Distilled spent grain (DSG), as the major by-product of baijiu making, contains melanoidins generated via the Maillard reaction. In this study, four melanoidin fractions (RF1‒RF4) were isolated successively from dried DSG (DDSG) using sodium hydroxide solution and water as extractants, and the content, preliminary structure, and ACE-inhibitory activities in vitro of melanoidins were first investigated. The antioxidant activity was also evaluated. The results indicated that the total content of melanoidins was 268.60 mg/g DDSG dry weight (dw) using a model system of glucose and serine as standard, and RF4 showed the highest content of melanoidins (174.30 mg/g DDSG dw). Functional groups like C=O, N‒H, C‒N, O‒H, C‒H, C‒O, C-C, and ‒C‒CO‒C‒ were present in the structure of melanoidins from RF4, as determined by Fourier transform infrared (FT-IR) assay. The highest antioxidant activities, as assessed by 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS•+
), ferric-reducing antioxidant power (FRAP), and 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) assays, and the highest angiotensin-converting enzyme (ACE) inhibitory activity (95.92% at 2 mg RF4/mL) were also exhibited by RF4. The RF4 was further fractionated by ultrafiltration based on molecular weight (MW). The more than 100 kDa melanoidins (RF4-6) exhibited the highest yield and antioxidant activity. The 3‒10 kDa melanoidins (RF4-2) were more efficient in ACE-inhibitory activity. Our study could raise awareness of the DDSG as a value-added resource.
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