immersion (DI)–SPME–GC–MS. The best (11.5 µm) sputtered carbon SPME fibers, with and without PDMS, were evaluated using the new evaluation mix and compared with the commercial CWR fiber and a previously sputtered/developed silicon fiber. The new probe mix helped elucidate differences among the fibers, which would have been missed by current commercial test mixes. The sputtered carbon SPME fibers showed similar functional group selectivity as commercial CWR fibers. However, the sputtered carbon fibers showed higher responses per volume compared with the commercial CWR fiber, indicating the porous morphology of the sputtered carbon has the ability to overcome large phase thickness/volume discrepancies and increase the relative recovery for various compounds. Full article

Growing consumer interest in hemp oilseed supplements requires quality control. Therefore, appropriate, effective and verified analytical methods are needed for the determination of some bioactive cannabinoids in them. The aim of the study is to present an extended (compared to our previous research) validated high performance liquid chromatography with diode array detection (HPLC-DAD) method for the determination of four cannabinoids (cannabidiol, cannabidiolic acid, cannabinol and delta-9-tetrahydrocannabinol) in an oil matrix, which was used to determine these cannabinoids in seven commercial hemp oil supplements. In our method, the isolation of the target compounds was based on liquid extraction with acetonitrile combined with the freezing (at −41 °C) of the oil phase. The results show that in some cases, the determined concentrations of cannabinoids in the tested supplements differ significantly from those declared by the manufacturers. As for the main medicinal cannabinoid (CBD) in hemp oil supplements, in two cases, the measured concentration was significantly lower (1.45 and 1.81%) than the declared (5 and 5%), and in the other supplements, the obtained results confirm the declared amount of CBD within the error range from 3.29 to 9.2%. Therefore, to ensure the safe and beneficial use of these supplements by consumers, it is necessary to monitor their cannabinoid composition. Full article

NanoMIPs that are prepared by solid phase synthesis have proven to be very versatile, but to date only limited attention has been paid to their use in solid phase extraction. Thus, since nanoMIPs show close similarities, in terms of binding behavior, to antibodies, it seems relevant to verify if it is possible to use them as mimics of the natural antibodies that are used in immunoextraction methods. As a proof-of-concept, we considered prepared nanoMIPs against fluoroquinolone ciprofloxacin. Several nanoMIPs were prepared in water with polymerization mixtures of different compositions. The polymer with the highest affinity towards ciprofloxacin was then grafted onto a solid support and used to set up a solid phase extraction–HPLC method with fluorescence detection, for the determination of fluoroquinolones in human urine. The method resulted in successful selection for the fluoroquinolone antibiotics, such that the nanoMIPs were suitable for direct extraction of the antibiotics from the urine samples at the µg mL⁻¹ level. They required no preliminary treatment, except for a 1 + 9 (v/v) dilution with a buffer of pH 4.5 and they had good analyte recovery rates; up to 85% with precision in the range of 3 to 4.5%, without interference from the matrix. These experimental results demonstrate, for the first time, the feasibility of the use of nanoMIPs to develop solid phase extraction methods. Full article

In this study, the manganese-doped manganese–cobalt–iron spinel was prepared by the sol–gel self-combustion method, and its physical and chemical properties were analyzed by XRD (X-ray diffraction analysis), SEM (scanning electron microscope), and VSM (vibrating sample magnetometer). The mercury removal performance of simulated flue gas was tested on a fixed bed experimental device, and the effects of Mn doping amount, fuel addition amount, reaction temperature, and flue gas composition on its mercury removal capacity were studied. The results showed that the best synthesized product was when the doping amount of Mn was the molar ratio of 0.5, and the average mercury removal efficiency was 87.5% within 120 min. Among the fuel rich, stoichiometric ratio, and fuel lean systems, the stoichiometric ratio system is most conductive to product synthesis, and the mercury removal performance of the obtained product was the best. Moreover, the removal ability of Hg⁰ was enhanced with the increase in temperature in the test temperature range, and both physical and chemical adsorption play key roles in the spinel adsorption of Hg⁰ in the medium temperature range. The addition of O₂ can promote the removal of Hg⁰ by adsorbent, but the continuous increase after the volume fraction reached 10% had little effect on the removal efficiency of Hg⁰. While SO₂ inhibited the removal of mercury by adsorbent, the higher the volume fraction, the more obvious the inhibition. In addition, in an oxygen-free environment, the addition of a small amount of HCl can promote the removal of mercury by adsorbent, but the addition of more HCl does not have a better promotion effect. Compared with other reported adsorbents, the adsorbent has better mercury removal performance and magnetic properties, and has a strong recycling performance. The removal efficiency of mercury can always be maintained above 85% in five cycles. Full article

In this study, a gum Arabic-magnetite nanocomposite (GA/MNPs) was synthesized using the solution method. The prepared nanocomposite was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and thermogravimetric analysis (TGA). The prepared composite was evaluated for the adsorption of lead(II) ions from aqueous solutions. The controlling factors such as pH, contact time, adsorbent dose, initial ion concentration, and temperature were investigated. The optimum adsorption conditions were found to be 0.3 g/50 mL, pH = 6.00, and contact time of 30 min. The experimental data well fitted the pseudo-second-order kinetic model and the Langmuir isotherm model. The maximum adsorption capacity was determined as 50.5 mg/g. Thermodynamic parameters were calculated postulating an endothermic and spontaneous process and a physio-sorption pathway. Full article

Background: The application of microorganisms as bioestimulants in order to increase the yield and/or quality of agricultural products is becoming a widely used practice in many countries. In this work, five plant growth-promoting rhizobacteria (PGPR), isolated from cultivated rice paddy soils, were selected for their plant growth-promoting capacities (e.g., auxin synthesis, chitinase activity, phosphate solubilisation and siderophores production). Two different tomato cultivars were inoculated, Tres Cantos and cherry. Plants were grown under greenhouse conditions and different phenotypic characteristics were analysed at the time of harvesting. Results: Tres Cantos plants inoculated with PGPR produced less biomass but larger fruits. However, the photosynthetic rate was barely affected. Several antioxidant activities were upregulated in these plants, and no oxidative damage in terms of lipid peroxidation was observed. Finally, ripe fruits accumulated less sugar but, interestingly, more lycopene. By contrast, inoculation of cherry plants with PGPR had no effect on biomass, although photosynthesis was slightly affected, and the productivity was similar to the control plants. In addition, antioxidant activities were downregulated and a higher lipid peroxidation was detected. However, neither sugar nor lycopene accumulation was altered. Conclusion: These results support the use of microorganisms isolated from agricultural soils as interesting tools to manipulate the level of important bioactive molecules in plants. However, this effect seems to be very specific, even at the variety level, and deeper analyses are necessary to assess their use for specific applications. Full article

Adenosine is a purine ribonucleoside with important roles in various physiological processes. A number of studies have indicated the importance of adenosine in cardiovascular diseases including syncope; however, the accurate determination of adenosine in human blood is challenging due to the molecule’s instability. In the present study, we report a simple method for the pre-treatment of blood samples and the development of a fast and efficient hydrophilic interaction chromatographic tandem mass spectrometry method for the analysis of adenosine in patient blood. During collection, samples were mixed directly with a solvent mixture containing 95% acetonitrile and 10 mM ammonium formate in a Vacutainer tube, resulting in successful prevention of adenosine metabolic processes and direct blood sample deproteinization. The method was validated according to bioanalytical industry guidelines and found to be accurate, repeatable, specific and sensitive with LLOQ 0.005 μg/mL, thus allowing its application in the analysis of real clinical samples. Full article

In the last few years, liquid chromatography coupled with mass spectrometry (LC/MS) has been increasingly used for screening purposes in forensic toxicology. These techniques have the advantages of low time/resource-consuming and high versatility and have been applied in numerous new multi-analytes methods. The new psychoactive substance (NPS) phenomenon provided a great impulse to this wide-range approach, but it is also important to keep the attention on “classical” psychoactive substances, such as benzodiazepines (BDZ). In this paper, a fully validated screening method in blood for the simultaneous detection of 163 substances (120 NPS and 43 other drugs) by a dynamic multiple reaction monitoring analysis through LC-MS/MS is described. The method consists of a deproteinization of 200 µL of blood with acetonitrile. The LC separation is achieved with a 100 mm long C18 column in 35 min. The method was very sensitive, with limits of quantification from 0.02 to 1.5 ng/mL. Matrix effects did not negatively affect the analytical sensitivity. This method proved to be reliable and was successfully applied to our routinary analytical activity in several forensic caseworks, allowing the identification and quantification of many BDZs and 3,4-methylenedioxypyrovalerone (MDPV). Full article

The aim of the work was to determine the degree of watermelon (Citrullus lanatus) thermostability according to the content of the present bioactive compounds and antioxidant properties. The watermelon samples were exposed to the following temperatures/time regimes: 40, 70, and 100 °C; 2, 5, and 15 min. The sample characteristics were monitored by spectrophotometric and chromatographic methods. Statistically significant (p < 0.05) differences were observed between the heat-treated samples compared to the heat-untreated control sample; differences were found almost between all samples. The total polyphenol content increased in all heat-treated samples. The highest total polyphenol content was observed among samples treated at 40 °C for 15 min (1.38 ± 0.01 mg/g). Lycopene content (measured by spectrophotometer) also increased in the same samples exposed to 40 °C for 5 min (65.45 ± 0.20 mg/kg), though higher temperatures (70 and 100 °C) resulted in lycopene degradation. Chromatographic method (measured by high-pressure liquid chromatography) showed lycopene degradation after each heating treatment. Not unambiguously, results and observations were not found in antioxidant activity due to oscillations in measured bioactive compounds. The obtained results emphasize processes in heat-treated watermelon, and they can be useful in the production of different products where this food commodity can be included. Full article

Liquid chromatography-tandem mass spectrometry (LC/MS/MS) is a more accurate technique for detecting proteins than electrophoresis-based methods such as western blotting. Because of its convenience, western blotting is commonly used for protein analysis in beef. We developed a method for detecting myosin light chain 3 (myl3) in beef samples, particularly dry-aged beef, using LC/MS/MS for quality testing. Musculus longissimus dorsi of Holstein was aged for 0, 2, 4, 5, 9, 11, 17, 20, and 24 weeks and used to measure the myl3 concentration. Because of the high molecular weight of myl3, the limitations of LC/MS/MS were overcome by implementing immunoprecipitation and digestion steps. Ultimately, a tryptic fragment of myl3 (13-mer), generated using immunoprecipitation and digestion by a biotinylated antibody, was detected using LC-MS/MS in positive ion mode through multiple reaction monitoring and analyte separation on a C18 column. Our method showed limits of detection and quantification of less than 0.3 and 0.8 μg/kg, respectively. However, differences in the myl3 concentrations according to the aging time were not significant (p > 0.05). After 12 weeks, myl3 disappeared in tested all samples, thus our analytical method can be used for accurate measurement of muscle protein in beef samples. Full article

(1) Background: Well-known monosodium glutamate (E-621, MSG), originally used as a food flavor enhancer, was approved approximately in all countries, but the toxicity versus the safety of (MSG) are still unclear due to variable scientific toxicological reports. Moreover, it was reported to trigger elevated frequencies of nausea and headaches in humans and provide deleterious effects on laboratory animals. The objectives of the present study were to (i) estimate the possible toxic effects of the food additive MSG (ii) and the ameliorating protective effects of the dietary supplement spirulina (Spirulina platensis) on the biochemical parameters of blood and the damage produced in organs of Swiss mice after applying a supplementary daily dose of MSG for 4 weeks. (2) Methods: The present study was conducted on 20 mature Swiss mice, which were randomly organized into four groups of five Swiss mice. The treatments were (I) the control group, in which Swiss mice were fed only animal feed and drinking water; group II MSG1, which received 1 mL of MSG; group III MSG0.5, which was treated with 0.5 mL of MSG; and (IV) the group MSGS, which was treated with 1 mL of monosodium glutamate and 1 mL of spirulina (aiming to reduce the MSG toxicity). (3) Results: At the end of the experiment, Swiss mice treated with MSG demonstrated a passiveness regarding behavioral aspects. As we hypothesized, the parameters of the spirulina group reached similar values to the control group, and no histopathological observations have been found. Altogether, our findings evidenced that monosodium glutamate leads to histopathological changes in Swiss mice kidneys and caused important modifications for all biochemical parameters of the blood serum. Noticeably, the potential protective effect of Spirulina platensis was proved and was described by using the FTIR spectroscopy technique. (4) Conclusions: A diet rich in antioxidants and other plant-derived bioactive compounds may provide healthy nutrition, alleviating the potential side effects of some food additives. Full article