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15 pages, 2163 KiB

Open AccessArticle

A Reliable Method Based on Liquid Chromatography–Tandem Mass Spectrometry for the Simultaneous Quantification of Neurotransmitters in Caenorhabditis elegans

by Ann-Kathrin Weishaupt, Laura Kubens, Lysann Ruecker, Tanja Schwerdtle, Michael Aschner and Julia Bornhorst

Molecules 2023, 28(14), 5373; https://doi.org/10.3390/molecules28145373 - 13 Jul 2023

Cited by 7 | Viewed by 2177

Abstract

Neurotransmitters like dopamine (DA), serotonin (SRT), γ-aminobutyric acid (GABA) and acetylcholine (ACh) are messenger molecules that play a pivotal role in transmitting excitation between neurons across chemical synapses, thus enabling complex processes in the central nervous system (CNS). Balance in neurotransmitter homeostasis is [...] Read more.

Neurotransmitters like dopamine (DA), serotonin (SRT), γ-aminobutyric acid (GABA) and acetylcholine (ACh) are messenger molecules that play a pivotal role in transmitting excitation between neurons across chemical synapses, thus enabling complex processes in the central nervous system (CNS). Balance in neurotransmitter homeostasis is essential, and altered neurotransmitter levels are associated with various neurological disorders, e.g., loss of dopaminergic neurons (Parkinson’s disease) or altered ACh synthesis (Alzheimer’s disease). Therefore, it is crucial to possess adequate tools to assess precise neurotransmitter levels, and to apply targeted therapies. An established in vivo model to study neurotoxicity is the model organism Caenorhabditis elegans (C. elegans), as its neurons have been well characterized and functionally are analogous to mammals. We have developed a liquid chromatography–tandem mass spectrometry (LC-MS/MS) method including a sample preparation assuring neurotransmitter stability, which allows a simultaneous neurotransmitter quantification of DA, SRT, GABA and ACh in C. elegans, but can easily be applied to other matrices. LC-MS/MS combined with isotope-labeled standards is the tool of choice, due to its otherwise unattainable sensitivity and specificity. Using C. elegans together with our analytically validated and verified method provides a powerful tool to evaluate mechanisms of neurotoxicity, and furthermore to identify possible therapeutic approaches. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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12 pages, 1806 KiB

Open AccessArticle

Spontaneous In-Source Fragmentation Reaction Mechanism and Highly Sensitive Analysis of Dicofol by Electrospray Ionization Mass Spectrometry

by Jun Xie, Yage Guo, Yongqiang Ma, Hongyun Jiang, Lan Zhang, Liangang Mao, Lizhen Zhu, Yongquan Zheng and Xingang Liu

Molecules 2023, 28(9), 3765; https://doi.org/10.3390/molecules28093765 - 27 Apr 2023

Cited by 3 | Viewed by 2916

Abstract

Although dicofol has been widely banned all over the world as a kind of organochlorine contaminant, it still exists in the environment. This study developed a high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS/MS) detection technique for dicofol, an environmental pollutant, for the [...] Read more.

Although dicofol has been widely banned all over the world as a kind of organochlorine contaminant, it still exists in the environment. This study developed a high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS/MS) detection technique for dicofol, an environmental pollutant, for the first time using in-source fragmentation. The results confirmed that m/z 251 was the only precursor ion of dicofol after in-source fragmentation, and m/z 139 and m/z 111 were reasonable product ions. The main factors triggering the in-source fragmentation were the H⁺ content and solution conductivity when dicofol entered the mass spectrometer. Density functional theory can be used to analyze and interpret the mechanism of dicofol fragmentation reaction in ESI source. Dicofol reduced the molecular energy from 8.8 ± 0.05 kcal/mol to 1.0 ± 0.05 kcal/mol, indicating that the internal energy release from high to low was the key driving force of in-source fragmentation. A method based on HPLC-MS/MS was developed to analyze dicofol residues in environmental water. The LOQ was 0.1 μg/L, which was better than the previous GC or GC-MS methods. This study not only proposed an HPLC-MS/MS analysis method for dicofol for the first time but also explained the in-source fragmentation mechanism of compounds in ESI source, which has positive significance for the study of compounds with unconventional mass spectrometry behavior in the field of organic pollutant analysis and metabonomics. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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15 pages, 1632 KiB

Open AccessArticle

A Highly Efficient Workflow for Detecting and Identifying Sequence Variants in Therapeutic Proteins with a High Resolution LC-MS/MS Method

by Lance Cadang, Chi Yan Janet Tam, Benjamin Nathan Moore, Juergen Fichtl and Feng Yang

Molecules 2023, 28(8), 3392; https://doi.org/10.3390/molecules28083392 - 12 Apr 2023

Viewed by 3908

Abstract

Large molecule protein therapeutics have steadily grown and now represent a significant portion of the overall pharmaceutical market. These complex therapies are commonly manufactured using cell culture technology. Sequence variants (SVs) are undesired minor variants that may arise from the cell culture biomanufacturing [...] Read more.

Large molecule protein therapeutics have steadily grown and now represent a significant portion of the overall pharmaceutical market. These complex therapies are commonly manufactured using cell culture technology. Sequence variants (SVs) are undesired minor variants that may arise from the cell culture biomanufacturing process that can potentially affect the safety and efficacy of a protein therapeutic. SVs have unintended amino acid substitutions and can come from genetic mutations or translation errors. These SVs can either be detected using genetic screening methods or by mass spectrometry (MS). Recent advances in Next-generation Sequencing (NGS) technology have made genetic testing cheaper, faster, and more convenient compared to time-consuming low-resolution tandem MS and Mascot Error Tolerant Search (ETS)-based workflows which often require ~6 to 8 weeks data turnaround time. However, NGS still cannot detect non-genetic derived SVs while MS analysis can do both. Here, we report a highly efficient Sequence Variant Analysis (SVA) workflow using high-resolution MS and tandem mass spectrometry combined with improved software to greatly reduce the time and resource cost associated with MS SVA workflows. Method development was performed to optimize the high-resolution tandem MS and software score cutoff for both SV identification and quantitation. We discovered that a feature of the Fusion Lumos caused significant relative under-quantitation of low-level peptides and turned it off. A comparison of common Orbitrap platforms showed that similar quantitation values were obtained on a spiked-in sample. With this new workflow, the amount of false positive SVs was decreased by up to 93%, and SVA turnaround time by LC-MS/MS was shortened to 2 weeks, comparable to NGS analysis speed and making LC-MS/MS the top choice for SVA workflow. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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15 pages, 954 KiB

Open AccessArticle

Determination of β₂-Agonist Residues in Fermented Ham Using UHPLC-MS/MS after Enzymatic Digestion and Sulfonic Resin Solid Phase Purification

by Chenggang Cai, Yannan Xiang, Siyi Tian, Zhongce Hu, Zhengyan Hu, Bingjie Ma and Pinggu Wu

Molecules 2023, 28(5), 2039; https://doi.org/10.3390/molecules28052039 - 21 Feb 2023

Cited by 6 | Viewed by 1569

Abstract

β₂-agonists are a class of synthetic sympathomimetic drugs with acute poisoning effects if consumed as residues in foods. To improve the efficiency of sample preparation and to overcome matrix-dependent signal suppression in the quantitative analysis of four β₂-agonists (clenbuterol, [...] Read more.

β₂-agonists are a class of synthetic sympathomimetic drugs with acute poisoning effects if consumed as residues in foods. To improve the efficiency of sample preparation and to overcome matrix-dependent signal suppression in the quantitative analysis of four β₂-agonists (clenbuterol, ractopamine, salbutamol, and terbutaline) residues in fermented ham, an enzyme digestion coupled cation exchange purification method for sample preparation was established using ultra-high performance liquid chromatography and tandem mass spectrometry (UHPLC-MS/MS). Enzymatic digests were subject to cleanup treatment on three different solid phase extraction (SPE) columns and a polymer-based strong cation resin (SCR) cartridge containing sulfonic resin was found to be optimal compared with silica-based sulfonic acid and polymer sulfonic acid resins based SPEs. The analytes were investigated over the linear range of 0.5 to 10.0 μg/kg with recovery rates of 76.0–102.0%, and a relative standard deviation of 1.8–13.3% (n = 6). The limit of detection (LOD) and the limit of quantification (LOQ) were 0.1 μg/kg and 0.3 μg/kg, respectively. This newly developed method was applied to the detection of β₂-agonist residues in 50 commercial ham products and only one sample was found to contain β₂-agonist residues (clenbuterol at 15.2 µg/kg). Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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11 pages, 1462 KiB

Open AccessArticle

Residual Behavior and Dietary Risk Assessment of Chlorfenapyr and Its Metabolites in Radish

by Mingna Sun, Xiaotong Yi, Zhou Tong, Xu Dong, Yue Chu, Dandan Meng and Jinsheng Duan

Molecules 2023, 28(2), 580; https://doi.org/10.3390/molecules28020580 - 6 Jan 2023

Cited by 2 | Viewed by 2103

Abstract

Chlorfenapyr, as a highly effective and low-toxicity insect growth regulation inhibitor, has been used to control cross-cruciferous vegetable pests. However, the pesticide residue caused by its application threatens human health. In this paper, the residue digestion and final residue of chlorfenapyr in radish [...] Read more.

Chlorfenapyr, as a highly effective and low-toxicity insect growth regulation inhibitor, has been used to control cross-cruciferous vegetable pests. However, the pesticide residue caused by its application threatens human health. In this paper, the residue digestion and final residue of chlorfenapyr in radish were studied in a field experiment. The results of the dynamic digestion test showed that the half-life of chlorfenapyr in radish leaves ranged from 6.0 to 6.4 days, and the digestion rate was fast. The median residual values of chlorfenapyr in radish and radish leaves at 14 days after treatment were 0.12 and 3.92 mg/kg, respectively. The results of the dietary intake risk assessment showed that the national estimated daily intake (NEDI) of chlorfenapyr in various populations in China were 0.373 and 5.66 µg/(kg bw·d), respectively. The risk entropy (RQ) was 0.012 and 0.147, respectively, indicating that the chronic dietary intake risk of chlorfenapyr in radish was low. The results of this study provided data support and a theoretical basis for guiding the scientific use of chlorfenapyr in radish production and evaluating the dietary risk of chlorfenapyr in vegetables. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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11 pages, 1392 KiB

Open AccessArticle

The Development of an Ultra-Performance Liquid Chromatography–Tandem Mass Spectrometry Method for Biogenic Amines in Fish Samples

by Tong Li, Ruiguo Wang and Peilong Wang

Molecules 2023, 28(1), 184; https://doi.org/10.3390/molecules28010184 - 26 Dec 2022

Cited by 7 | Viewed by 2652

Abstract

Biogenic amines (BAs) are a group of substances that are formed from amino acids by decarboxylation or amination and transamination of aldehydes and ketones. They may have either an aliphatic, aromatic, or heterocyclic structure. Their quantity determines their effects and optimum amounts are [...] Read more.

Biogenic amines (BAs) are a group of substances that are formed from amino acids by decarboxylation or amination and transamination of aldehydes and ketones. They may have either an aliphatic, aromatic, or heterocyclic structure. Their quantity determines their effects and optimum amounts are essential for physiological functions, but excess BAs causes various toxic effects throughout the human body. In our study, to rapidly determine 14 BAs (histamine, tyramine, dopamine, tryptamine, serotonin, putrescine, spermine, spermidine, octopamine, benzylamine, 1-Phenylethanamine, cadaverine, 2-Phenethylamine, and agmatine) in real fish samples, an ultra-performance liquid chromatography–tandem mass spectrometry method was established. The fish sample was extracted by acetonitrile with 0.1% formic acid and stable biogenic amine derivatives could be obtained by benzoyl chloride derivatization with a shorter reaction time. The method showed good linearity with a linear range of 3–4 orders of magnitude and regression coefficients ranging from 0.9961 to 0.9999. The calculated LODs ranged from 0.1 to 20 nM and the LOQs ranged from 0.3 to 60 nM. Satisfactory recovery was obtained from 84.6% to 119.3%. The proposed method was employed to determine the concentration levels of biogenic amine derivatives in different fish. The results indicated that this method was suitable for the analysis of biogenic amines. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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10 pages, 1525 KiB

Open AccessArticle

Development of a Proton-Enhanced ESI UPLC-MS/MS Method for the Determination of Tetrodotoxin

by Tong Li, Ruiguo Wang and Peilong Wang

Molecules 2022, 27(24), 8967; https://doi.org/10.3390/molecules27248967 - 16 Dec 2022

Viewed by 1666

Abstract

Tetrodotoxin (TTX) is a kind of low-molecular-weight non-protein neurotoxin. It is one of the most potent neurotoxins found in nature, and it is found in puffer fish and various marine biota. The low sensitivity of previous analytical methods limited their application in puffer [...] Read more.

Tetrodotoxin (TTX) is a kind of low-molecular-weight non-protein neurotoxin. It is one of the most potent neurotoxins found in nature, and it is found in puffer fish and various marine biota. The low sensitivity of previous analytical methods limited their application in puffer fish organ samples. This study established a method for the accurate and fast determination of TTX by reversed ultra-performance liquid chromatography coupled with proton-enhanced electron spray ionization–tandem mass spectrometry. The method yields good peak shapes, high sensitivity and low coeluted interferences. The method was successfully applied to determine TTX in puffer fish tissue samples of about 0.2 g. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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15 pages, 903 KiB

Open AccessArticle

Dissipation and Dietary Risk Assessment of Pydiflumetofen Residues in Soybean

by Liping Wei, Xingang Hou, Zhiguang Hou, Xiaolong Yu, Xiumei Wang, Qinghui Zhao, Hemin Gao, Hanju Liu, Xiaodong Zheng and Zhongbin Lu

Molecules 2022, 27(23), 8465; https://doi.org/10.3390/molecules27238465 - 2 Dec 2022

Cited by 1 | Viewed by 1579

Abstract

In this study, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method, combined with high-performance liquid chromatography–tandem mass spectrometry, was chosen for detecting pydiflumetofen residues in soybean plants, soybeans and soil, and assessing the risk of short- and long-term dietary intake. Pydiflumetofen [...] Read more.

In this study, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method, combined with high-performance liquid chromatography–tandem mass spectrometry, was chosen for detecting pydiflumetofen residues in soybean plants, soybeans and soil, and assessing the risk of short- and long-term dietary intake. Pydiflumetofen concentrations ranging from 0.001–0.5 mg/L exhibited good linearity (r > 0.997). At varying doses, the average pydiflumetofen recovery rates and relative standard deviations among soybean plants, soybeans, and soil ranged from 83.9 ± 1.1% to 99.5 ± 3.3% and from 0.77 to 7.77%, respectively. The sensitivity, accuracy, and precision of the chosen methodology met the requirements of pesticide residue analysis. The results of the degradation dynamics test showed that the half-life of pydiflumetofen (t_1/2) in soybean plants and in soil were 3.6 to 5.7 and from 7.9 to 25.7 d, respectively. Assessment of the concentration of pydiflumetofen residues in soybeans revealed acute and chronic dietary exposure risks of 0.06 and 7.54%, respectively. As these values are very low, pydiflumetofen residues in soybeans present an acceptable risk to public health. The results of this study will help to guide the practical application of pydiflumetofen and minimize the environmental risks associated with its use. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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12 pages, 1709 KiB

Open AccessArticle

Development and Validation of an LC-MS/MS Method for Simultaneous Determination of Short Peptide-Based Drugs in Human Blood Plasma

by Elizaveta N. Fisher, Evgeny S. Melnikov, Vladimir Gegeckori, Natalya V. Potoldykova, Dmitry V. Enikeev, Kirill A. Pavlenko, Snezana Agatonovic-Kustrin, David W. Morton and Galina V. Ramenskaya

Molecules 2022, 27(22), 7831; https://doi.org/10.3390/molecules27227831 - 14 Nov 2022

Cited by 7 | Viewed by 3128

Abstract

A novel HPLC-ESI-MS/MS method for simultaneous gonadotropin-releasing hormone (GnRH) analogs and somatostatin analog quantitation was developed and validated. The developed method was successfully applied to pharmacokinetic studies. The sample preparation process included solid-phase extraction (SPE). Effective chromatographic separation of the analytes and internal [...] Read more.

A novel HPLC-ESI-MS/MS method for simultaneous gonadotropin-releasing hormone (GnRH) analogs and somatostatin analog quantitation was developed and validated. The developed method was successfully applied to pharmacokinetic studies. The sample preparation process included solid-phase extraction (SPE). Effective chromatographic separation of the analytes and internal standard (dalargin) was achieved with a C18 column, using a gradient elution with two mobile phases: 0.1% v/v formic acid (aqueous solution) and 0.1% v/v formic acid (acetonitrile solution). The linearity of the method was demonstrated within a concentration range of 0.5–20 ng/mL, with correlation coefficients between 0.998–0.999 for goserelin, buserelin, triptorelin, and octreotide, respectively. The relative standard deviation (RSD, %) values for method accuracy and precision did not exceed 20% at the lower level of quantitation (LLOQ) or 15% at other concentration levels. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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12 pages, 2241 KiB

Open AccessArticle

Simultaneous Determination of 108 Pesticide Residues in Three Traditional Chinese Medicines Using a Modified QuEChERS Mixed Sample Preparation Method and HPLC-MS/MS

by Xuyan Fan, Tao Tang, Song Du, Ningning Sang, Hao Huang, Chenghui Zhang and Xueping Zhao

Molecules 2022, 27(21), 7636; https://doi.org/10.3390/molecules27217636 - 7 Nov 2022

Cited by 12 | Viewed by 2573

Abstract

A rapid, efficient, simple, and high-throughput method for the simultaneous determination of 108 pesticide residues in three traditional Chinese medicines (TCMs) was established, comprising an improved QuEChERS method in combination with HPLC-MS/MS based on mixed samples. A quantity of 10 mL of acetonitrile [...] Read more.

A rapid, efficient, simple, and high-throughput method for the simultaneous determination of 108 pesticide residues in three traditional Chinese medicines (TCMs) was established, comprising an improved QuEChERS method in combination with HPLC-MS/MS based on mixed samples. A quantity of 10 mL of acetonitrile was used as extraction solvent, and 10 mg of amino-modified multi-walled carbon nanotubes (MWCNTs-NH₂) and 150 mg of anhydrous magnesium sulfate (MgSO₄) were selected as sorbents for dispersive solid phase extraction. The performance of the method was verified according to the analytical quality control standards of SANTE/11813/2017 guidelines. With good linearity (R² > 0.9984) in the range of 2–200 μg/L for all pesticides in the selected matrices, and good accuracy, precision, and high sensitivity, the recoveries were in the range of 70–120% for more than 95% of the pesticides, with a relative standard deviation (RSD) of less than 16.82% for all. The limit of detection (LOD) and limit of quantification (LOQ) of the method were 0.01–3.87 μg/kg and 0.07–12.90 μg/kg, respectively, for Fritillaria thunbergii Miq (F. thunbergii), Chrysanthemum Morifolium Ramat (C. morifolium), and Dendrobium officinale Kimura et Migo (D. officinale). The method was successfully applied to 60 batches of actual samples from different regions. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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13 pages, 3510 KiB

Open AccessArticle

Development of an Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Method for Hydroxylated Polychlorinated Biphenyls in Animal-Derived Food

by Wenyu Zhao, Na Cui, Yuan Huang, Zihao Wang, Peilong Wang, Haijun Liang, Ruiguo Wang and Xiaoou Su

Molecules 2022, 27(21), 7247; https://doi.org/10.3390/molecules27217247 - 25 Oct 2022

Cited by 3 | Viewed by 1519

Abstract

Hydroxylated polychlorinated biphenyls (OH-PCBs) are a group of metabolites biotransformed from polychlorinated biphenyls by animals with higher toxicities than their parent compounds. The present work developed and validated an analytical method for determinating penta-, hexa-, and hepta-chlorine substituted OH-PCBs in animal-derived food based [...] Read more.

Hydroxylated polychlorinated biphenyls (OH-PCBs) are a group of metabolites biotransformed from polychlorinated biphenyls by animals with higher toxicities than their parent compounds. The present work developed and validated an analytical method for determinating penta-, hexa-, and hepta-chlorine substituted OH-PCBs in animal-derived food based on ultra-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) with isotope-dilution. The target analytes were extracted with a 50% n-hexane/dichloromethane (v/v), purified by sulfuric acid-silica gel, and separated by 5% hydrated silica gel, achieving a final concentration of 100 times before injection to LC–MS/MS. The limits of detection (LOD) and quantification (LOQ) for target OH-PCBs were within the ranges of 0.003–0.010 μg/kg and 0.009–0.030 μg/kg, respectively. Average recoveries ranged between 76.7% and 116.5%, with relative standard deviations of less than 18.4%. The proposed method is simple, time-saving, sensitive, and accurate, making it a powerful tool for risk monitoring of OH-PCBs in animal-derived food. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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9 pages, 1279 KiB

Open AccessArticle

Autotoxicity of Endogenous Organic Acid Stress in Two Ganoderma lucidum Cultivars

by Pan Zou, Yongze Guo, Shu Ding, Zhaowei Song, Hanyuan Cui, Yue Zhang, Zhijun Zhang and Xiaoming Chen

Molecules 2022, 27(19), 6734; https://doi.org/10.3390/molecules27196734 - 9 Oct 2022

Cited by 7 | Viewed by 11077

Abstract

Ganoderma lucidum has been used as a rare medical mushroom for centuries in China, due to its health-promoting properties. Successive cropping obstacles are common in the cultivation of G. lucidum, although the remaining nutrients in the germ substrate are sufficient for a [...] Read more.

Ganoderma lucidum has been used as a rare medical mushroom for centuries in China, due to its health-promoting properties. Successive cropping obstacles are common in the cultivation of G. lucidum, although the remaining nutrients in the germ substrate are sufficient for a second fruiting. Here, we aimed to study the metabolite profile of G. lucidum via nontargeted metabonomic technology. Metabonomic data revealed that organic acids played an important role in the cropping obstacles of G. lucidum, which is accordance with the pH decrease in the germ substrate. A Kyoto encyclopedia of genes and genomes (KEGG) enrichment analysis indicated that most differential acids participated in the metabolic pathways. Five acids were all significantly upregulated by two MS with high energy (MS^E) modes in two cultivars, among which 5-hydroxy-2-oxo-4-ureido-2,5-dihydro-1H-imidazole-5-carboxylic acid is also involved in purine metabolism regulation and microbial metabolism in diverse environments. Taken together, this work illustrated the organic acid stress generated by G. lucidum, which formed the autotoxicity feedback, and resulted in cropping obstacles. Determining the cause of the cropping obstacles in G. lucidum will promote the utilization rate of fungus substrate to realize the sustainable use of this resource. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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14 pages, 2327 KiB

Open AccessArticle

An Innovative Chiral UPLC-MS/MS Method for Enantioselective Determination and Dissipation in Soil of Fenpropidin Enantiomers

by Rui Li, Yanqing Zhang, Yanhong Li, Zihao Chen, Zhen Wang and Minghua Wang

Molecules 2022, 27(19), 6530; https://doi.org/10.3390/molecules27196530 - 2 Oct 2022

Cited by 5 | Viewed by 1669

Abstract

As a chiral piperidine fungicide, fenpropidin has been widely used to control plant diseases. However, there are rare studies that have investigated fenpropidin at the enantiomer level. In this study, the single-factor analysis combined with a Box-Behnken design was used to obtain the [...] Read more.

As a chiral piperidine fungicide, fenpropidin has been widely used to control plant diseases. However, there are rare studies that have investigated fenpropidin at the enantiomer level. In this study, the single-factor analysis combined with a Box-Behnken design was used to obtain the optimal enantio-separation parameters of the fenpropidin enantiomers on ultra-performance liquid chromatography-tandem mass spectrometry. The absolute configuration of two fenpropidin enantiomers was confirmed for the first time using electron circular dichroism and optical activity. On the Lux cellulose-3 column, S-(-)-fenpropidin flowed out before R-(+)-fenpropidin. The enantio-separation mechanism was revealed by molecular docking. A modified QuEChERS method was developed for the trace determination of the fenpropidin enantiomers in seven food and environmental substrates. The average recoveries were 71.5–106.1% with the intra-day and inter-day relative standard deviations of 0.3–8.9% and 0.5–8.0%. The method was successfully verified by enantioselective dissipation of fenpropidin in soil under the field. R-(+)-fenpropidin dissipated faster than S-(-)-fenpropidin, and the half-lives were 19.8 d and 22.4 d. This study established a brand-new effective chiral analysis method for the fenpropidin enantiomers, providing a basis for accurate residue monitoring and the risk assessment of fenpropidin. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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13 pages, 1418 KiB

Open AccessArticle

Dissipation and Residue of Metalaxyl-M and Azoxystrobin in Scallions and Cumulative Risk Assessment of Dietary Exposure to Hepatotoxicity

by Yida Chai, Rong Liu, Xiaoying Du and Longfei Yuan

Molecules 2022, 27(18), 5822; https://doi.org/10.3390/molecules27185822 - 8 Sep 2022

Cited by 4 | Viewed by 1924

Abstract

Metalaxyl-M and azoxystrobin have been used to control various fungal diseases on scallion and other crops. In view of the adverse toxic effects of both on the mammalian liver, it is necessary to conduct a cumulative risk assessment of their dietary exposure to [...] Read more.

Metalaxyl-M and azoxystrobin have been used to control various fungal diseases on scallion and other crops. In view of the adverse toxic effects of both on the mammalian liver, it is necessary to conduct a cumulative risk assessment of their dietary exposure to consumers. The residues of metalaxyl-M and azoxystrobin on scallion were determined by a quick, easy, cheap, effective, rugged, and safe method (QuEChERS) combined with high-performance liquid chromatography tandem mass spectrometry (LC-MS/MS). The half-lives were about 1.15 and 3.89 days, respectively, and the final residues after a seven-day harvest interval were <0.001–0.088 mg/kg and 0.190–4.687 mg/kg, respectively. The cumulative dietary risk quotient of the two fungicides to Chinese consumers calculated by the probability model is 13.94%~41.25%. According to the results of the contribution analysis, the risk posed by azoxystrobin is much greater than that of metalaxyl-M. Although metalaxyl-M and azoxystrobin do not pose a cumulative risk to Chinese consumers, the risk to children and adolescents is significantly higher than that to adults. This suggests that in future research, more consideration should be given to the cumulative risk of compounds to vulnerable groups. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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17 pages, 2285 KiB

Open AccessArticle

Effect of Thermal Processing on the Metabolic Components of Black Beans on Ultra-High-Performance Liquid Chromatography Coupled with High-Field Quadrupole-Orbitrap High-Resolution Mass Spectrometry

by Yuchao Feng, Xia Fan, Shu Zhang, Miao Yu, Tong Wu, Ying Liang, Changyuan Wang and Hongzhi Yang

Molecules 2022, 27(12), 3919; https://doi.org/10.3390/molecules27123919 - 18 Jun 2022

Cited by 5 | Viewed by 2041

Abstract

An ultra-high-performance liquid chromatography coupled with high-field quadrupole-orbitrap mass spectrometry (UHPLC-QE-MS) histological platform was used to analyze the effects of two thermal processing methods (cooking and steaming) on the nutritional metabolic components of black beans. Black beans had the most amino acids, followed [...] Read more.

An ultra-high-performance liquid chromatography coupled with high-field quadrupole-orbitrap mass spectrometry (UHPLC-QE-MS) histological platform was used to analyze the effects of two thermal processing methods (cooking and steaming) on the nutritional metabolic components of black beans. Black beans had the most amino acids, followed by lipids and polyphenols, and more sugars. Multivariate statistical analysis indicated that heat processing significantly affected the metabolic component content in black beans, with effects varying among different components. Polyphenols, especially flavonoids and isoflavones, were highly susceptible. A total of 197 and 210 differential metabolites were identified in both raw black beans and cooked and steamed black beans, respectively. Cooking reduced the cumulative content of amino acids, lipids, polyphenols, sugars, and nucleosides, whereas steaming reduced amino acid and lipid content, slightly increased polyphenol content, and significantly increased sugar and nucleoside content. Our results indicated that metabolic components were better retained during steaming than cooking. Heat treatment had the greatest impact on amino acids, followed by polyphenols, fatty acids, sugars, and vitamins, indicating that cooking promotes the transformation of most substances and the synthesis of a few. The results of this study provide a basis for further research and development of nutritional products using black beans. Full article

(This article belongs to the Special Issue Application of LC-MS/MS in Biochemistry II)

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