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MICROCHEMICAL JOURNAL · 2021 · IF 4.821

Evaluation of the matrix effect of pH value and sugar content on the analysis of pesticides in tropical fruits by UPLC-MS/MS

Jing Zhao,Jingjing Pu,Xiaopeng Wu,Boyu Chen,Yan He,Yue Zhang,Bingjun Han

Matrix effect (ME) is a critical factor that can significantly compromise the accuracy of pesticide residue analyses performed using ultra-performance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS). In this study, five pesticides of different types, namely difenoconazole (triazoles), chlorpyrifos (organophosphates), thiram (dithiocarbamates), carbaryl (carbamates), and pyraclostrobin (strobilurins), were selected to investigate the UPLC-MS/MS MEs in five typical tropical fruits. The MEs and possible mechanisms of the main influence factors, i.e., pH value and sugar content, were studied for the pesticide residues in the tropical fruits. The proposed method was validated in terms of linearity, limit of detection (LOD), recovery, and precision. In the range of 0.005–0.5 μg mL −1 , the coefficients of determination (r) were better than 0.999, while the LODs and recoveries ranged from 0.16 to 4.4 μg kg −1 and from 75% to 120%, respectively. Results show that among the five typical tropical fruits, the ME was largest in longan, followed by that in banana; pineapple and guava showed lower MEs than those in banana, whereas papaya had the lowest. Chlorpyrifos has the largest ME, followed by thiram and difenoconazole, and the other pesticides have very small MEs. Moreover, the MEs can be reduced by adjusting the pH value and sugar content of the sample matrix. This study can be applied to assess the influence of MEs on the analysis results.

CAS / MDL: 64-18-6
研究领域: 分析化学 · 食品科学
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RESEARCH ON CHEMICAL INTERMEDIATES · 2022 ·Vol. 49 ·期 1 ·23-42 · IF 3.134

Synergistic and efficient degradation of acid red 73 by using UV, H2O2, and PDS under neutral conditions: water matrix effects and transformation pathways

Lin Yingzi,Hou Ao,Li Hao,Shi Chunyan,Chen Lei,Yuan Baoling,Liu Yi,Wang Yu,Liu Xiaochen

Dye wastewater with high concentration, large molecular weight, complex structure, and certain toxicity has brought a serious burden to the environment. In this study, acid red 73 dye (AR73) was used as the model pollutant to compare the degradation effects of different systems on AR73. The influence factors of a UV/hydrogen peroxide/peroxydisulfate (UV/H 2 O 2 /PDS) composite system, such as H 2 O 2 dosage, initial concentration of AR73, initial pH value, anion concentration, and actual water, on the degradation of AR73 were investigated. Compared with other systems, the UV/H 2 O 2 /PDS composite system had the best degradation effect of AR73, with a degradation efficiency of 98.98%, which conforms to the pseudo-first-order reaction kinetic model, the pseudo-first-order reaction kinetic constant ( k obs ) is 0.1339 min −1 . And the synergy coefficients in this complex system were all greater than 2. Specifically, the degradation efficiency of the UV/H 2 O 2 /PDS composite system for AR73 was the highest when the initial pH was neutral. The presence of anions inhibited the degradation of AR73, and the real water reduced the degradation efficiency for AR73. Electron spin resonance (ESR) detection and free radicals capture test demonstrated that hydroxyl radical ( · OH) was the main reactive species in AR73 degradation, and its 80.66–84.93% contribution. With the destruction of the structure of AR73 by free radicals, anilines, phenols, and oxalic acid were found to be the main intermediate products during the degradation of AR73 by gas-phase mass spectrometry and UV–vis spectrograms. The changes in toxicity during the degradation of AR73 by the UV/H 2 O 2 /PDS complex system were also assessed.

研究领域: 环境科学 · 化学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Active chlorine mediated ammonia oxidation in an electrified SnO2–Sb filter: Reactivity, mechanisms and response to matrix effects

Zhipeng Liu,Yewen Tao,Zhong Zhang,Jiazhou He,Kui Yang,Jinxing Ma

Ammonia pollution control has gained increasing attention as a result of the existential threat to the environment. The electrochemical advanced oxidation process has demonstrated to be an attractive and environmentally benign platform for aqueous ammonia removal because it only requires electricity and water as a clean “reagent”. Herein, we developed a porous SnO 2 –Sb filter toward high-efficient ammonia conversion. Despite the introduction of enhanced convection, chlorine-mediated ammonia oxidation dominated the reaction mechanism of the electrified SnO 2 –Sb filter at circumneutral pH. At an extremely short hydraulic contact time (1.0–5.1 min), ammonia was primarily oxidized to N 2 with no chloramines detected. Matrix effect assays showed that the chloride–to–ammonia ratio was vital to determine the removal rate and product selectivity. A pH buffer, HCO 3 − , might prompt ammonia removal whilst inhibiting chlorate formation. In contrast, the ammonia removal performance of the SnO 2 –Sb filter deteriorated in the presence of dissolved organic matter ( e.g. , humic acid). The matrix effects significantly influenced the process efficiency to treat municipal sewage and lake water. The results of this study can advance our understanding of electrochemical ammonia oxidation and provide insight into the effective implementation and optimization of the flow-through process.

研究领域: 环境科学 · 化学工程
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BIOMEDICAL CHROMATOGRAPHY · 2025 ·Vol. 39 ·期 2 ·e6067 · IF 1.7

Evaluation of the Impact of HIFU on Peptide Bond Formation: A Study Using SPE-LC-MS/MS Methodology

Jiale Liu,Rongfei Yuan,Qi Wang,Hai Qiao,Yuling Yang,Siyu Yang,Hua Zhang,Chang Chen

High-intensity focused ultrasound (HIFU) is a noninvasive soft tissue ablation technique, which utilizes ultrasound energy to induce thermal coagulation necrosis in targeted tissues. Whether this high energy causes side effects in vivo, such as the formation of peptide bonds, has not been fully investigated. Glycylglycine is the simplest dipeptide and hence is often used as a model compound for peptide studies. In this study, we developed and validated a sensitive quantification method based on ion-exchange solid-phase extraction, liquid chromatography, and tandem mass spectrometry (SPE-LC-MS/MS) for the analysis of glycylglycine without derivatization, and then used it to evaluate whether HIFU promoted peptide bond formation in aqueous solution (without enzymes) and plasma (with enzymes). The results showed that strong cation exchange SPE significantly reduced the matrix effect and improved the sensitivity of the LC-MS/MS method. No formation of glycylglycine in the aqueous solution or plasma was observed following HIFU irradiation.

CAS / MDL: 14091-11-3 103616-89-3
研究领域: 生物化学 · 医学工程
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ANALYST · 2024 ·Vol. 149 ·期 11 ·3140-3151 · IF 3.6

Prediction of mass spectrometry ionization efficiency based on COSMO-RS and machine learning algorithms

Cheng-Zhen Nie,Hao Liu,Xu-Hui Huang,Da-Yong Zhou,Xu-Song Wang,Lei Qin

Non-targeted analysis of high-resolution mass spectrometry (MS) can identify thousands of compounds, which also gives a huge challenge to their quantification. The aim of this study is to investigate the impact of mass spectrometry ionization efficiency on various compounds in food at different solvent ratios and to develop a predictive model for mass spectrometry ionization efficiency to enable non-targeted quantitative prediction of unknown compounds. This study covered 70 compounds in 14 different mobile phase ratio environments in positive ion mode to analyze the rules of the matrix effect. With the organic phase ratio from low to high, most compounds changed by 1.0 log units in log IE. The addition of formic acid enhanced the signal but also promoted the matrix effect, which often occurred in compounds with strong ionization capacity. It was speculated that the matrix effect was mainly in the form of competitive charge and charged droplet’ gasification sites during MS detection. Subsequently, we present a log IE prediction method built using the COSMO-RS software and the artificial neural network (ANN) algorithm to address this difficulty and overcome the shortcomings of previous models, which always ignore the matrix effect. This model was developed following the principles of QSAR modeling recommended by the Organization for Economic Cooperation and Development (OECD). Furthermore, we validated this approach by predicting the log IE of 70 compounds, including those not involved in the log IE model development. The results presented demonstrate that the method we put forward has an excellent prediction accuracy for log IE (R2pred = 0.880), which means that it has the potential to predict the log IE of new compounds without authentic standards.

CAS / MDL: 64-18-6
研究领域: 分析化学 · 食品科学 · 机器学习
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INDUSTRIAL CROPS AND PRODUCTS · 2022 · IF 6.449

Accurate identification and quantification of ultra-multi-target flavours in essential oils through a combination of retention index distribution-based parallel dual-column GC-MS/MS and analyte protectants

Lining Pan,Yaqiong Qin,Mantang Chen,Huimin Liu,Shaofeng Liu,Xuehui Sun,Xiaoyu Wang,Li Chen,Fuwei Xie,Huapeng Cui,Tao Wang,Ruihong Liu,Peijian Sun

Comprehensively characterising the flavour composition of essential oils (EOs) is critical due to its wide application in food , cosmetics and medicine industries. The present research aims to obtain accurate identification and quantification of 592 flavours in EOs from different plant sources using parallel dual-column gas chromatography-tandem mass spectrometry (GC-MS/MS). A strategy based on retention index distribution was introduced to simplify the optimisation process of separation distribution on the dual columns and elution distribution within the analysis process for analytes. Each analyte was identified as a unique and resolved peak through the complementary separation capacity of dual columns and the specific monitoring ability of the MS/MS transitions. To improve the accuracy of quantitative analysis, a combination of 1,2-octanediol, 1,2-nonanediol, 1,2-tetradecanediol, and phytantriol was used as analyte protectants (APs) for matrix effect compensation. The addition of APs effectively eliminated the differences in the peak response of the same analyte in pure solvent and EO samples from different plant sources. The proposed method demonstrated good linearity with correlation coefficient values above 0.999 for 72.5% analytes, high sensitivity with limit of quantifications below 10 ng/mL for 77.7% analytes, good accuracy with recoveries between 80% and 120% for 97.3% analytes, and high repeatability with relative standard deviations between 0.1% and 10.0% for 96.6% analytes at all three spiked levels. Compared to GC/MS in analysis of marigold, lavender , and fennel oils, this parallel dual-column GC-MS/MS method is a much more reliable and powerful tool for accurately identifying and quantifying ultra-multi-target flavours in EOs, which is critical for fully characterising their flavour composition, precisely controlling the quality of EO materials and further developing a new flavouring technology.

研究领域: 食品科学 · 分析化学
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TALANTA · 2019 · IF 4.916

Multi-capillary column high-pressure photoionization time-of-flight mass spectrometry and its application for online rapid analysis of flavor compounds

Xuan Chen,Lei Hua,Jichun Jiang,Fan Hu,Ningbo Wan,Haiyang Li

High-pressure photoionization time-of-flight mass spectrometry (HPPI-TOFMS) is a versatile and highly sensitive analytical technique for online and real-time analysis of trace volatile organic compounds in complex mixtures. However, discrimination of isomers is usually a great challenge for the soft ionization method, and matrix effect is also inevitable under high pressure in the HPPI source. In this work, we describe a first attempt to develop a two-dimensional (2D) hyphenated instrument by coupling of a multi-capillary column (MCC) with a HPPI-TOFMS to overcome these problems. The capability of the MCC-HPPI-TOFMS for discrimination of isomeric compounds and elimination of the matrix effect was demonstrated by analyzing flavor mixtures. With the merits of fast separation, soft ionization and high detection sensitivity, satisfactory effects in the 2D analysis were achieved, despite the relatively low chromatographic resolution of MCC. As a result, three isomers, eucalyptol, l -menthone and linalool , in a flavor mixture were successfully categorized within 90 s, and the matrix effect caused by solvent ethanol was significantly eliminated as well. The limits of detection (LODs) down to sub-ppbv level were achieved for the investigated five flavor compounds without any enrichment process, and an excellent repeatability was obtained with the relative standard deviations (RSDs) of signal intensities ≤5%. The MCC-HPPI-TOFMS system was preliminarily applied for rapid and online analysis of flavor compounds in the exhaled gas of a volunteer after mouth rinsing with a gargle product. The rapid changes of the three flavor compounds, as well as the steady endogenous metabolite acetone, in the exhaled gas were successfully determined with a time-resolution of only 1.5 min.

CAS / MDL: 142-19-8 78-70-6
研究领域: 分析化学 · 食品科学
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CHEMOMETRICS AND INTELLIGENT LABORATORY SYSTEMS · 2019 · IF 2.786

Probe technique-based generalized multivariate standard addition strategy for the analysis of fluorescence signals with matrix effects

Sheng-Xian Li,Ying-Qi Wang,Zeng-Ping Chen,Yao Chen

The presence of practically unavoidable matrix effects from the spectroscopically inactive compounds (which may enhance or suppress intensities of spectral measurements of samples) and background interference effects from the spectroscopically active compounds other than the analytes of interest in real-world complex samples can significantly affect the accuracy of quantitative results of optical chem/biosensing techniques, and hence greatly hinder their applications to real-world complex samples. In this contribution, a probe technique-based generalized multivariate standard addition strategy was designed for the analysis of fluorescence signals with both matrix effects and background interference effects. The performance of the proposed strategy was tested on a proof-of-concept system of quantifying Zn 2+ in real-world samples such as rice and zinc gluconate oral solution using a selective fluorescence probe dansylaminoethyl-cyclen and compared with the classical univariate standard addition method. Experimental results demonstrated that one standard addition sample was enough for the proposed strategy to provide satisfactory quantitative results (consistent with the results of ICP-MS) for Zn 2+ in the real test samples, which were by far better than the corresponding results of the classical univariate standard addition method. The main contributions of this research are 1) to greatly improve the accuracy of quantitative results of optical chem/biosensing techniques, and 2) to open up an avenue for quantitative analysis of small-volume biological samples or some precious samples using invasive techniques in fields such as biomedical sciences, clinical diagnosis and archeology, etc.

研究领域: 分析化学 · 生物医学
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JOURNAL OF CHROMATOGRAPHY A · 2025 · IF 4

Development of a procedure based on dispersive solid phase extraction and LC-MS/MS for the analysis of perfluoroalkyl and polyfluoroalkyl substances in food contact materials

Yang Yang,Jin Wang,Jia Qiu,Yan Luo,Chun Yang,Shali Tang,Hui Cao,Qian Wang,Xiaojing Lai

To monitor per- and polyfluoroalkyl substances (PFAS) in food contact materials (FCMs), an LC-MS/MS method for the simultaneous detection of 35 PFAS was developed and validated in paper and plastic products. Chromatographic and mass spectrometry parameters, extraction solvents, matrix effects in details were studied. The impact of matrix effects on PFAS concentration was analyzed, revealing that the matrix enhancement effect was more significant for some PFAS with low concentrations. In order to eliminate the matrix effect and enhance detection accuracy, a straightforward pretreatment method combining methanol ultrasonic extraction with dispersive solid-phase extraction (d-SPE) was established. PFHpA, PFDA, PFTriDA, PFTeDA, PF-3,7-DMOA, HFPO-DA, PFHxS, PFHpS, PFOS, 4:2 FTS, 6:2 FTS, 8:2 FTS, 10:2 FTS, and 6:2 diPAP required further d-SPE extraction with PSA, and other substances could be directly extracted by methanol ultrasonic treatment. The recoveries of the established method for all compounds ranged from 62.40 to 135.80%, with a relative standard deviation (RSD) of 0.15% to 16.81%. The limit of quantitation was between 0.005 and 0.02 mg·kg −1 . The method was applied to detect PFAS in 119 FCMs, resulting in the identification of 15 PFAS.

CAS / MDL: 64-18-6
研究领域: 分析化学 · 食品安全
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