Separations

13 pages, 847 KiB

Open AccessArticle

Optimized and Validated DBS/MAE/LC–MS Method for Rapid Determination of Date-Rape Drugs and Cocaine in Human Blood Samples—A New Tool in Forensic Analysis

by Paweł Stelmaszczyk, Ewa Gacek and Renata Wietecha-Posłuszny

Separations 2021, 8(12), 249; https://doi.org/10.3390/separations8120249 - 18 Dec 2021

Cited by 13 | Viewed by 3765

Abstract

The aim of this work was to develop a new method for the determination of selected substances from the date-rape drugs group: ketamine, benzodiazepines and cocaine. The method is based on the dried blood spot method which seems to be a suitable tool [...] Read more.

The aim of this work was to develop a new method for the determination of selected substances from the date-rape drugs group: ketamine, benzodiazepines and cocaine. The method is based on the dried blood spot method which seems to be a suitable tool in the analysis of tested substances. The extraction process based on microwave-assisted extraction was optimized to enable optimal conditions for the isolation of a wide range of analytes from blood samples collected on DBS cards. The extraction with ethyl acetate with a buffer of pH = 9 carried out at a temperature of 50 °C for 15 min ensured high extraction efficiency of the tested analytes. The optimized method was validated. Limits of detection (LOD = 4.38–21.1 ng/mL) and quantification (LOQ = 14.6–70.4 ng/mL), inter- and intra-day precision (CV = 1.37–13.4% and 3.39–14.8%, respectively), recovery (RE = 93.0–112.4%) and matrix effect (ME = 98.4–101.6%) were determined. The validation results indicate the possibility of using the proposed method in the analysis of real blood samples collected from victims of sexual assault. Full article

(This article belongs to the Section Bioanalysis/Clinical Analysis)

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19 pages, 4778 KiB

Open AccessArticle

How Coffee Capsules Affect the Volatilome in Espresso Coffee

by Giuseppe Greco, Estefanía Núñez-Carmona, Marco Abbatangelo, Patrizia Fava and Veronica Sberveglieri

Separations 2021, 8(12), 248; https://doi.org/10.3390/separations8120248 - 17 Dec 2021

Cited by 13 | Viewed by 3280

Abstract

Coffee capsules have become one of the most used methods to have a coffee in the last few years. In this work, coffee was prepared using a professional espresso coffee machine. We investigated the volatilome of four different polypropylene coffee capsule typologies (Biologico, [...] Read more.

Coffee capsules have become one of the most used methods to have a coffee in the last few years. In this work, coffee was prepared using a professional espresso coffee machine. We investigated the volatilome of four different polypropylene coffee capsule typologies (Biologico, Dolce, Deciso, Guatemala) with and without capsules in order to reveal the possible differences in the VOCs spectra. The volatilome of each one was singularly studied through an analysis by gas chromatography and mass spectrometry (GC–MS), checking the abundance of different VOCs in coffee extracted with and without a capsule protection and compared to its related sample. Furthermore, ANOVA and Tukey tests were applied to statistically identify and individuate the possible differences. As a result, it was found that coffee capsules, offer advantages of protecting coffee from oxidation or rancidity and, consequently extended shelf life as well as did not cause a reduction of volatile compounds intensity. Therefore, it is possible to conclude that the aroma of polypropylene coffee capsule extraction is not damaged compared to a traditional espresso. Full article

(This article belongs to the Special Issue Spectroscopic, Chromatographic, and Chemometric Techniques Applied in Food Products Characterization)

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11 pages, 3517 KiB

Open AccessArticle

Target Screening of Hydroxylated and Nitrated Polycyclic Aromatic Hydrocarbons in Surface Water Using Orbitrap High–Resolution Mass Spectrometry in a Lake in Hebei, China

by Zheyuan Shi, Zhu Rao, Jun Zhao, Ming Liang, Tao Zhu, Yuan Wang and Hamidreza Arandiyan

Separations 2021, 8(12), 247; https://doi.org/10.3390/separations8120247 - 16 Dec 2021

Cited by 3 | Viewed by 2478

Abstract

Polycyclic aromatic hydrocarbon (PAH) derivatives are mutagenic, carcinogenic, teratogenic and bioaccumulative pollutants. Investigations on hydroxylated PAHs (OH–PAHs) and Nitrated PAHs (NPAHs) in surface water are not enough. In this study, optimization and validation of an analytical method targeting nine kinds of OH–PAHs and [...] Read more.

Polycyclic aromatic hydrocarbon (PAH) derivatives are mutagenic, carcinogenic, teratogenic and bioaccumulative pollutants. Investigations on hydroxylated PAHs (OH–PAHs) and Nitrated PAHs (NPAHs) in surface water are not enough. In this study, optimization and validation of an analytical method targeting nine kinds of OH–PAHs and one kind of nitrated PAH in environmental water samples are presented. The method was validated for linearity, limits of detection and quantification and recovery using spiked matrix. The linear range of most target compounds was 0.1–200 ng∙mL⁻¹. However, the linear range of 1–hydroxy pyrene and 3–hydroxy benzo[a]pyrene started at 1 ng∙mL⁻¹ and the linear range of 1–hydroxy phenanthrene and 9–hydroxy benzo[a]pyrene could not reach 200 ng∙mL⁻¹. All the correlation coefficients (r²) were over 0.997. The instrumental limits of detection (LOD) and method detection limits (MDL) ranged from 0.01 to 0.67 ng∙mL⁻¹ and 1.11 to 2.26 ng∙L⁻¹, respectively. With this method, a lake in Hebei province, China, were screened. Three kinds of target compounds were detected. The average concentration was around 2.5 ng∙L⁻¹, while the highest concentration reached 286.54 ng∙L⁻¹. Full article

(This article belongs to the Special Issue UHPLC-MS/MS Methods for the Identification of Emerging Contaminant Transformation Products in Surface Water)

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11 pages, 3096 KiB

Open AccessArticle

Eco-Friendly Separation of Antihyperlipidemic Combination Using UHPLC Particle-Packed and Monolithic Columns by Applying Green Analytical Chemistry Principles

by Naser F. Al-Tannak and Ahmed Hemdan

Separations 2021, 8(12), 246; https://doi.org/10.3390/separations8120246 - 14 Dec 2021

Cited by 1 | Viewed by 2152

Abstract

Efficient separation of pharmaceuticals and metabolites with the adequate resolution is a key factor in choosing the most suitable chromatographic method. For quality control, the analysis time is a key factor, especially in pharmacokinetic studies. High back pressure is considered as one of [...] Read more.

Efficient separation of pharmaceuticals and metabolites with the adequate resolution is a key factor in choosing the most suitable chromatographic method. For quality control, the analysis time is a key factor, especially in pharmacokinetic studies. High back pressure is considered as one of the most important factors in chromatography’s flow control, especially in UHPLC. The separation of the anti-hyperlipidemic mixtures was carried out using two columns: a column silica-based particle packed UHPLC and a monolithic column. The systematic suitability of the two columns was compared for the separation of Fenofibrate, its active metabolite, Fenofibric acid and Pravastatin using Atorvastatin as an internal standard. Separation on both columns was obtained using ethanol: buffer potassium dihydrogen orthophosphate pH = 3 (adjusted with orthophosphoric acid) (75:25 v/v) as mobile phase and flow rate 0.8 mL/min. The analytes’ peak detection was achieved by using a PDA detector at 287 nm, 214 nm, 236 nm, and 250 nm for Fenofibrate, Fenofibric acid, Pravastatin, and Atorvastatin, respectively. Reduction of back-pressure was achieved with the monolithic column, where the analytes could be completely separated in less than 1.5 min at a flow rate of 5 mL/min. The principles of Green Analytical Chemistry (GAC) were followed throughout the developed method using environmentally safe solvents. Full article

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15 pages, 2918 KiB

Open AccessArticle

Hemp Chemotype Definition by Cannabinoids Characterization Using LC-ESI(+)-LTQ-FTICR MS and Infrared Multiphoton Dissociation

by Filomena Lelario, Raffaella Pascale, Giuliana Bianco, Laura Scrano and Sabino Aurelio Bufo

Separations 2021, 8(12), 245; https://doi.org/10.3390/separations8120245 - 13 Dec 2021

Cited by 6 | Viewed by 3093

Abstract

The development and application of advanced analytical methods for a comprehensive analysis of Cannabis sativa L. extracts plays a pivotal role in order to have a reliable evaluation of their chemotype definition to guarantee the efficacy and safety in pharmaceutical use. This paper [...] Read more.

The development and application of advanced analytical methods for a comprehensive analysis of Cannabis sativa L. extracts plays a pivotal role in order to have a reliable evaluation of their chemotype definition to guarantee the efficacy and safety in pharmaceutical use. This paper deals with the qualitative and quantitative determination of cannabidiol (CBD), tetrahydrocannabinol (THC), cannabinol (CBN), tetrahydrocannabivarin (THCV), cannabidivarin (CBDV), and cannabigerol (CBG) based on a liquid chromategraphy-mass spectrometry (LC-MS) method using electrospray ionization in positive mode (ESI+), coupled with a hybrid quadrupole linear ion trap (LTQ) and Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS). For the first time, structural information of phytocannabinoids is available upon precursor ions’ isolation within the FTICR trapping cell and subsequent fragmentation induced by infrared multiphoton dissociation (IRMPD). Such fragmentation and accurate mass measurement of product ions, alongside collision-induced dissociation (CID) within LTQ, was advantageous to propose a reliable fragmentation pattern for each compound. Then, the proposed LC-ESI(+)-LTQ-FTICR MS method was successfully applied to the hemp chemotype definition of three registered Italian accessions of hemp C. sativa plants (Carmagnola C.S., Carmagnola, and Eletta Campana), thus resulting in the Eletta Campana accession being the best one for cannabis product manufacturing. Full article

(This article belongs to the Section Analysis of Natural Products and Pharmaceuticals)

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14 pages, 1119 KiB

Open AccessArticle

Effect of Ultrasound-Assisted Pretreatment on Extraction Efficiency of Essential Oil and Bioactive Compounds from Citrus Waste By-Products

by Harloveleen Kaur Sandhu, Prachi Sinha, Neela Emanuel, Nishant Kumar, Rokayya Sami, Ebtihal Khojah and Amina A. M. Al-Mushhin

Separations 2021, 8(12), 244; https://doi.org/10.3390/separations8120244 - 13 Dec 2021

Cited by 30 | Viewed by 5361

Abstract

Waste or by-product use is in focus for reducing the environmental threat and acquiring wealth out of waste. The current study aim was to investigate the effects of ultrasound pretreatment on the extraction of bioactive compounds and composition of essential oils extracted from [...] Read more.

Waste or by-product use is in focus for reducing the environmental threat and acquiring wealth out of waste. The current study aim was to investigate the effects of ultrasound pretreatment on the extraction of bioactive compounds and composition of essential oils extracted from citrus waste. The response surface methodology (RSM) was used to optimize higher yield extraction parameters. Pretreatment of ultrasound-assisted extraction recovered 33% enhanced yield with reduced time and was economical as compared to conventional hydro-distilled process. The functional quality of essential oil was determined using FTIR and GC-MS. Antioxidants from citrus peel and pulp/pomace were extracted and analyzed by spectroscopic techniques. The quantification of bioactive compounds from citrus waste was performed using high performance liquid chromatography (HPLC). Mass transfer rate of antioxidants from peel and pomace were 30% increased as a result of ultrasound-assisted treatment. The significantly (p ≤ 0.05) higher TPC (735.54 mg/100 g) and antioxidant activity (44.26%) was recorded in Citrus sinensis Pulp and peel respectively. The bioactive compounds such as hesperidin (31.52 mg/100 g) was significantly higher in (p ≤ 0.05) in Citrus sinensis pulnd extract. Vanillin was found 1.21 mg/100 g in peel extract of citrus fruit, moreover vanillin was not detected in pulp extract. Myrecitin was not detected in both the samples. The bioactive natural compounds extracted from citrus peel can be used in food and pharma sector as natural anti-oxidantcompounds. Full article

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9 pages, 4796 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Green Stability Indicating Organic Solvent-Free HPLC Determination of Remdesivir in Substances and Pharmaceutical Dosage Forms

by Adel Ehab Ibrahim, Sami El Deeb, Emad Mahmoud Abdelhalim, Ahmed Al-Harrasi and Rania Adel Sayed

Separations 2021, 8(12), 243; https://doi.org/10.3390/separations8120243 - 12 Dec 2021

Cited by 26 | Viewed by 5152

Abstract

A green liquid chromatographic method is considered in this work to minimize the environmental impact of waste solvents. One important principle is to replace or eliminate the use of hazardous organic solvents. Organic impurities in any active pharmaceutical ingredient could arise either during [...] Read more.

A green liquid chromatographic method is considered in this work to minimize the environmental impact of waste solvents. One important principle is to replace or eliminate the use of hazardous organic solvents. Organic impurities in any active pharmaceutical ingredient could arise either during the process of its synthesis, or as degradation products developed throughout the shelf-life. Remdesivir (RDS) is an antiviral drug, approved by the US Food and Drug Adminstration (-FDA), to treat SARS-Cov-2 virus during its pandemic crisis. We studied the stability of remdesivir against several degradation pathways using the organic solvent-free liquid chromatographic technique. Separation was performed on RP-C18 stationary phase using mixed-micellar mobile phase composed of a mixture of 0.025 M Brij-35, 0.1 M sodium lauryl sulfate (SLS), and 0.02 M disodium hydrogen phosphate, adjusted to pH 6.0. The mobile phase flow rate was 1 mL min⁻¹, and detection was carried out at a wavelength of 244 nm. We profiled the impurities that originated in mild to drastic degradation conditions. The method was then validated according to International Conference of Harmonization (ICH) guidelines within a linearity range of 5–100 μg mL⁻¹ and applied successfully for the determination of the drug in its marketed dosage form. A brief comparison was established with reported chromatographic methods, including a greenness assessment on two new metrics (GAPI and AGREE). This study is the first to be reported as eco-friendly, solvent-free, and stability indicating LC methodology for RDS determination and impurity profiling. Full article

(This article belongs to the Special Issue Chromatographic and Electrophoretic Methods in Current Biomedical Analysis)

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14 pages, 4230 KiB

Open AccessArticle

Estimation of Bed Expansion and Separation Density of Gas–Solid Separation Fluidized Beds Using a Micron-Sized-Particle-Dense Medium

by Xuchen Fan and Chenyang Zhou

Separations 2021, 8(12), 242; https://doi.org/10.3390/separations8120242 - 10 Dec 2021

Cited by 7 | Viewed by 3453

Abstract

Coal is the dominant energy resource in China. With the Chinese policy of committing to reducing peak carbon dioxide emissions and achieving carbon neutrality, coal separation has recently become a hot topic, especially the fluidized separation of fine particles. In this study, micron-sized [...] Read more.

Coal is the dominant energy resource in China. With the Chinese policy of committing to reducing peak carbon dioxide emissions and achieving carbon neutrality, coal separation has recently become a hot topic, especially the fluidized separation of fine particles. In this study, micron-sized particles were introduced to ameliorate the properties of the traditional fluidized bed. The expansion characteristics of the micron-sized-particle-dense medium were explored. A bed expansion prediction model of the micron-sized-particle-dense medium was established, and the prediction error was about 10%, providing a theoretical basis for understanding the distribution characteristics of the bed. This model also helped predict the bed density in the presence of a micron-sized-particle-dense medium, and the prediction accuracy was between 85% and 92%, providing a theoretical basis for selecting and popularizing fluidized beds for industrial separation. Full article

(This article belongs to the Special Issue Forefront of Mineral Resource Separation Technology)

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13 pages, 2763 KiB

Open AccessArticle

Isolation and Purification of a Hydrophobic Non-Ribosomal Peptide from an Escherichia coli Fermentation Broth

by Arne Michael Oestreich, Sebastian Reinhardt, Doreen Gerlach, Rong Fan and Peter Czermak

Separations 2021, 8(12), 241; https://doi.org/10.3390/separations8120241 - 9 Dec 2021

Viewed by 2717

Abstract

Non-ribosomal peptide synthases (NRPSs) generate versatile bioactive peptides by incorporating non-proteinogenic amino acids and catalyzing diverse modifications. Here, we developed an efficient downstream process for the capture, intermediate purification and polishing of a rhabdopeptide (RXP) produced by the NRPS VietABC. Many typical unit [...] Read more.

Non-ribosomal peptide synthases (NRPSs) generate versatile bioactive peptides by incorporating non-proteinogenic amino acids and catalyzing diverse modifications. Here, we developed an efficient downstream process for the capture, intermediate purification and polishing of a rhabdopeptide (RXP) produced by the NRPS VietABC. Many typical unit operations were unsuitable due to the similar physical and chemical properties of the RXP and related byproducts. However, we were able to capture the RXP from a fermentation broth using a hydrophobic resin (XAD-16N), resulting in a 14-fold increase in concentration while removing salts as well as polar and weak non-polar impurities. We then used ultra-high-performance liquid chromatography (UHPLC) for intermediate purification, with optimized parameters determined using statistical experimental designs, resulting in the complete removal of hydrophobic impurities. Finally, the UHPLC eluents were removed by evaporation. Our three-step downstream process achieved an overall product recovery of 81.7 ± 8.4%. Full article

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12 pages, 535 KiB

Open AccessArticle

Efficacy of Oregano Essential Oil Extract in the Inhibition of Bacterial Lipopolysaccharide (LPS)-Induced Osteoclastogenesis Using RAW 264.7 Murine Macrophage Cell Line—An In-Vitro Study

by Krishnamachari Janani, Kavalipurapu Venkata Teja, Mohammad Khursheed Alam, Deepti Shrivastava, Azhar Iqbal, Osama Khattak, Khalid Al-Johani, May Othman Hamza, Jerry Jose, Mohmed Isaqali Karobari and Kumar Chandan Srivastava

Separations 2021, 8(12), 240; https://doi.org/10.3390/separations8120240 - 7 Dec 2021

Cited by 3 | Viewed by 4311

Abstract

Gram-negative, anaerobic bacterias are predominate in periapical infections. The bacterial lipopolysaccharide (LPS) initiates the process of inflammation and periapical bone resorption. Usage of various medicaments retards or inactivates the bacterial endotoxin (LPS). However, the results are not highly effective. In recent years, owing [...] Read more.

Gram-negative, anaerobic bacterias are predominate in periapical infections. The bacterial lipopolysaccharide (LPS) initiates the process of inflammation and periapical bone resorption. Usage of various medicaments retards or inactivates the bacterial endotoxin (LPS). However, the results are not highly effective. In recent years, owing to antimicrobial resistance, the shift from conventional agents to herbal agents has been increased tremendously in research. Keeping this in mind, the present study was formulated to evaluate the efficacy of oregano essential oil in inhibiting bacterial LPS- induced osteoclastogenesis. Four different concentrations (0 ng/mL, 25 ng/mL, 50 ng/mL, and 100 ng/mL) of oregano essential oil extract were added into 96-well culture plate. Under light microscope, quantification of osteoclast cells was performed. One-way ANOVA with post-hoc Tukey test was carried out on SPSS v21. A significant reduction (p < 0.001) in the osteoclast was observed in the experimental groups compared to no oregano essential oil extract (control). A dose-dependent significant reduction (p < 0.001) in osteoclast formation was observed among the experimental groups, with lesser osteoclast seen in group IV with 100 ng/mL of oregano essential oil extract. Thus, it can be concluded that oregano essential oil extract can be utilized as a therapeutic agent that can target bacterial LPS-induced osteoclastogenesis. However, randomized controlled studies should be conducted to assess the potential use of this extract in the periapical bone resorption of endodontic origin. Full article

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14 pages, 2719 KiB

Open AccessArticle

GC-MS Method for Quantification and Pharmacokinetic Study of Four Volatile Compounds in Rat Plasma after Oral Administration of Commiphora myrrh (Nees) Engl. Resin and In Vitro Cytotoxic Evaluation

by Ali S. Alqahtani, Rashed N. Herqash, Faleh Alqahtani, Syed Rizwan Ahamad, Fahd A. Nasr and Omar M. Noman

Separations 2021, 8(12), 239; https://doi.org/10.3390/separations8120239 - 7 Dec 2021

Cited by 4 | Viewed by 3112

Abstract

A rapid, simple, and sensitive gas chromatography–tandem mass spectrometry (GC–MS) method was established and validated for simultaneous determination of four volatile compounds, namely curzerene, methoxyfuranodiene, β-elemene, and α-pinene in rat plasma samples after oral administration of the resin extract of Commiphora myrrh [...] Read more.

A rapid, simple, and sensitive gas chromatography–tandem mass spectrometry (GC–MS) method was established and validated for simultaneous determination of four volatile compounds, namely curzerene, methoxyfuranodiene, β-elemene, and α-pinene in rat plasma samples after oral administration of the resin extract of Commiphora myrrh using limonene as an internal standard (IS). Liquid-liquid extraction using hexane and ethyl acetate (1:1) mixture as an extracting agent was used for the samples extraction procedure. The GC–MS system was operated under selective ion monitoring (SIM) mode using Perkin Elmer Elite 5MS column (30 m × 0.25 mm × 0.25 µm film thickness). Specificity, linearity, precision, accuracy, extraction recovery, and stability were used to validate the developed method. The assay showed good linearity (r² ≥ 0.998), and the lowest limits of quantification (LLOQ) were 3.97–21.38 ng/mL for the four analytes. This assay was successfully applied to pharmacokinetic studies of the four volatile compounds in rat plasma. The antiproliferative activity of these volatile compounds was evaluated against lung carcinoma (A549) and colon (LoVo) cell lines, were each compound caused variable inhibition on cells proliferation and methoxyfuranodiene exerted the strong antiproliferative activity against both cell line according to IC₅₀ values. Full article

(This article belongs to the Special Issue Separations in Biomedical Analysis)

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10 pages, 3000 KiB

Open AccessArticle

A Method to Separate Two Main Antioxidants from Lepidium latifolium L. Extracts Using Online Medium Pressure Chromatography Tower and Two-Dimensional Inversion/Hydrophobic Interaction Chromatography Based on Online HPLC-DPPH Assay

by Xiu Wang, Yupei Zhang, Nan Wu, Jingya Cao, Yanduo Tao and Ruitao Yu

Separations 2021, 8(12), 238; https://doi.org/10.3390/separations8120238 - 6 Dec 2021

Cited by 8 | Viewed by 2788

Abstract

Free radicals, including 1,1-diphenyl-2-picrylhydrazyl, mediate oxidative stress to cause many chronic diseases (including cardiovascular diseases, diabetes and cancer). The extract of traditional Tibetan medicine Lepidium latifolium L. (L. latifolium) was reported to have free radical inhibition ability. Therefore, a system method [...] Read more.

Free radicals, including 1,1-diphenyl-2-picrylhydrazyl, mediate oxidative stress to cause many chronic diseases (including cardiovascular diseases, diabetes and cancer). The extract of traditional Tibetan medicine Lepidium latifolium L. (L. latifolium) was reported to have free radical inhibition ability. Therefore, a system method was established to separate the ethanol extract of L. latifolium to prepare two main antioxidant compounds. First of all, silica gel and a medium-pressure liquid chromatography tower were used for pre-treatment of the ethanol extract of L. latifolium to obtain the main antioxidant active component fraction 4 through online high-performance liquid chromatography-1,1-diphenyl-2-picrylhydrazyl (HPLC-DPPH) assay. Then, fraction 4-1 was obtained by one-dimensional preparation using Megres C18 chromatographic column, and two active compounds with IC₅₀ values 59.9 and 71.3 μg/mL were obtained by two-dimensional preparation using Click XIon chromatographic column. Through the study of the chemical components and separation methods of L. latifolium, the combination of HPLC-DPPH assay and two-dimensional preparative liquid chromatography was realized, providing a reference for the separation of active compounds from L. latifolium. Full article

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13 pages, 1795 KiB

Open AccessArticle

Development and Application of Molecularly Imprinted Polymers for the Selective Extraction of Chlordecone from Bovine Serum

by Pauline Bosman, Audrey Combès, Marine Lambert, Gwenaëlle Lavison-Bompard and Valérie Pichon

Separations 2021, 8(12), 237; https://doi.org/10.3390/separations8120237 - 4 Dec 2021

Cited by 5 | Viewed by 2600

Abstract

The widespread use of chlordecone (CLD), an organochlorine pesticide, until the 1990s to protect banana crops in the French West Indies led to significant pollution of water and soil and, subsequently, of bovine intended for human consumption. Carcasses are submitted to official controls [...] Read more.

The widespread use of chlordecone (CLD), an organochlorine pesticide, until the 1990s to protect banana crops in the French West Indies led to significant pollution of water and soil and, subsequently, of bovine intended for human consumption. Carcasses are submitted to official controls based on perirenal fat CLD determination. In order to allow for pre-slaughter controls, a selective analytical method based on a molecularly imprinted polymer (MIP) associated to the LC/MS-MS method was developed to determine the level of CLD in bovine serum that can be collected before slaughter. Different synthesis conditions were therefore assayed by varying the nature of the monomer and of the porogen, and the most promising MIP in terms of selective retention for CLD (extraction recovery close to 100%) was completely characterized by solid-phase extraction (repeatability of the extraction procedure, of the synthesis, and of the cartridge filling) in pure medium. The capacity of the MIP was determined at 0.13 µmol g⁻¹ of MIP. After application of a spiked bovine serum sample on the MIP, the selective retention was maintained (87 and 21%, respectively, on the MIP and on the corresponding non-imprinted polymer). Moreover, extraction on the MIP led to a cleaner extract compared to those issued from a conventional C18 sorbent. Full article

(This article belongs to the Special Issue Molecularly Imprinted Polymers: Selective Extraction Materials for Sample Preparation)

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13 pages, 1978 KiB

Open AccessArticle

Simultaneous Determination of 23 Mycotoxins in Broiler Tissues by Solid Phase Extraction UHPLC-Q/Orbitrap High Resolution Mass Spectrometry

by Youyou Yang, Zhuolin He, Lei Mu, Yunfeng Xie and Liang Wang

Separations 2021, 8(12), 236; https://doi.org/10.3390/separations8120236 - 4 Dec 2021

Cited by 2 | Viewed by 2413

Abstract

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. [...] Read more.

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

(This article belongs to the Special Issue Advances of Accurate Quantification Methods in Food Analysis)

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10 pages, 236 KiB

Open AccessArticle

Green Aspects of Ion Chromatography versus Other Methods in the Analysis of Common Inorganic Ions

by Rajmund Michalski and Paulina Pecyna-Utylska

Separations 2021, 8(12), 235; https://doi.org/10.3390/separations8120235 - 3 Dec 2021

Cited by 5 | Viewed by 2931

Abstract

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 [...] Read more.

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

(This article belongs to the Section Environmental Separations)

10 pages, 2423 KiB

Open AccessArticle

3D Printed Skin-Wash Sampler for Sweat Sampling in Cystic Fibrosis Diagnosis Using Capillary Electrophoretic Ion Ratio Analysis

by Miriam Malá, Petra Itterheimová, Lukáš Homola, Jana Vinohradská and Petr Kubáň

Separations 2021, 8(12), 234; https://doi.org/10.3390/separations8120234 - 3 Dec 2021

Cited by 5 | Viewed by 2750

Abstract

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 [...] Read more.

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 article belongs to the Section Bioanalysis/Clinical Analysis)

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19 pages, 3946 KiB

Open AccessArticle

Identification of Tentative Traceability Markers with Direct Implications in Polyphenol Fingerprinting of Red Wines: Application of LC-MS and Chemometrics Methods

by Laurentiu Mihai Palade, Constantin Croitoru, Camelia Albu, Gabriel Lucian Radu and Mona Elena Popa

Separations 2021, 8(12), 233; https://doi.org/10.3390/separations8120233 - 3 Dec 2021

Cited by 5 | Viewed by 3129

Abstract

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 [...] Read more.

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

(This article belongs to the Special Issue Application of Chromatography and Different Extraction Techniques in Analysis of Polyphenolic Compounds)

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16 pages, 6538 KiB

Open AccessArticle

Development of a Method for the Measurement of Human Scent Samples Using Comprehensive Two-Dimensional Gas Chromatography with Mass Detection

by Petra Pojmanová, Nikola Ladislavová and Štěpán Urban

Separations 2021, 8(12), 232; https://doi.org/10.3390/separations8120232 - 3 Dec 2021

Cited by 4 | Viewed by 3473

Abstract

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 [...] Read more.

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

(This article belongs to the Special Issue Comprehensive Separations of Complex Mixtures by Gas Chromatography/Mass Spectrometry)

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8 pages, 2153 KiB

Open AccessArticle

What You Extract Is What You Get: Different Methods of Protein Extraction from Hemp Seeds

by Annalisa Givonetti, Chiara Cattaneo and Maria Cavaletto

Separations 2021, 8(12), 231; https://doi.org/10.3390/separations8120231 - 2 Dec 2021

Cited by 4 | Viewed by 5336

Abstract

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 [...] Read more.

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

(This article belongs to the Special Issue Extraction and Analysis of Plant Active Ingredients)

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13 pages, 1802 KiB

Open AccessReview

NMR Tracing of Food Geographical Origin: The Impact of Seasonality, Cultivar and Production Year on Data Analysis

by Olimpia Masetti, Angela Sorbo and Luigi Nisini

Separations 2021, 8(12), 230; https://doi.org/10.3390/separations8120230 - 1 Dec 2021

Cited by 14 | Viewed by 3184

Abstract

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 [...] Read more.

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

(This article belongs to the Special Issue Food Quality and Safety: Advances in Analytical Methods and Applications)

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18 pages, 4256 KiB

Open AccessArticle

Effect of Temperature on Diluate Water in Batch Electrodialysis Reversal

by Germán Eduardo Dévora-Isiordia, Alejandra Ayala-Espinoza, Luis Alberto Lares-Rangel, María Isela Encinas-Guzmán, Reyna Guadalupe Sánchez-Duarte, Jesús Álvarez-Sánchez and María del Rosario Martínez-Macías

Separations 2021, 8(12), 229; https://doi.org/10.3390/separations8120229 - 1 Dec 2021

Cited by 2 | Viewed by 3176

Abstract

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 [...] Read more.

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

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15 pages, 5838 KiB

Open AccessArticle

Evaluation of New, Sputtered Carbon SPME Fibers with a Multi-Functional Group Test Mixture

by Dhananjay I. Patel, Tuhin Roychowdhury, Collin Jacobsen, Colton Myers, Jason S. Herrington and Matthew R. Linford

Separations 2021, 8(12), 228; https://doi.org/10.3390/separations8120228 - 23 Nov 2021

Cited by 1 | Viewed by 2805

Abstract

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 [...] Read more.

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

(This article belongs to the Special Issue Recent Advances in Green Sample Preparation Techniques)

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11 pages, 2367 KiB

Open AccessArticle

HPLC-DAD Analysis of Hemp Oil Supplements for Determination of Four Cannabinoids: Cannabidiol, Cannabidiolic Acid, Cannabinol and Delta 9-Tetrahydrocannabinol

by Katarzyna Madej, Aleksandra Chmiołek, Kamila Szlachta and Wojciech Piekoszewski

Separations 2021, 8(12), 227; https://doi.org/10.3390/separations8120227 - 23 Nov 2021

Cited by 10 | Viewed by 5298

Abstract

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) [...] Read more.

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

(This article belongs to the Special Issue Separation and Quantitative Analysis of Natural Product Extracts)

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Separations, Volume 8, Issue 12 (December 2021) – 23 articles

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