摘要
为探究糖熏色素5-(葡萄糖基-α-1-6-葡萄糖)-羟甲基糠醛(5-(α-D-glucopyranosyl-(1-6)-α-D-glucopyranosyloxymenthyl)-2-furancarboxaldehyde,5-GGMF)的形成途径,采用量子化学计算对蔗糖的热分解反应位点、葡萄糖与5-羟甲基糠醛(5-hydroxymethylfurfural,5-HMF)及两分子葡萄糖间的脱水反应方式、5-HMF和5-GGMF的形成路径进行分析。结果表明:蔗糖热分解的初始位置为果糖基-氧键的裂解;葡萄糖与5-HMF或两分子葡萄糖间发生相互作用时,均是范德华力在复合物中起主导作用,且都会因为强氢键作用促进分子间脱水反应的发生;蔗糖形成5-HMF时,其热解后形成的葡萄糖部分比果糖部分生成5-HMF需要更大的活化能且反应速率更低,因此果糖部分更容易形成5-HMF,而在果糖部分形成5-HMF的两条路径中,路径5比路径4更容易发生,因为路径5在能量上和反应动力学上都表现出明显的优势;在蔗糖形成5-GGMF的途径中,转糖基化路径能垒总体较低,相较于二糖脱水路径和三糖脱水路径都更加有利,其中路径C2,即蔗糖热解生成果糖和葡萄糖,然后葡萄糖与5-HMF反应先生成5-葡萄糖氧甲基糠醛,后者再与一分子游离的葡萄糖生成5-GGMF,此路径最有利于5-GGMF的生成,无论是从能垒角度,还是动力学上的可行性。本研究结果可为今后控制和干预糖熏产品的色泽提供理论依据和参考。
In order to explore the formation pathways of 5-(α-D-glucopyranosyl-(1-6)-α-D-glucopyranosyloxymenthyl)-2-furancarboxaldehyde(5-GGMF),a pigment formed during the process of sugar smoking,the thermal decomposition reaction site of sucrose,the dehydration reaction modes between glucose and 5-hydroxymethylfurfural(5-HMF)and between two molecules of glucose,and the formation pathways of 5-HMF and 5-GGMF were analyzed by quantum chemical calculation.The results showed that the initial position of thermal decomposition of sucrose was the cleavage of fructosyl-oxygen bond.van der Waals force played a leading role in the complexes formed by the interaction between glucose and 5-HMF and between two molecules of glucose,and the intermolecular dehydration reaction was promoted by strong hydrogen bonding.The formation of 5-HMF from the glucose moiety formed after the pyrolysis of sucrose needed more activation energy than from the fructose moiety formed with a lower reaction rate,indicating that the fructose moiety was more prone to form 5-HMF.Among the two formation pathways of 5-HMF from the fructose moiety,pathway 5 was more prone to occur than pathway 4,because pathway 5 showed obvious advantages in energy and reaction kinetics.In the formation pathways of 5-GGMF from sucrose,the energy barrier of the transglycosylation pathway was overall lower,which was more favorable than the disaccharide dehydration and trisaccharide dehydration pathways.Among them,pathway C2,including three steps:the pyrolysis of sucrose to produce fructose and glucose,the reaction of glucose with 5-HMF to form 5-glucosyloxymethylfurfural(5-GMF),and the reaction of 5-GMF with a molecule of free glucose to produce 5-GGMF,was most conducive to the generation of 5-GGMF from both an energy barrier and kinetic perspective.The results of this study can provide a theoretical basis and reference for controlling and intervening in the color of sugar smoked products in the future.
作者
叶国庆
牛玉敏
范朝侠
杨慧
刘登勇
YE Guoqing;NIUYumin;FAN Chaoxia;YANG Hui;LIU Dengyong(College of Food Science and Engineering,Bohai University,Jinzhou 121013,China)
出处
《食品科学》
EI
CAS
CSCD
北大核心
2024年第10期62-71,共10页
Food Science
基金
辽宁省“揭榜挂帅”科技计划(重点)项目(2022JH1/10900011,2021JH1/10400033)。
关键词
糖熏色素
5-(葡萄糖基-α-1-6-葡萄糖)-羟甲基糠醛
量子化学
密度泛函理论
sugar smoking pigment
5-(α-D-glucopyranosyl-(1-6)-α-D-glucopyranosyloxymenthyl)-2-furancarboxaldehyde
quantum chemistry
density functional theory
