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      Dissipation of Emamectin Benzoate Residues in Rice and Rice-Growing Environments

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          Abstract

          The experiment developed the ultra-high-performance liquid chromatography–tandem mass spectrometry (UPLC/MS/MS) method for testing emamectin benzoate, and studied the metabolism of emamectin benzoate in rice plants and rice-growing environments via application of this testing method. The dissipation curve of emamectin benzoate standard substance was good at 0.5–200 μg L −1, and its correlation coefficient was greater than 0.99. In the concentration range of 0.1–50 μg kg −1, the average recovery rate of plants, soil, and field water was 82 %–102 %, and relative standard deviation (RSD) was between 0.3 % and 15.9 %. Half-lives in rice plants and soil were 0.8–2.8 days and 1.9–3.8 days, respectively, and emamectin benzoate was not detected in rice or rice hull. The experiment showed that emamectin benzoate is harmless to human health at the concentration recommended by the manufacturer.

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          Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC-MS/MS.

          In recent years, high-performance liquid chromatography (HPLC) with tandem mass spectrometric (MS/MS) detection has been demonstrated to be a powerful technique for the quantitative determination of drugs and metabolites in biological fluids. However, the common and early perception that utilization of HPLC-MS/MS practically guarantees selectivity is being challenged by a number of reported examples of lack of selectivity due to ion suppression or enhancement caused by the sample matrix and interferences from metabolites. In light of these serious method liabilities, questions about how to develop and validate reliable HPLC-MS/MS methods, especially for supporting long-term human pharmacokinetic studies, are being raised. The central issue is what experiments, in addition to the validation data usually provided for the conventional bioanalytical methods, need to be conducted to confirm HPLC-MS/MS assay selectivity and reliability. The current regulatory requirements include the need for the assessment and elimination of the matrix effect in the bioanalytical methods, but the experimental procedures necessary to assess the matrix effect are not detailed. Practical, experimental approaches for studying, identifying, and eliminating the effect of matrix on the results of quantitative analyses by HPLC-MS/MS are described in this paper. Using as an example a set of validation experiments performed for one of our investigational new drug candidates, the concepts of the quantitative assessment of the "absolute" versus "relative" matrix effect are introduced. In addition, experiments for the determination of, the "true" recovery of analytes using HPLC-MS/MS are described eliminating the uncertainty about the effect of matrix on the determination of this commonly measured method parameter. Determination of the matrix effect allows the assessment of the reliability and selectivity of an existing HPLC-MS/MS method. If the results of these studies are not satisfactory, the parameters determined may provide a guide to what changes in the method need to be made to improve assay selectivity. In addition, a direct comparison of the extent of the matrix effect using two different interfaces (a heated nebulizer, HN, and ion spray, ISP) under otherwise the same sample preparation and chromatographic conditions was made. It was demonstrated that, for the investigational drug under study, the matrix effect was clearly observed when ISP interface was utilized but it was absent when the HN interface was employed.
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            Matrix effects: the Achilles heel of quantitative high-performance liquid chromatography-electrospray-tandem mass spectrometry.

            High-performance liquid chromatography coupled by an electrospray ion source to a tandem mass spectrometer (HPLC-ESI-MS/MS) is the current analytical method of choice for quantitation of analytes in biological matrices. With HPLC-ESI-MS/MS having the characteristics of high selectivity, sensitivity, and throughput, this technology is being increasingly used in the clinical laboratory. An important issue to be addressed in method development, validation, and routine use of HPLC-ESI-MS/MS is matrix effects. Matrix effects are the alteration of ionization efficiency by the presence of coeluting substances. These effects are unseen in the chromatogram but have deleterious impact on methods accuracy and sensitivity. The two common ways to assess matrix effects are either by the postextraction addition method or the postcolumn infusion method. To remove or minimize matrix effects, modification to the sample extraction methodology and improved chromatographic separation must be performed. These two parameters are linked together and form the basis of developing a successful and robust quantitative HPLC-ESI-MS/MS method. Due to the heterogenous nature of the population being studied, the variability of a method must be assessed in samples taken from a variety of subjects. In this paper, the major aspects of matrix effects are discussed with an approach to address matrix effects during method validation proposed.
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              Advances in analytical toxicology: the current role of liquid chromatography-mass spectrometry in drug quantification in blood and oral fluid.

              H Maurer (2004)
              This paper reviews procedures for quantification of drugs in the biosamples blood, plasma, serum, or oral fluid (saliva, etc.) using liquid chromatography coupled with single-stage or tandem mass spectrometry (LC-MS, LC-MS-MS). Such procedures are important prerequisites for competent toxicological judgment and consultation in clinical and forensic toxicology. They cover blood (plasma, serum) analysis of amphetamines and related designer drugs, anesthetics, anticonvulsants, benzodiazepines, opioids, serotonergic drugs, tricyclic antidepressants, neuroleptics, antihistamines, beta-blockers, muscle relaxants, and sulfonylurea-type antidiabetics, and oral fluid analysis of amphetamines and related designer drugs, cocaine, benzoylecgonine, codeine, morphine, enantiomers of methadone and its main metabolite 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), the nicotine metabolites cotinine and hydroxycotinine, and finally risperidone and its metabolite 9-hydroxyrisperidone. Basic information on the procedures is given in two tables and an example of quantification is illustrated in two figures. The pros and cons of such LC-MS procedures including sample work-up and ion suppression effects are critically discussed.
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                Author and article information

                Journal
                Molecules
                Molecules
                molecules
                Molecules
                MDPI
                1420-3049
                23 January 2020
                February 2020
                : 25
                : 3
                : 483
                Affiliations
                Key Laboratory of Test Technology on Food Quality and Safety of Shandong Province, Institute of Agricultural Quality Standards and Testing Technology Research, Shandong Academy of Agricultural Sciences, 202 Gongyebeilu Road, Jinan 250100, China; zhbsdengligang@ 123456shandong.cn (L.D.); zhbschenlu@ 123456shandong.cn (L.C.); zhbsguanshuai@ 123456shandong.cn (S.G.); zhbsliujunhua@ 123456shandong.cn (J.L.); zhbsLiangjingyun@ 123456shandong.cn (J.L.)
                Author notes
                [* ]Correspondence: zhbslixia@ 123456shandong.cn (X.L.); zhbslizengmei@ 123456shandong.cn (Z.L.); Tel.: +0531-6665-7913 (X.L.); +0531-6665-7913 (Z.L.)
                Article
                molecules-25-00483
                10.3390/molecules25030483
                7037347
                31979297
                fa5b4155-ab08-4781-b22b-f3d2655abda6
                © 2020 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 25 November 2019
                : 16 January 2020
                Categories
                Article

                emamectin benzoate,rice,residue,degradation,uplc-ms/ms
                emamectin benzoate, rice, residue, degradation, uplc-ms/ms

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