Chair of Food Chemistry and Molecular and Sensory Science, Technical University of Munich, Lise-Meitner-Str. 34, D-85354 Freising, Germany.
Bavarian Center for Biomolecular Mass Spectrometry, Gregor-Mendel-Straße 4, D-85354 Freising, Germany.
J Agric Food Chem. 2024 Jul 24;72(29):16423-16437. doi: 10.1021/acs.jafc.4c01000. Epub 2024 Jul 15.
A sensitive high-performance liquid chromatography-triple quadrupole mass spectrometry (HPLC-MS/MS) method, leveraging both technique and internal calibration, was developed for the simultaneous and comprehensive quantitative analysis of 46 antioxidants and antioxidant precursors in different beer types without any cleanup procedure. Combined with their antioxidant activity, a dose-activity estimation exposed a group of 10 key antioxidants, namely, tryptophan, tyrosine, hordatine A, hordatine B, procyanidin B, prodelphinidin B, tachioside (3-methoxy-4-hydroxyphenyl-β-d-glucopyranoside), (+)-catechin, tyrosol, and ferulic acid. To study the effect of antioxidants in spiking and aging studies, another liquid chromatography-MS (LC-MS)-based method was developed, monitoring markers for oxidation in beer. A positive effect of the antioxidants on the flavor stability at naturally relevant concentrations was shown by a slowing of oxygen-dependent aging reactions highlighted in beer storage trials under oxygen atmosphere. Thereby, a doubling of the natural concentration of all investigated antioxidants in beer revealed a limit inhibition of 67% on the degradation of isocohumulone to hydroxy-alloisocohumulone.
建立了一种灵敏的高效液相色谱-三重四极杆质谱（HPLC-MS/MS）方法，利用技术和内标校准，可同时全面定量分析 46 种不同啤酒类型中的抗氧化剂和抗氧化前体，无需任何净化程序。结合其抗氧化活性，通过剂量-活性评估，确定了 10 种关键抗氧化剂，即色氨酸、酪氨酸、霍达汀 A、霍达汀 B、原花青素 B、原儿茶素 B、落新妇苷（3-甲氧基-4-羟基苯基-β-d-吡喃葡萄糖苷）、（+）-儿茶素、酪醇和阿魏酸。为了研究抗氧化剂在添加和老化研究中的作用，还开发了另一种基于液相色谱-质谱（LC-MS）的方法，监测啤酒中氧化的标志物。通过在含氧气氛下的啤酒储存试验，突出显示了抗氧化剂对氧气依赖性老化反应的风味稳定性的积极影响，从而证明了在自然相关浓度下，抗氧化剂对风味稳定性具有积极作用。因此，将所有研究的抗氧化剂在啤酒中的天然浓度提高一倍，可将异葎草酮降解为羟基-异葎草酮的抑制率限制在 67%。
