Effect of Exogenous Glucose at Different Concentrations on the Formation of Dark-Brown Humic-like Substances in the Maillard Reaction Pathway Based on the Abiotic Condensation of Precursors Involving δ-MnO2

Abstract

The Maillard reaction is a type of nonenzymatic browning process and is an important pathway for the formation of humic-like substances (HLSs). Glucose is one of the three crucial precursors for the Maillard reaction, and a change in glucose concentration can inevitably affect the humification pathway, thereby regulating the composition and quality of HLSs. To verify the scientific hypothesis, the method of liquid shake-flask culture was adopted. Both catechol and glycine with fixed concentrations were added to a phosphate buffer including δ-MnO2, and only the concentration of glucose was adjusted in the sterile culture system. The obtained supernatant fluid and dark-brown residue were collected dynamically through the centrifugation method. The E4/E6 ratio and total organic C (TOC) of the supernatant fluid, the humus composition, and FTIR spectra for the dark-brown residue, and the elemental composition of humic-like acid (HLA) extracted from the dark-brown residue were analyzed to reveal the effect of varying glucose concentrations on the abiotic humification pathways for the Maillard reaction and the characteristics of relevant products under abiotic processes. The results reveal that (1) the exogenous addition of glucose at different concentrations simplifies the molecular structure in the supernatant fluid, and the TOC content is decreased to varying degrees, among which the addition of 0.24 mol/L glucose leads to the formation of simpler organic molecules in the supernatant compared to that for the other treatments, and the addition of 0.03 mol/L glucose shows the largest decrease in TOC content; (2) Under the coexistence of glycine and catechol, CHLA treated with the addition of glucose at different concentrations shows an upward trend in the course of the culture, which is significantly higher than that obtained for the CK control. The addition of 0.12 mol/L glucose results in the largest increase in CHLA. During the culture period, the structure of HLA molecules from each treatment first become complex and then gradually become simpler. Finally, the molecular structure of HLA treated with different concentrations of glucose becomes more complex, but the structure of HLA molecules from the CK control tends to be simplified. The addition of glucose can improve the condensation degree of HLA molecules, among which the addition of 0.12 mol/L glucose shows the most significant effect. With increasing exogenous glucose concentration, the number of N-containing compounds in the HLA molecules further decreases, while the number of O-containing functional groups increases. (3) The greater the concentration of glucose added, the higher the proportion of aromatic C structures in the dark-brown residue. During this process, the Mn-O bond lattice vibration of the δ-MnO2 layered structure is greatly enhanced. The organic molecules in the dark-brown residue and δ-MnO2 are bound to each other through intermolecular hydrogen bonding. The CHLA/CFLA ratio for each treatment increases to varying degrees after the culture period, indicating that the addition of glucose is more conducive to the improvement of humus quality than the CK control, among which the addition of 0.12 mol/L glucose shows the best effect.