基于链长的白酒酒糟醇溶蛋白反胶束萃取：乙醇、离子强度和离液剂的协同作用

Chain Length-Dependent Reverse Micelle Extraction of Prolamins From Baijiu Jiuzao: Synergistic Effects of Ethanol, Ionic Strength, and Chaotropic Agent.

作者信息

Yu TingTing, Yang FuRong, Wang Fang, Chen YongMei, Liu Yi, Hu Nan

机构信息

College of Chemical Engineering, Sichuan University of Science and Engineering, Zigong, China.

出版信息

J Sep Sci. 2025 Aug;48(8):e70242. doi: 10.1002/jssc.70242.

DOI:10.1002/jssc.70242

PMID:40762092

Abstract

This study investigated the chain length-dependent extraction efficiency of two cationic surfactants-dodecyltrimethylammonium bromide (C12, 12-carbon chain) and cetyltrimethylammonium bromide (C16, 16-carbon chain)-for reverse micelle extraction of prolamins from Baijiu Jiuzao (Chinese Baijiu distillers' grains). Although pH variations (4.0-9.0) had negligible effects, ethanol, ionic strength, and chaotropic agent demonstrated distinct chain length-dependent behaviors: ethanol increased C12's forward extraction efficiency by 10.6% (absolute) while enhancing C16's backward efficiency by 8.7%. Potassium chloride enhanced C16's forward efficiency by 4.7%, while potassium bromide significantly improved C12's backward efficiency by 15.9%. Guanidine hydrochloride consistently promoted C16 in both extraction phases. Dynamic light scattering demonstrated significant differences (p < 0.05) in reverse micelle sizes: C12 formed smaller empty reverse micelles (1.5 ± 0.2 nm) compared to C16 (2.5 ± 0.5 nm). During forward extraction, reverse micelles expanded significantly to 217.9 ± 6.3 nm (C12) and 311.2 ± 43.2 nm (C16). Backward extraction released prolamin particles of 449.0 ± 16.2 nm (C12) and 650.4 ± 29.7 nm (C16), confirming the size-exclusion-driven release mechanism. The more compact C12 reverse micelles correlated with lower total prolamin yield (26.6 ± 0.1% vs. 32.2 ± 0.1% for C16, p < 0.01) and substantially diminished bovine serum albumin recovery (5.2 ± 0.2% vs. 45.3 ± 2.5%, p < 0.01). Sodium dodecyl sulfate-polyacrylamide gel electrophoresis analysis corroborated these findings, further demonstrating that reverse micelle-extracted prolamins formed thermally stable dimers resistant to reductive cleavage. Combined with dynamic light scattering data (particle size range: 400-700 nm in the backward-extraction aqueous phase), these findings demonstrate that prolamin aggregates after reverse micelle extraction. These findings demonstrate that surfactant chain length as a key parameter for optimizing reverse micellar systems, where shorter-chain surfactants facilitate selective extraction, whereas longer chains enhance yields.

摘要

本研究考察了两种阳离子表面活性剂——十二烷基三甲基溴化铵（C12，含12个碳链）和十六烷基三甲基溴化铵（C16，含16个碳链）——从白酒酒槽（中国白酒酒糟）中反胶束萃取醇溶蛋白时，链长依赖性的萃取效率。尽管pH值变化（4.0 - 9.0）的影响可忽略不计，但乙醇、离子强度和离液剂表现出明显的链长依赖性行为：乙醇使C12的正向萃取效率提高了10.6%（绝对值），同时使C16的反向萃取效率提高了8.7%。氯化钾使C16的正向萃取效率提高了4.7%，而溴化钾使C12的反向萃取效率显著提高了15.9%。盐酸胍在两个萃取阶段均持续促进C16的萃取。动态光散射表明反胶束尺寸存在显著差异（p < 0.05）：与C16（2.5 ± 0.5 nm）相比，C12形成的空反胶束较小（1.5 ± 0.2 nm）。在正向萃取过程中，反胶束显著膨胀至217.9 ± 6.3 nm（C12）和311.2 ± 43.2 nm（C16）。反向萃取释放出尺寸为449.0 ± 16.2 nm（C12）和650.4 ± 29.7 nm（C16）的醇溶蛋白颗粒，证实了尺寸排阻驱动的释放机制。更紧凑的C12反胶束与较低的总醇溶蛋白产率相关（C12为26.6 ± 0.1%，C16为32.2 ± 0.1%，p < 0.01），并且牛血清白蛋白回收率大幅降低（C12为5.2 ± 0.2%，C16为45.3 ± 2.5%，p < 0.01）。十二烷基硫酸钠 - 聚丙烯酰胺凝胶电泳分析证实了这些发现，进一步表明反胶束萃取的醇溶蛋白形成了抗还原裂解的热稳定二聚体。结合动态光散射数据（反向萃取水相中的粒径范围：400 - 700 nm），这些发现表明反胶束萃取后醇溶蛋白会聚集。这些发现表明表面活性剂链长是优化反胶束体系的关键参数，其中短链表面活性剂有利于选择性萃取，而长链则提高产率。