研究报告

丝氨酸/甲硫氨酸-葡萄糖美拉德反应中杂环产物的高分辨质谱解析与毒性预测

  • 刘笛 ,
  • 刘霞 ,
  • 赵晓磊 ,
  • 何金兴 ,
  • 韩中惠
展开
  • (齐鲁工业大学(山东省科学院)食品科学与工程学院,山东省健康食品资源挖掘与创制重点实验室(筹),山东 济南,250353)
第一作者:硕士研究生(韩中惠副教授为通信作者, E-mail:zhhan@qlu.edu.cn)

收稿日期: 2026-01-09

  修回日期: 2026-02-11

  网络出版日期: 2026-07-31

基金资助

山东省重点研发计划项目(2023CXGC010712);国家自然科学基金项目(32102101)

High-resolution mass spectrometry analysis and toxicity prediction of heterocyclic products in the serine/methionine-glucose Maillard reaction

  • LIU Di ,
  • LIU Xia ,
  • ZHAO Xiaolei ,
  • HE Jinxing ,
  • HAN Zhonghui
Expand
  • (College of Food Science and Engineering, Qilu University of Technology (Shandong Academy of Sciences), Shandong Key Laboratory of Healthy Food Resources Exploration and Creation, Jinan 250353, China)

Received date: 2026-01-09

  Revised date: 2026-02-11

  Online published: 2026-07-31

摘要

美拉德反应会生成大量杂环类化合物,但当前研究仅关注其风味贡献,缺乏对产物种类、结构的系统解析及毒理学评价。该文以丝氨酸/甲硫氨酸-葡萄糖美拉德反应中的杂环产物为研究对象。采用静电场轨道阱超高分辨质谱仪对反应体系中的杂环产物进行筛选分析,借助Van Krevelen图进行杂环产物可视化分析,并运用Discovery Studio软件评估杂环产物的潜在毒性。结果表明,丝氨酸/甲硫氨酸-葡萄糖体系分别产生了198、159种杂环产物,丝氨酸-葡萄糖产物主要包括CHON和CHON1+x类型;甲硫氨酸-葡萄糖产物主要包括CHON、CHON1+x、CHONS和CHON1+xS类型。通过可视化分析发现,2个体系都以CHON1+x类为主,根据杂环产物结构主要分为吡咯、咪唑、吡嗪类。在所有杂环产物中发现有16种具有较高的致突变性、潜在发育毒性、皮肤致敏性。该研究揭示了氨基酸结构与杂环产物数量与组成的关系,并对产物进行了初步毒性评估,为进一步阐明热加工食品中杂环危害物的形成机制及安全性评价提供数据支撑与方法支持。

本文引用格式

刘笛 , 刘霞 , 赵晓磊 , 何金兴 , 韩中惠 . 丝氨酸/甲硫氨酸-葡萄糖美拉德反应中杂环产物的高分辨质谱解析与毒性预测[J]. 食品与发酵工业, 2026 , 52(13) : 240 -249 . DOI: 10.13995/j.cnki.11-1802/ts.045791

Abstract

The Maillard reaction yields a variety of heterocyclic compounds, yet current research predominantly focuses on their flavor contributions, while systematic analyses of their product species, structures, and toxicological properties are insufficient.In this study, heterocyclic products formed in serine/methionine-glucose Maillard reaction systems were investigated.Q-Exactive Orbitrap high-resolution mass spectrometry (HRMS) was used to screen and identify heterocyclic products in the reaction systems.Product distributions were visualized using the Van Krevelen diagram, and the potential toxicity of the heterocyclic products was evaluated using Discovery Studio software.The results showed that the serine/methionine-glucose system produced 198 and 159 heterocyclic products, respectively.The serine-glucose products mainly consisted of CHON and CHON1+x types, while methionine-glucose products mainly consisted of CHON, CHON1+x, CHONS and CHON1+xS types.Visualization analysis revealed that both systems were primarily characterized by CHON1+x type products, which were further classified into pyrrole, imidazole, and pyrazine derivatives based on their structural profiles.Among all heterocyclic compounds, 16 exhibited high mutagenicity, potential developmental toxicity, and skin sensitization potential.This study elucidated the relationship between amino acid structures and the quantity and composition of heterocyclic compounds, and performed preliminary toxicity assessments.These findings provide data and methodological support for further elucidating the formation mechanisms and safety evaluation of heterocyclic hazards in heat-processed foods.

参考文献

[1] AKBARI N, SHAFAROODI H, JAHANBAKHSH M, et al.4-Methylimidazole, a carcinogenic component in food, amount, methods used for measurement:A systematic review[J].Food Chemistry:X, 2023, 18:100739.
[2] 李玉美, 刘玉花, 魏冰, 等.美拉德反应及其对饼干烘烤过程的影响[J].食品工业, 2023, 44(8):5-8.
LI Y M, LIU Y H, WEI B, et al.Maillard reaction and its effect on the baking process of biscuit[J].The Food Industry, 2023, 44(8):5-8.
[3] WANG F S, WANG S R, QIN C Y, et al.Preparation, flavor compounds, and antioxidant activity of hawthorn fruit-derived Maillard reaction products[J].Applied Biological Chemistry, 2025, 68:49.
[4] RANNOU C, LAROQUE D, RENAULT E, et al.Mitigation strategies of acrylamide, furans, heterocyclic amines and browning during the Maillard reaction in foods[J].Food Research International, 2016, 90:154-176.
[5] ZULHAQ PARADIMAN A, TAHIR M M, DIRPAN A.Formation of acrylamide compounds in food products from Maillard reactions:A review article[J].BIO Web of Conferences, 2024, 96:01030.
[6] CAO H, CHEN B H, INBARAJ B S, et al.Preventive potential and mechanism of dietary polyphenols on the formation of heterocyclic aromatic amines[J].Food Frontiers, 2020, 1(2):134-151.
[7] JING M L, JIANG Q Q, ZHU Y M, et al.Effect of acrolein, a lipid oxidation product, on the formation of the heterocyclic aromatic amine 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) in model systems and roasted tilapia fish patties[J].Food Chemistry:X, 2022, 14:100315.
[8] ZAOUI M, LOUADJ L, FERRAND N, et al.Carcinogenic effect of low doses of polycyclic and heterocyclic aromatic hydrocarbons and amines and lack of protection by inulin supplementation[J].Food and Chemical Toxicology, 2024, 185:114454.
[9] XING H R, YAYLAYAN V.Mechanochemistry of Strecker degradation:Interaction of glyoxal with amino acids[J].Food Chemistry, 2024, 439:138071.
[10] 曹联飞, 何程豪, 孙玉敬.大蜜蜂和黑大蜜蜂蜂蜜的理化指标及抗氧化活性分析[J].食品与发酵工业, 2021, 47(9):262-267.
CAO L F, HE C H, SUN Y J.Physicochemical and antioxidant properties of honeys produced by Apis dorsata and Apis laboriosa[J].Food and Fermentation Industries, 2021, 47(9):262-267.
[11] SÁNCHEZ-GIRALDO M, VIOQUE-AMOR M, GÓMEZ-DÍAZ R, et al.Effect of carbohydrate formulas on instrumental and sensory parameters in dry-fermented Iberian pork sausages[J].Foods, 2025, 14(2):248.
[12] SHU C K.Pyrazine formation from serine and threonine[J].Journal of Agricultural and Food Chemistry, 1999, 47(10):4332-4335.
[13] PINSORN P, SANACHAI K, RUNGROTMONGKOL T, et al.Sulfur metabolism in durian pulps:Factors contributing to the production of volatile sulfur compounds during fruit ripening[J].Postharvest Biology and Technology, 2023, 206:112533.
[14] AL-BAARRI A N, LEGOWO A M, WIDAYAT.The browning value changes and spectral analysis on the Maillard reaction product from glucose and methionine model system[J].IOP Conference Series:Earth and Environmental Science, 2018, 102:012003.
[15] 喻世涛, 刘建华, 姚建武, 等.三种氨基酸对罗汉果美拉德反应物挥发性成分的影响[J].香料香精化妆品, 2020(5):5-10.
YU S T, LIU J H, YAO J W, et al.Effects of three amino acids on volatile components of Maillard reaction product from Momordica grosvenori[J].Flavour Fragrance Cosmetics, 2020(5):5-10.
[16] SHEN Y, HU L T, XIA B, et al.Effects of different sulfur-containing substances on the structural and flavor properties of defatted sesame seed meal derived Maillard reaction products[J].Food Chemistry, 2021, 365:130463.
[17] EI-CHORAB H A, EI-HADAAD A F.Effect of Serine on Chemical Composition and Antioxidant Activity of Beef fat/ Cysteine Model Systems[J].Egyptian Journal of Chemistry, 2013, 53(4):581-596.
[18] GLÜCK J, BUHRKE T, FRENZEL F, et al.In silico genotoxicity and carcinogenicity prediction for food-relevant secondary plant metabolites[J].Food and Chemical Toxicology, 2018, 116:298-306.
[19] LÖFFLER P, SCHYMANSKI E L, HENSCHEL H, et al.In silico frontiers shaping the next generation of transformation product prediction and toxicological assessment[J].Environmental Science & Technology, 2025, 59(36):19095-19106.
[20] 王思怿, 范宾.TOPKAT和TEST软件在化学物毒性预测中的应用[J].职业卫生与应急救援, 2017, 35(1):1-5;72.
WANG S Y, FAN B.Application of TOPKAT and TEST software in prediction of chemical toxicity[J].Occupational Health and Emergency Rescue, 2017, 35(1):1-5;72.
[21] 卢苑. 高效液相色谱法测定蜂蜜中的果糖和葡萄糖[J].食品安全导刊, 2024(34):79-81.
LU Y.Determination of fructose and glucose in honey by high performance liquid chromatography[J].China Food Safety Magazine, 2024(34):79-81.
[22] 颜雨涵, 黄啸天, 张依琳, 等.氨基酸与糖醇结构对褐变反应的影响及机制研究[J].食品与发酵工业, 2025, 51(1):167-173.
YAN Y H, HUANG X T, ZHANG Y L, et al.Effect and mechanism of the structure of amino acids and sugar alcohols on browning reaction[J].Food and Fermentation Industries, 2025, 51(1):167-173.
[23] LIU J Y, QU Y C, LIU Y, et al.Dynamic changes and formation mechanisms of volatile compounds in the Maillard reaction between theanine and fructose in tea[J].Food Research International, 2026, 227:118208.
[24] EDELHOCH H, BERNSTEIN R S, WILCHEK M.The fluorescence of tyrosyl and tryptophanyl diketopiperazines[J].Journal of Biological Chemistry, 1968, 243(22):5985-5992.
[25] ETXABIDE A, KILMARTIN P A, MATÉ J I, et al.Analysis of advanced glycation end products in ribose-, glucose- and lactose-crosslinked gelatin to correlate the physical changes induced by Maillard reaction in films[J].Food Hydrocolloids, 2021, 117:106736.
[26] ADAMS A, POLIZZI V, VAN BOEKEL M, et al.Formation of pyrazines and a novel pyrrole in Maillard model systems of 1, 3-dihydroxyacetone and 2-oxopropanal[J].Journal of Agricultural and Food Chemistry, 2008, 56(6):2147-2153.
[27] HUANG M G, LIU P, SONG S Q, et al.Contribution of sulfur-containing compounds to the colour-inhibiting effect and improved antioxidant activity of Maillard reaction products of soybean protein hydrolysates[J].Journal of the Science of Food and Agriculture, 2011, 91(4):710-720.
[28] PATHANIA S, NARANG R K, RAWAL R K.Role of sulphur-heterocycles in medicinal chemistry:An update[J].European Journal of Medicinal Chemistry, 2019, 180:486-508.
[29] CERNY C.The role of sulfur chemistry in thermal generation of aroma[M].Flavour Development, Analysis and Perception in Food and Beverages.Amsterdam:Elsevier,2015:187-210.
[30] ZHU C M, KONG L R, SHEN Q L, et al.The genotoxicity of selected heterocyclic nitrogen compounds:A quantitative structure-activity relationship study[J].Toxicological & Environmental Chemistry, 1998, 65(1-4):145-152.
文章导航

/

〈 〉