A simultaneous derivatization of 3-monochloropropanediol and 1,3-dichloropropane with hexamethyldisilazane–trimethylsilyl trifluoromethanesulfonate at room temperature for efficient analysis of food sample analysis

Abstract

This paper reports the application of hexamethyldisilazane-trimethylsilyl trifluoromethanesulfonate (HMDS-TMSOTf) for the simultaneous silylation of 3-monochloro-1,2-propanediol (3-MCPD) and 1,3-dicholoropropanol (1,3-DCP) in solid and liquid food samples. 3-MCPD and 1,3-DCP are chloropropanols that have been established as Group 2B carcinogens in clinical testing. They can be found in heat-processed food, especially when an extended high-temperature treatment is required. However, the current AOAC detection method is time-consuming and expensive. Thus, HMDS-TMSOTf was used in this study to provide a safer, and cost-effective alternative to the HFBI method. Three important steps are involved in the quantification of 3-MCPD and 1,3-DCP: extraction, derivatization and quantification. The optimization of the derivatization process, which involved focusing on the catalyst volume, derivatization temperature, and derivatization time was performed based on the findings obtained from both the Box-Behnken modeling and a real experimental set up. With the optimized conditions, the newly developed method was used for actual food sample quantification and the results were compared with those obtained via the standard AOAC method. The developed method required less samples and reagents but it could be used to achieve lower limits of quantification (0.0043mgL(-1) for 1,3-DCP and 0.0011mgL(-1) for 3-MCPD) and detection (0.0028mgL(-1) for 1,3-DCP and 0.0008mgL(-1) for 3-MCPD). All the detected concentrations are below the maximum tolerable limit of 0.02mgL(-1). The percentage of recovery obtained from food sample analysis was between 83% and 96%. The new procedure was validated with the AOAC method and showed a comparable performance. The HMDS-TMSOTf derivatization strategy is capable of simultaneously derivatizing 1,3-DCP and 3-MCPD at room temperature, and it also serves as a rapid, sensitive, and accurate analytical method for food samples analysis.

A boronic acid–modified C60 derivatization reagent for the rapid detection of 3‐monochloropropane‐1,2‐diol using matrix‐assisted laser desorption/ionization‐mass spectrometry

“…Due to the potential carcinogenicity of 3-MCPD, many countries have set a maximum acceptable concentration of 3-MCPD at three levels: 0.02, 0.2, and 1.0 μg mL À1 . 4 It can be observed that the developed method can meet the real sample detection requirements.…”

“…A comparison with other derivatization techniques was performed to evaluate the performance of the developed method. 4,12,13,24,40 Compared with the traditional techniques such as HPLC and GC-MS, the proposed method has a relatively high sensitivity and a superiority in the analysis time, the sample pretreatment processes, and the requirement of the amount of foodstuffs (Table 2). Therefore, the developed method can be employed as a high-throughput strategy in real applications to screen samples with illegal amounts of 3-MCPD.…”

“…2,3 3-MCPD was labeled as a group 2B carcinogen by the International Agency for Research on Cancer due to its potential carcinogenicity. [4][5][6] The European Food Safety Agency has set a tolerable daily intake limit of 2 μg kg À1 body weight per day for 3-MCPD. 7 Therefore, the development of accurate and efficient analytical methods to monitor the content of 3-MCPD in foodstuff is needed.…”

“…17 Therefore, chemical derivatization strategies were widely used to overcome these obstacles. Derivatization reagents previously used in the analysis of 3-MCPD include acetone, 18 phenylboronic acid (PBA), [19][20][21] heptafluorobutyrylimidazole (HFBI), 22,23 heptafluorobutyric anhydride (HFBA), 24,25 hexamethyldisilazane, 4 and trimethylsilimidazole. 26,27 Among them, HFBI and HFBA derivatization reagents exhibit limited selectivity because they react with all nucleophilic compounds, whereas PBA-containing boronic acid group is a highly selective derivatization reagent that can react with cis-diol specifically.…”

Simultaneous Analysis of 3-MCPD and 1,3-DCP in Asian Style Sauces Using QuEChERS Extraction and Gas Chromatography–Triple Quadrupole Mass Spectrometry

“…Additionally, the low molecular weights of 3-MCPD and 1,3-DCP result in low m / z fragmentation patterns following mass spectrometer (MS) ionization. Derivatizing agents previously used in the simultaneous analysis of 3-MCPD and 1,3-DCP include N -methyl- N -(trimethylsilyl) trifluoroacetamide (MSTFA), bis­(trimethylsilyl) trifluoroacetamide (BSTFA), , heptafluorobutyric anhydride (HFBA), , heptafluorobutyrylimidazole (HFBI), ,− hexamethyldisilazine-trimethylsilyl trifluoromethanesulfonate (HDMS-TMSOTf), HFBA modified with trimethylamine (HFBA-Et 3 N), and 1-trimethylsilylimidazole (TSIM) . Phenylboronic acid (PBA) can be used to derivatize 3-MCPD but not 1,3-DCP because PBA needs two hydroxyl groups to form the cyclic phenyl boronate derivative .…”