Heterocyclic amines (HCAs) and acrylamide are unintended hazardous substances generated by heating or processing of foods and are known as carcinogenic and mutagenic agents by the animal experiments. A simple method was established for a rapid and accurate determination of 12 types of HCAs (IQ, MeIQ...
Heterocyclic amines (HCAs) and acrylamide are unintended hazardous substances generated by heating or processing of foods and are known as carcinogenic and mutagenic agents by the animal experiments. A simple method was established for a rapid and accurate determination of 12 types of HCAs (IQ, MeIQ, Glu-P-1, Glu-P-2, MeIQx, Trp-P-1, Trp-P-2, PhIP, $A{\alpha}C$, $MeA{\alpha}C$, Harman and Norharman) and acrylamide in three food matrices (non-fat liquid, non-fat solid and fat solid) by isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS). In every sample, a mixture of internal standards including $IQ-d_3$, $MeIQx-d_3$, $PhIP-d_3$, $Trp-P-2-^{13}C_2-^{15}N$ and $MeA{\alpha}C-d_3$ was spiked for quantification of HCAs and $^{13}C_3$-acrylamide was also spiked for the analysis of acrylamide. HCAs and acrylamide in sample were extracted with acetonitrile and water, respectively, and then two solid-phase extraction cartridges, ChemElut: HLB for HCAs and Accucat: HLB for acrylamide, were used for efficiently removing interferences such as pigment, lipid, polar, nonpolar and ionic compounds. Established method was validated in terms of recovery, accuracy, precision, limit of detection, limit of quantitation, and linearity. This method showed good precision (RSD < 20%), accuracy (71.8~119.1%) and recovery (66.0~118.9%). The detection limits were 0.995, showing excellent linearity. These methods for the detection of HCAs and acrylamide by LC-MS/MS were applied to real samples and were successfully used for quantitative monitoring in the total diet study and this can be applied to risk assessment in various food matrices.
Heterocyclic amines (HCAs) and acrylamide are unintended hazardous substances generated by heating or processing of foods and are known as carcinogenic and mutagenic agents by the animal experiments. A simple method was established for a rapid and accurate determination of 12 types of HCAs (IQ, MeIQ, Glu-P-1, Glu-P-2, MeIQx, Trp-P-1, Trp-P-2, PhIP, $A{\alpha}C$, $MeA{\alpha}C$, Harman and Norharman) and acrylamide in three food matrices (non-fat liquid, non-fat solid and fat solid) by isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS). In every sample, a mixture of internal standards including $IQ-d_3$, $MeIQx-d_3$, $PhIP-d_3$, $Trp-P-2-^{13}C_2-^{15}N$ and $MeA{\alpha}C-d_3$ was spiked for quantification of HCAs and $^{13}C_3$-acrylamide was also spiked for the analysis of acrylamide. HCAs and acrylamide in sample were extracted with acetonitrile and water, respectively, and then two solid-phase extraction cartridges, ChemElut: HLB for HCAs and Accucat: HLB for acrylamide, were used for efficiently removing interferences such as pigment, lipid, polar, nonpolar and ionic compounds. Established method was validated in terms of recovery, accuracy, precision, limit of detection, limit of quantitation, and linearity. This method showed good precision (RSD < 20%), accuracy (71.8~119.1%) and recovery (66.0~118.9%). The detection limits were 0.995, showing excellent linearity. These methods for the detection of HCAs and acrylamide by LC-MS/MS were applied to real samples and were successfully used for quantitative monitoring in the total diet study and this can be applied to risk assessment in various food matrices.
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제안 방법
In this study, for the analysis of acrylamide and 12 species of HCAs (IQ, MeIQ, Glu-P-1, Glu-P-2, MeIQx, PhIP, Trp-P-1, Trp-P-2, AαC, MeAαC, Harman, and Norharman) using LC-MS/MS in the various agricultural matirces, foodstuffs are divided into three groups: non-fat solid, non-fat liquid, and fat solid. This study aimed to achieve significant accuracy, precision, and recovery by applying different internal standards to each analyte. Moreover, the performance of the established analytical method was evaluated in terms of linearity, accuracy, precision, limit of detection (LOD), and limit of quantitation (LOQ), and its applicability to real samples was investigated to confirm it as the analytical method of monitoring HCAs and acrylamide for the risk assessment in the total diet study.
LC-MS/MS analysis. The HCA analysis was performed using an Agilent 1260 series HPLC system (Agilent Technologies, Palo Alto, CA, USA) coupled to API 3200 triple quadrupole mass spectrometer (MDS Sciex, Concord, ON, Canada) equipped with electrospray ionization (ESI). All the analytes were separated by an Atlantis T3 column (2.
The acrylamide analysis was performed by using a Shimadzu 20AD HPLC system (Kyoto, Japan) coupled to API 3200 triple quadrupole mass spectrometer (MDS Sciex, Concord, ON, Canada) equipped with electrospray ionization (ESI). Analytes were separated with matrices using an Aqua C18 column (2 × 250 mm, i.
Matrix samples for validation were apple juice, peanut butter and rice porridge purchased from the retail markets. All samples were analysed according to the optimized procedure.
In the preliminary study, we performed optimization of appropriate cartridges, elution solvents, and solvent composiotions, which are not shown. Cartridges of HLB, QuEChERS (PSA 400 mg, MgSO41200 mg), QuEChERS (PSA 400 mg, MgSO4 1200 mg, GCB 400 mg), and Chem Elut were examined and combination of Chem Elut and HLB was used as it gave best result. As the eluent for Chem Elut, methylene chloride:ethylacetate (3 : 1) was selected from the comparison of the several solvent compositions (methylene chloride:ethylacetate, 1 : 0, 3 : 1, 4 : 1, 1 : 1, 1 : 4, 0 : 1).
In addition, methanol contents as the eluent of HLB was compared with the 30, 50, 70, 90% methanol containing 2% acetic acid and 90% methanol was selected because it showed best recovery for all analytes In the preliminary study of acrylamide, we firstly examined FDA method which represents for all foods and found that this method can be applied to three matrices (non-fat solid, non-fat liquid and fat solid) without any modifications. HLB clean-up after water extraction was used and followed by Accucat clean-up according to the FDA method through all samples in this study.
Method validation. To evaluate the effectiveness of the newly developed analytical method fitted to the three matrices, validation was performed using the parameters such as selectivity, recovery, accuracy, precision, linearity, LOD, and LOQ and verified with the criteria assigned in the CODEX guideline CAC/GL 71-2009. Samples fortified with all the analytes at their target concentrations (low, medium and high) were extracted and analyzed for the method verification.
To evaluate the effectiveness of the newly developed analytical method fitted to the three matrices, validation was performed using the parameters such as selectivity, recovery, accuracy, precision, linearity, LOD, and LOQ and verified with the criteria assigned in the CODEX guideline CAC/GL 71-2009. Samples fortified with all the analytes at their target concentrations (low, medium and high) were extracted and analyzed for the method verification.
Five replicates of the fortified samples (10, 50 and 100 ng for HCAs and 10, 100 and 500 ng/g for acrylamide) were determined for recovery, accuracy, and intra-day precision. Inter-day precision was analysed on the five different days in the same way.
Highly reproducible accurate results demonstrate the reliability of this method for residue analyses. Analyte-free matrices were used to evaluate the extraction recovery. Using the peak areas of analytes obtained by diluted standard solutions spiked into extracts after the extraction as A, and the peak areas of the diluted standard solutions spiked before extraction as B, the extraction recoveries were calculated as extraction recovery (%) = B/A × 100.
Application to real samples. To evaluate the applicability of the proposed method, eight types of agricultural products (apple juice, vinegar, flour, cereal, jam, chocolates, cookie and potato chip) purchased from 18 retail markets from nine cities (South Korea) were analysed by the optimized analytical procedures.
In this study, for the analysis of acrylamide and 12 species of HCAs (IQ, MeIQ, Glu-P-1, Glu-P-2, MeIQx, PhIP, Trp-P-1, Trp-P-2, AαC, MeAαC, Harman, and Norharman) using LC-MS/MS in the various agricultural matirces, foodstuffs are divided into three groups: non-fat solid, non-fat liquid, and fat solid.
대상 데이터
Every standard solution (1 mg/mL) was dissolved in methanol, and the mixture solution was prepared by the dilution, and all the standard solutions were stored in a refrigerator (−4℃) until analysis. Caffeic acid, ammonium formate, and formic acid were purchased from Sigma-Aldrich (St. Louis, MO, USA). All the HPLC grade solvents for the pretreatment and mobile phase were purchased from J.
Oasis HLB cartridge (60 mg, 3 mL) was purchased from Waters Corporation (Dublin, Ireland). Power Sonic 420 sonicator purchased from Hawshin Technology (Gwangju, Korea) and C-SK shaker purchased from Changshin Scientific (Pocheon, Korea) were used for the pretreatment. For concentrating the extracts, a GMG-2000 evaporator from EYELA (Tokyo, Japan) was used.
Oasis HLB cartridge (200 mg, 6 mL) was purchased from Waters Corporation (Dublin, Ireland). A centrifuge machine was purchased from Hanil Science Industrial (Incheon, Korea).
Sample preparation. Eight types of agricultural products (apple juice, vinegar, flour, cereal, jam, chocolates, cookies, and potato chip) were analysed in this study. Representative foods were collected from 18 mega-markets in nine metropolitan cities (Seoul, Pusan, Incheon, Daegu, Daejeon, Kwangju, Ulsan, Suwon and Changwon) nationwide and made into composites by pooling them for total diet study.
Eight types of agricultural products (apple juice, vinegar, flour, cereal, jam, chocolates, cookies, and potato chip) were analysed in this study. Representative foods were collected from 18 mega-markets in nine metropolitan cities (Seoul, Pusan, Incheon, Daegu, Daejeon, Kwangju, Ulsan, Suwon and Changwon) nationwide and made into composites by pooling them for total diet study. Matrix samples for validation were apple juice, peanut butter and rice porridge purchased from the retail markets.
To determine the LOD and LOQ, 10 ng of HCA and acrylamide standards were spiked into each matrix, and five replicates were analysed. The LOD was calculated as 3.
In this study, among the 12 HCAs and acrylamide, only harman, norharman and acrylamide were detected from eight samples. Harman and norharman were detected in the range of ND-8.
이론/모형
Acrylamide: The pretreatment of acrylamide was performed by the FDA method (24) for the three matrices (rice porridge, apple juice and peanut butter).
성능/효과
) in agricultural foods. The established method was successfully evaluated using the parameters according to the CODEX guideline CAC/GL 71-2009 and showed good precision, accuracy and recovery. Detection limits were in the adequate range for all analytes and this method was successfully applied to real samples.
In conclusion, analytical methods using the LC-MS/MS MRM mode to detect 12 species of HCAs (IQ, MeIQ, Glu-P-1, Glu-P-2, MeIQx, Trp-P-1, Trp-P-2, PhIP, AaC, MeAaC, Harman, and Norharman) and acrylamide formed mainly by the Maillard reaction were established using six isotope labelled internal standards (IQ-d3, MeIQx-d3, PhIP-d3, Tr-pP-2-13C2-15N, MeAaC-d3, and AA-13C3) in agricultural foods. The established method was successfully evaluated using the parameters according to the CODEX guideline CAC/GL 71-2009 and showed good precision, accuracy and recovery.
후속연구
Detection limits were in the adequate range for all analytes and this method was successfully applied to real samples. It could be used as a promising analytical method to monitor HCAs and acrylamide for the risk assessment in the total diet study and the results of real sample analysis may be used as a preliminary data for the strategy on the reduction of hazardous compounds in the food.
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