Abstract

The recovery of antioxidant polyphenols from light, dark and mix brewer’s spent grain (BSG) using conventional maceration, microwave and ultrasound assisted extraction was investigated. Total polyphenols were measured in the crude (60% acetone), liquor extracts (saponified with 0.75% NaOH) and in their acidified ethyl acetate (EtOAc) partitioned fractions both by spectrophotometry involving Folin–Ciocalteu reagent and liquid-chromatography-tandem mass spectrometry (LC-MS/MS) methods. Irrespective of the extraction methods used, saponification of BSG yielded higher polyphenols than in the crude extracts. The EtOAc fractionations yielded the highest total phenolic content (TPC) ranging from 3.01 ± 0.19 to 4.71 ± 0.28 mg gallic acid equivalent per g of BSG dry weight. The corresponding total polyphenols quantified by LC-MS/MS ranged from 549.9 ± 41.5 to 2741.1 ± 5.2 µg/g of BSG dry weight. Microwave and ultrasound with the parameters and equipment used did not improve the total polyphenol yield when compared to the conventional maceration method. Furthermore, the spectrophotometric quantification of the liquors overestimated the TPC, while the LC-MS/MS quantification gave a closer representation of the total polyphenols in all the extracts. The total polyphenols were in the following order in the EtOAc fractions: BSG light > BSG Mix > BSG dark, and thus suggested BSG light as a sustainable, low cost source of natural antioxidants that may be tapped for applications in food and phytopharmaceutical industries.

Highlights

  • Brewers’ spent grain (BSG) is generated in millions of tonnes every year as the major by-product of the brewing industry, with an annual global production estimated to be 39 million tonnes, of whichEU generates ~8 million tonnes [1,2]

  • By other authors, on the crude extracts of light and dark BSG have shown total phenolic content (TPC) in a similar range [24,34]. These relatively low TPC levels in the crude extracts are because of the fact that the BSG contains a high amount of lignin ranging from 19.4–49.2 g/100 g that is connected to its cell wall polysaccharides by phenolic acids [10,16,35]

  • The UPLC-MS/MS data have shown that the saponification followed by acidification and subsequent liquid-liquid partitioning (EtOAc) is the best procedure for polyphenol recovery and enrichment from BSG irrespective of extraction method

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Summary

Introduction

Brewers’ spent grain (BSG) is generated in millions of tonnes every year as the major by-product of the brewing industry, with an annual global production estimated to be 39 million tonnes, of whichEU generates ~8 million tonnes [1,2]. BSG is used as a low-value animal feed with a market value of. Hemicellulose, lignin, protein and lipids as the main components, BSG contains low molecular weight phenolic compounds that have been associated with a wide array of health-benefiting properties [4,5]. A number of extraction methods, optimized and applied towards the recovery of polyphenols from BSG, have been comprehensively reviewed by several authors [3,6,7]. Depending on the types of BSG produced as a result of different cooking temperatures (70–250 ◦ C), the polyphenol contents differ between the lightly roasted malt producing light or pale BSG and the deeply roasted malts producing dark or black BSG. Since BSG predominantly contains bound phenolics, chemical or enzymatic hydrolysis protocols are routinely

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