College of Agriculture, Jilin Agricultural Science and Technology University, Jilin 132101, China.
Agricultural Technology Extension Station of Jiaohe City, Jiaohe 132500, China.
Molecules. 2024 May 3;29(9):2115. doi: 10.3390/molecules29092115.
The polyphenol-Maillard reaction is considered one of the important pathways in the formation of humic-like substances (HLSs). Glucose serves as a microbial energy source that drives the humification process. However, the effects of changes in glucose, particularly its concentration, on abiotic pathways remain unclear. Given that the polyphenol-Maillard reaction requires high precursor concentrations and elevated temperatures (which are not present in soil), gibbsite was used as a catalyst to overcome energetic barriers. Catechol and glycine were introduced in fixed concentrations into a phosphate-buffered solution containing gibbsite using the liquid shake-flask incubation method, while the concentration of glucose was controlled in a sterile incubation system. The supernatant fluid and HLS components were dynamically extracted over a period of 360 h for analysis, thus revealing the influence of different glucose concentrations on abiotic humification pathways. The results showed the following: (1) The addition of glucose led to a higher degree of aromatic condensation in the supernatant fluid. In contrast, the supernatant fluid without glucose (Glu0) and the control group without any Maillard precursor (CK control group) exhibited lower degrees of aromatic condensation. Although the total organic C (TOC) content in the supernatant fluid decreased in all treatments during the incubation period, the addition of Maillard precursors effectively mitigated the decreasing trend of TOC content. (2) While the C content of humic-like acid (C) and the C/C ratio (the ratio of humic-like acid to fulvic-like acid) showed varying increases after incubation, the addition of Maillard precursors resulted in a more noticeable increase in C content and the C/C ratio compared to the CK control group. This indicated that more FLA was converted into HLA, which exhibited a higher degree of condensation and humification, thus improving the quality of HLS. The addition of glycine and catechol without glucose or with a glucose concentration of 0.06 mol/L was particularly beneficial in enhancing the degree of HLA humification. Furthermore, the presence of glycine and catechol, as well as higher concentrations of glucose, promoted the production of N-containing compounds in HLA. (3) The presence of Maillard precursors enhanced the stretching vibration of the hydroxyl group (-OH) of HLA. After the polyphenol-Maillard reaction of glycine and catechol with glucose concentrations of 0, 0.03, 0.06, 0.12, or 0.24 mol/L, the aromatic C structure in HLA products increased, while the carboxyl group decreased. The presence of Maillard precursors facilitated the accumulation of polysaccharides in HLA with higher glucose concentrations, ultimately promoting the formation of Al-O bonds. However, the quantities of phenolic groups and phenols in HLA decreased to varying extents.
多酚-美拉德反应被认为是形成类腐殖质物质(HLS)的重要途径之一。葡萄糖是微生物能量的来源,它驱动腐殖化过程。然而,葡萄糖变化的影响,特别是其浓度,对非生物途径仍不清楚。鉴于多酚-美拉德反应需要高前体浓度和升高的温度(土壤中不存在),水铝石被用作催化剂来克服能量障碍。儿茶酚和甘氨酸以固定浓度引入含有水铝石的磷酸盐缓冲溶液中,使用液体摇瓶孵育法,而葡萄糖的浓度在无菌孵育系统中进行控制。在 360 小时的时间内动态提取上清液和 HLS 成分进行分析,从而揭示不同葡萄糖浓度对非生物腐殖化途径的影响。结果表明:(1)葡萄糖的添加导致上清液中芳香族缩合程度更高。相比之下,没有葡萄糖的上清液(Glu0)和没有任何美拉德前体的对照(CK 对照组)表现出较低的芳香族缩合程度。虽然在孵育期间所有处理的上清液中总有机碳(TOC)含量均下降,但美拉德前体的添加有效缓解了 TOC 含量下降的趋势。(2)尽管孵育后类腐殖酸(C)的 C 含量和 C/C 比(类腐殖酸与富里酸的比值)呈不同程度的增加,但与 CK 对照组相比,美拉德前体的添加导致 C 含量和 C/C 比的增加更为显著。这表明更多的 FLA 转化为 HLA,其表现出更高程度的缩合和腐殖化,从而提高了 HLS 的质量。在没有葡萄糖或葡萄糖浓度为 0.06mol/L 的情况下添加甘氨酸和儿茶酚特别有利于增强 HLA 腐殖化的程度。此外,甘氨酸和儿茶酚的存在以及较高的葡萄糖浓度促进了 HLA 中含氮化合物的生成。(3)美拉德前体的存在增强了 HLA 中羟基(-OH)的伸缩振动。在 0、0.03、0.06、0.12 或 0.24mol/L 的葡萄糖浓度下,甘氨酸和儿茶酚与葡萄糖的多酚-美拉德反应后,HLA 产物中的芳香族 C 结构增加,而羧基减少。美拉德前体的存在促进了 HLA 中多糖的积累,在较高的葡萄糖浓度下,最终促进了 Al-O 键的形成。然而,HLA 中酚基团和酚类的数量在不同程度上减少。