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中国精品科技期刊2020

薄荷醇基低共熔剂提取皇菊叶黄素制备叶黄素-薄荷醇共晶的研究

Extraction of Lutein from Chrysanthemum by Menthol-based Deep Eutectic Solvents to Synthesize the Lutein-Menthol Cocrystal

  • 摘要: 为建立一种绿色高效的天然叶黄素提取方法并提升其稳定性,本研究利用薄荷醇基低共熔剂(deep eutectic solvents,DESs)提取皇菊叶黄素并制备叶黄素-薄荷醇共晶,首先对比 6 种薄荷醇基 DES(薄荷醇-乙酸、薄荷醇-丙酸、薄荷醇-辛酸、薄荷醇-癸酸、薄荷醇-己酸、薄荷醇-乳酸)对皇菊叶黄素的提取效率,筛选出最优溶剂类型;在此基础上,以乙醇含量、料液比、提取温度、提取时间为单因素考察变量,结合响应面法优化提取工艺参数;同时对提取所得叶黄素溶液进行抗氧化活性评价,开展叶黄素-薄荷醇共晶与市售叶黄素粉末的光、热稳定性差异,并采用液相色谱串联质谱法(LC-MS/MS)对共晶进行组分定性定量分析。结果表明:薄荷醇-乙酸(DES-1)为最佳低共熔溶剂;优化后的最佳提取条件为乙醇含量47%(V/V)、料液比 1:45(g/mL)、提取温度 69 ℃,该条件下叶黄素提取量可达 644.11±1.99 μg/g。DES-1 提取制备的叶黄素溶液对羟自由基和 DPPH 自由基的清除率分别达 77.52%、84.58%,显著高于传统乙醇提取法(P<0.01)。在 30 ℃/75% RH 热环境与4500 Lux/25 ℃光照条件下,叶黄素-薄荷醇共晶的叶黄素保留率分别为 84.34% 和 33.73%,均显著高于市售叶黄素,形成的共晶结构不仅能物理阻碍氧气渗透,同时叶黄素两端的醇羟基还会与薄荷醇上羟基形成强氢键作用,从而显著提升稳定性。经 LC-MS/MS 鉴定,共晶中共检出叶黄素、叶黄素棕榈酸酯等 33 种叶黄素类组分,其中游离叶黄素含量最高,提取量达 107.93±11.36 μg/g。本研究制备的叶黄素-薄荷醇共晶显著提高叶黄素稳定性,可为叶黄素的实际开发利用提供更多可能。

     

    Abstract: To establish an eco-friendly and efficient method for extracting natural lutein while enhancing its stability, this study employed menthol-based deep eutectic solvents (DESs) for the extraction of lutein from chrysanthemum and the preparation of lutein-menthol cocrystals. The feasibility of this approach was evaluated through the analysis of the antioxidant activity of the extracted lutein solutions, as well as the stability and composition of the cocrystals. Firstly, the extraction efficiency of six DESs (menthol-acetic acid, menthol-propionic acid, menthol-octanoic acid, menthol-decanoic acid, menthol-hexanoic acid, and menthol-lactic acid) for lutein was compared, identifying the optimal eutectic solvent. Subsequently, single-factor investigations were conducted on ethanol content, solid-to-liquid ratio, extraction temperature, and extraction time, and the extraction process parameters were optimized by using the response surface method. At the same time, the antioxidant activity of the extracted lutein solution was evaluated, and the differences in light and heat stability between the lutein-piperonal complex and the commercially available lutein powder were investigated. The cocrystal was analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results indicated that menthol-acetic acid (DES-1) was the optimal eutectic solvent; the optimized extraction conditions were 47% (V/V) ethanol content, a material-to-liquid ratio of 1:45 (g/mL), and an extraction temperature of 69 ℃, under which the extraction yield of lutein can reached 644.11±1.99 μg/g. The lutein solution extracted and prepared with DES-1 exhibits scavenging rates of 77.52% and 84.58% for hydroxyl radicals and DPPH radicals, respectively, which were significantly higher than those achieved by traditional ethanol extraction methods (P<0.01). Under thermal conditions of 30 ℃ at 75% relative humidity and light conditions of 4500 Lux at 25 ℃, the lutein retention rates for the lutein-menthol cocrystal were 84.34% and 33.73%, both of which were significantly higher than those of commercially available lutein. The formed cocrystal structure could physically hinder oxygen penetration, while the hydroxyl groups at both ends of lutein can form strong hydrogen bonds with the hydroxyl groups of menthol, thereby significantly enhancing stability. Identification through LC-MS/MS revealed a total of 33 lutein-related components in the cocrystal, including lutein and lutein palmitate, with the highest content of free lutein reaching 107.93±11.36 μg/g. The lutein-menthol cocrystal prepared in this study significantly enhances the stability of lutein and may provide more possibilities for the practical development and utilization of lutein.

     

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