Unveiling the γ-carboxyl role of glutamic acid in pyrazine formation from N-(1-deoxy-α-D-ribulos-1-yl)-glutamic acid: Mechanistic insights via integrated experimental and density functional theory approaches

文献类型： 外文期刊

第一作者： Zhan, Huan

作者： Zhan, Huan;Zhang, Li;Xu, Maosen;Yi, Xinyue;Li, Yangu;Zhao, Zongze;Diao, Yuduan

作者机构：

关键词： Amadori rearrangement product; Density functional theory; alpha-Dicarbonyls; gamma-Carboxyl deprotonation; Pyrazines; Strecker degradation

期刊名称：FOOD CHEMISTRY （ 影响因子：9.8； 五年影响因子：9.7 ）

ISSN： 0308-8146

年卷期： 2025 年 492 卷

页码：

收录情况： SCI

摘要： This study deciphers the gamma-carboxyl group's pivotal role in controlling pyrazine formation during thermal degradation of glutamic acid-derived Amadori rearrangement product (ARP). Integrated density functional theory (DFT) and pH-controlled experiments revealed gamma-carboxyl deprotonation (pKa = 4.29) initiates electronic effects that activate the amino group's nucleophilic capacity (-NH3+ to -NHS-like reactivity) remotely through orbital polarization and highest occupied molecular orbital (HOMO) energy elevation (-1.39 eV), enabling efficient alpha-dicarbonyl interactions. Comparative thermal treatments of Glu-derived ARP with supplementary amino acids revealed distinct flavor modulation pathways: lysine catalyzed alpha-dicarbonyl generation, boosting pyrazine yields, while glycine favored pyrrole derivatives via methylamine-mediated retro-aldol cleavage inhibition. pH-Dependent experiments confirmed that gamma-carboxyl deprotonation (pKa = 4.29) electronically activates the amino group even in its protonated state (-NH3+), bypassing direct deprotonation. The present work advances mechanistic understanding of Maillard reaction pathways and propose pH adjustment and amino acid supplementation as strategic tools for the regulation and improvement of ARP flavor formation.

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