CN111909050A - 一种花椒多烯酰胺类单体及香味成分的富集分离方法 - Google Patents
一种花椒多烯酰胺类单体及香味成分的富集分离方法 Download PDFInfo
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Abstract
本发明提供一种花椒多烯酰胺类单体及香味成分的富集分离方法,包括如下步骤:(1)分子蒸馏富集:对花椒油进行分子蒸馏,分离出轻组分和重组分,轻组分即香味成分,重组分即多烯酰胺类成分富集产物;(2)动态轴向压缩色谱分离:将步骤(1)所得多烯酰胺类成分富集产物溶解于溶剂中,过滤后进行动态轴向压缩色谱分离,洗脱剂洗脱,将洗脱液浓缩干燥,得到多烯酰胺类单体。本发明首次将分子蒸馏富集技术和动态轴向色谱分离技术结合,通过分子蒸馏从花椒油中分离出多烯酰胺类成分富集产物及香味成分,再并结合动态轴向压缩色谱分离技术从多烯酰胺类成分富集产物中成功分离制备出多烯酰胺类单体。
Description
技术领域
本发明涉及天然产物提取分离技术领域,特别涉及一种花椒多烯酰胺类单体及香味成分的富集分离方法。
背景技术
药食两用的花椒为芸香科植物青花椒(Zanthoxylum schinifolium.)或花椒(Zanthoxylum bungeanum)的干燥成熟果皮,《本草纲目》中记载其具有温中散寒、芳香健胃、除湿止痛、杀虫解毒、止痒解腥等作用。
花椒主要化学成分包括挥发油类、酰胺类、黄酮类等。其中酰胺类多为不饱和脂肪酸酰胺,称为多烯酰胺类,是花椒麻味及药理作用的主要有效成分,也是花椒属植物特有成分。食用角度上,多烯酰胺类物质是花椒麻味的来源;药用角度上,其具有抗炎、抗菌、调节血脂、抗肿瘤等药理作用。多烯酰胺类化合物化学性质不稳定,易发生氧化或聚合反应、异构体转化等等。随着我国农业产业结构调整,花椒资源快速增加,如何提升花椒的附加产业链价值成为产业界的重点难点。
花椒多烯酰胺类主要包括羟基-α-山椒素、羟基-β-山椒素和羟基-γ-山椒素等单体,各单体结构式如下:
目前多烯酰胺类单体分离纯化常采用有机溶剂萃取法、柱层析法等,安全性低、操作复杂、损失较高。如中国专利(CN109674012A)公开了利用碱性氧化铝层析柱除杂得到纯净花椒多烯酰胺类物质,其存在需反复滤渣重结晶,收率低,未能分离单体等不足。中国专利(CN104030937A)公开了正己烷、环己烷、异辛烷等溶剂加热回流并冷却结晶得到多烯酰胺类物质,其存在加热回流阶段引入易燃易爆的异辛烷、正己烷等溶剂;未能分离单体等不足。中国专利(CN109645426A)公开了一种酶辅助提取、大孔树脂纯化花椒多烯酰胺类物质的方法,其存在提取效率低、未能分离单体等不足。中国专利(CN106977416A、CN107033017A)分别公开了利用甲醇恒温振荡提取、正己烷萃取以及紫外照射处理过得到羟基-α-山椒素、羟基-γ-山椒素单体,存在操作较复杂、不能同时分离得到多种单体、分离效率低等问题。中国专利(CN105481711A)制备羟基-β-山椒素单体也存在操作较复杂、不能同时分离得到多种单体、分离效率低等问题。中国专利(CN104026538A)公开了一种通过分子蒸馏获得花椒芳香油和花椒麻素(多烯酰胺类)的方法,其存在分离纯度不高、未能分离单体等不足;且该方法仅适用于分离多烯酰胺类成分含量较高的原料,对于多烯酰胺类成分含量低的原料则难以分离。
因此,从花椒中高效提取多烯酰胺类单体具有重要的意义。
发明内容
针对现有技术存在的问题,本发明的目的在于提供一种花椒多烯酰胺类单体的富集分离方法,能够从多烯酰胺类成分含量低的原料中分离出花椒多烯酰胺类单体和香味成分,所得多烯酰胺类单体具有高收率和高纯度。
本发明采取的技术方案是:
一种花椒多烯酰胺类单体及香味成分的富集分离方法,包括如下步骤:
(1)分子蒸馏富集:对花椒油进行分子蒸馏,分离出轻组分和重组分,轻组分即香味成分,重组分即多烯酰胺类成分富集产物;
(2)动态轴向压缩色谱分离:将步骤(1)所得多烯酰胺类成分富集产物溶解于溶剂中,过滤后进行动态轴向压缩色谱分离,洗脱剂洗脱,将洗脱液浓缩干燥,得到多烯酰胺类单体。
相对于现有技术,本发明首次将分子蒸馏富集技术和动态轴向色谱分离技术结合,通过分子蒸馏从花椒油中分离出多烯酰胺类成分富集产物及香味成分,再并结合动态轴向压缩色谱分离技术从多烯酰胺类成分富集产物中成功分离制备出多烯酰胺类单体。
步骤(1)中,花椒油分子蒸馏的蒸馏温度为70~120℃,真空度为1~30Pa,刮膜转速为150~300r/min,冷凝温度为0~30℃。通过控制分子蒸馏条件,可在花椒油中多烯酰胺类成分含量极低的情况下有效地将多烯酰胺类成分和香味成分进行分离,其中若真空度过高,则轻组分收率越高,重组分收率越低,且轻组分重杂质越多。
步骤(2)中,所述动态轴向压缩色谱分离用的色谱填料选自C30、UniQ10、UniSil10、UniPSA10、UniPS10、UniPSN10、聚酰胺中的一种或几种。发明人通过筛选得知,C30、UniQ10、UniSil10、UniPSA10、UniPS10、UniPSN10、聚酰胺能够对多烯酰胺类成分进行有效吸附和分离,而其他填料出现难以吸附多烯酰胺类成分或吸附多烯酰胺类成分后难以进行分离的情况。
步骤(2)中,所述动态轴向压缩色谱分离所用洗脱剂为乙醇-水,所述洗脱剂中乙醇的体积分数为50%~80%。当乙醇体积分数过小,洗脱能力越差,洗脱时间越长;乙醇体积分数过大,洗脱效果越差,不利成分分离。
步骤(2)中,所述洗脱剂的流速为30~60mL/min。流速过大或过小均不利于洗脱分离。
步骤(2)中,色谱分离柱压缩规格为30×250mm。根据设备大小及生产规模,可适当调整色谱分离柱压缩的规格。
步骤(2)中,所述浓缩干燥温度为60~70℃。
所述用于分子蒸馏的花椒油中多烯酰胺类成分总含量≥5%。本发明同样适用于多烯酰胺类成分含量低于5%的花椒油,因为考虑生产周期、成本等原因,采用多烯酰胺类成分总含量≥5%的花椒油较经济实惠;通过对其进行前处理将多烯酰胺类成分总含量提高至≥5%后同样可用于本发明的技术分离制备多烯酰胺类成分。
所述花椒油由超临界CO2流体萃取、超声波辅助提取、试剂回流提取、高压破碎提取、渗漉提取中的任意一种方法提取得到。
所述多烯酰胺类单体包括羟基-α-山椒素、羟基-β-山椒素和羟基-γ-山椒素。
所述香味成分包括4-萜烯醇、α-松油醇、桃金娘烯醛、异枞萜、芳樟醇、β-榄香烯、β-石竹烯、罗汉柏烯、α-石竹烯。
相对于现有技术,本发明具有如下有益效果:
(1)本发明能够从多烯酰胺类成分含量低的花椒油原料中将多烯酰胺类成分和香味成分分离,并分离出高纯度、高收率的多烯酰胺类单体。
(2)采用分子蒸馏富集技术对花椒油中的分离香味成分并富集多烯酰胺类物质,解决了现用工艺采用溶剂萃取或大孔树脂吸附存在有机用量大、毒性大、效率低等问题。采用动态轴向压缩色谱分离技术对分子蒸馏富集馏分进行定向分离,解决现有硅胶柱层析、重结晶等工艺存在的效率、收率低、工艺不稳定、有机溶剂用量大等问题。
(3)本发明工艺稳定、可行,具有生产效率高、纯度及收率高、绿色环保等优点,可用于大批量工业化生产,具有很强的实用价值。
附图说明
图1为实施例1花椒油的HPLC图;
图2为实施例1的香味成分的GC-MC图;
图3为实施例1的多烯酰胺类馏分的HPLC图;
图4为实施例1多烯酰胺类馏分的动态轴向压缩色谱分离色谱图;
图5为实施例1的羟基-γ-山椒素的HPLC图;
图6为实施例1的羟基-α-山椒素的HPLC图;
图7为实施例1的羟基-β-山椒素的HPLC图。
具体实施方式
为更好地理解本发明,下面通过以下实施例对本发明作进一步具体的阐述,但不可理解为对本发明的限定,对于本领域的技术人员根据上述发明内容所作的一些非本质的改进与调整,也视为落在本发明的保护范围内。
本发明提供一种花椒多烯酰胺类单体及香味成分的富集分离方法,包括如下步骤:
(1)分子蒸馏富集:取花椒油,加至分子蒸馏装置恒温槽,升温至一定的蒸馏温度,调节真空度,控制刮膜转速、冷凝温度,开始蒸馏过程,分离出轻组分和重组分,轻组分即香味成分,重组分即多烯酰胺类成分富集产物(多烯酰胺类馏分)。
(2)动态轴向压缩色谱分离:将步骤(1)的多烯酰胺类馏分用溶剂溶解,过滤,装至工业色谱进样罐中,工业色谱中装填合适的填料,色谱分离柱压缩成30×250mm规格,使用洗脱剂(所用洗脱剂与前述溶解多烯酰胺类馏分的溶剂相同)在检测波长268nm下进行洗脱,根据出峰时间和色谱峰的高度,确定羟基-α-山椒素、羟基-β-山椒素和羟基-γ-山椒素三种多烯酰胺类单体的洗脱液的收集起止时间,并将洗脱液减压浓缩干燥,即得羟基-α-山椒素、羟基-β-山椒素和羟基-γ-山椒素三种多烯酰胺类单体。
步骤(1)和步骤(2)中的富集分离条件如表1所示:
表1.富集分离条件
其中,各实施例和对比例所用花椒油以花椒为原料,经不同的提取方法得到,其中实施例1花椒油的HPLC图如图1所示。各实施例的花椒油成分分析见表2:
表2.花椒油提取方法及成分
分子蒸馏富集结果:
各实施例和对比例经步骤(1)收集得到的香味成分和多烯酰胺类馏分重量及收率如下表3所示:
表3.香味成分和多烯酰胺类馏分重量及收率
对其中的香味成分进行检测,其中实施例1的香味成分的GC-MC图如图2所示。通过分析可知,香味成分主要由4-萜烯醇、α-松油醇、桃金娘烯醛、异枞萜、芳樟醇、β-榄香烯、β-石竹烯、罗汉柏烯、α-石竹烯组成。
对其中的多烯酰胺类馏分进行分析,其中实施例1的多烯酰胺类馏分的HPLC图如图3所示。各实施例的多烯酰胺类馏分中成分含量如表4所示:
表4.多烯酰胺类馏分成分分析
通过比较表4和表2可以看出,经过在一定条件下进行分子蒸馏,可有效提高羟基-γ-山椒素、羟基-α-山椒素和羟基-β-山椒素三种多烯酰胺类单体的含量,且当将分子蒸馏中的真空度降低后,多烯酰胺类馏分中三种多烯酰胺类单体的含量发生明显的降低(对比例1)。
根据表2~4可以计算得到经过分子蒸馏后羟基-γ-山椒素、羟基-α-山椒素和羟基-β-山椒素三种多烯酰胺类单体的转移率,结果如表5所示:
转移率V1的计算公式为:
其中m1为多烯酰胺类馏分重量,w1为多烯酰胺类馏分中羟基-γ-山椒素、羟基-α-山椒素或羟基-β-山椒素的含量;m0为花椒油重量,w0为花椒油中羟基-γ-山椒素、羟基-α-山椒素或羟基-β-山椒素的含量。
表5.多烯酰胺类单体在分子蒸馏步骤中的转移率
根据表5可知,经过分子蒸馏,羟基-γ-山椒素、羟基-α-山椒素和羟基-β-山椒素三种多烯酰胺类单体得到极大的富集。
动态轴向压缩色谱分离结果:
实施例1多烯酰胺类馏分的动态轴向压缩色谱分离色谱图如图4所示,相比图3,动态轴向压缩色谱分离色谱图的中羟基-γ-山椒素、羟基-α-山椒素和羟基-β-山椒素三种多烯酰胺类单体的出峰时间延长,且色谱峰分离度提高。
各实施例和对比例经步骤(2)收集、浓缩干燥后得到的三种多烯酰胺类单体重量如下表6所示:
表6.经动态轴向压缩色谱分离得到三种多烯酰胺类单体重量
对经动态轴向压缩色谱分离得到的三种多烯酰胺类单体进行分析,其中实施例1的羟基-γ-山椒素、羟基-α-山椒素和羟基-β-山椒素的HPLC图依次如图5~7所示。
经检测,经动态轴向压缩色谱分离得到的三种多烯酰胺类单体纯度如下表7所示:
表7.经动态轴向压缩色谱分离得到三种多烯酰胺类单体纯度
根据分析结果可知,通过对分子蒸馏后的馏分进行动态轴向压缩色谱分离,能够有效地将羟基-γ-山椒素、羟基-α-山椒素和羟基-β-山椒素三种多烯酰胺类单体进行分离,且相较分子蒸馏富集后的馏分显著提高了三种多烯酰胺类单体的纯度。
经计算,三种多烯酰胺类单体在动态轴向压缩色谱分离步骤中的转移率如下表8所示:
三种多烯酰胺类单体在动态轴向压缩色谱分离步骤中的转移率V2的计算公式为:
其中m2为动态轴向压缩色谱分离后浓缩干燥得到的羟基-γ-山椒素、羟基-α-山椒素或羟基-β-山椒素重量,w2为动态轴向压缩色谱分离后浓缩干燥得到的羟基-γ-山椒素、羟基-α-山椒素或羟基-β-山椒素的纯度。
m1-0为动态轴向压缩色谱分离的上样分离量,为10g;w1为多烯酰胺类馏分中羟基-γ-山椒素、羟基-α-山椒素或羟基-β-山椒素的百分含量。
表8.多烯酰胺类单体在动态轴向压缩色谱分离步骤中的转移率
三种多烯酰胺类单体在整个富集分离过程(分子蒸馏富集+动态轴向压缩色谱分离)中的总转移率如下表9所示:
三种多烯酰胺类单体的总转移率V3的计算公式为:V3=V1×V2。
表9.多烯酰胺类单体的总转移率
可见,经过分子蒸馏和动态轴向压缩色谱分离,羟基-γ-山椒素、羟基-α-山椒素和羟基-β-山椒素三种多烯酰胺类单体得到极大的富集和分离。
Claims (10)
1.一种花椒多烯酰胺类单体及香味成分的富集分离方法,其特征在于:包括如下步骤:
(1)分子蒸馏富集:对花椒油进行分子蒸馏,分离出轻组分和重组分,轻组分即香味成分,重组分即多烯酰胺类成分富集产物;
(2)动态轴向压缩色谱分离:将步骤(1)所得多烯酰胺类成分富集产物溶解于溶剂中,过滤后进行动态轴向压缩色谱分离,洗脱剂洗脱,将洗脱液浓缩干燥,得到多烯酰胺类单体。
2.根据权利要求1所述花椒多烯酰胺类单体及香味成分的富集分离方法,其特征在于:步骤(1)中,所述分子蒸馏的蒸馏温度为70~120℃,真空度为1~30Pa,刮膜转速为150~300r/min,冷凝温度为0~30℃。
3.根据权利要求1所述花椒多烯酰胺类单体及香味成分的富集分离方法,其特征在于:步骤(2)中,所述动态轴向压缩色谱分离用的色谱填料选自C30、UniQ10、UniSil10、UniPSA10、UniPS10、UniPSN10、聚酰胺中的一种或几种。
4.根据权利要求1所述花椒多烯酰胺类单体及香味成分的富集分离方法,其特征在于:步骤(2)中,所述动态轴向压缩色谱分离所用洗脱剂为乙醇水溶液。
5.根据权利要求4所述花椒多烯酰胺类单体及香味成分的富集分离方法,其特征在于:所述洗脱剂中乙醇的体积分数为50%~80%。
6.根据权利要求5所述花椒多烯酰胺类单体及香味成分的富集分离方法,其特征在于:步骤(2)中,所述洗脱剂的流速为30~60mL/min。
7.根据权利要求1所述花椒多烯酰胺类单体及香味成分的富集分离方法,其特征在于:步骤(2)中,所述浓缩干燥温度为60~70℃。
8.根据权利要求1所述花椒多烯酰胺类单体及香味成分的富集分离方法,其特征在于:所述用于分子蒸馏的花椒油中多烯酰胺类成分总含量≥5%。
9.根据权利要求1~8任意一项所述花椒多烯酰胺类单体及香味成分的富集分离方法,其特征在于:所述多烯酰胺类单体包括羟基-α-山椒素、羟基-β-山椒素和羟基-γ-山椒素。
10.根据权利要求1~8任意一项所述花椒多烯酰胺类单体及香味成分的富集分离方法,其特征在于:所述香味成分包括4-萜烯醇、α-松油醇、桃金娘烯醛、异枞萜、芳樟醇、β-榄香烯、β-石竹烯、罗汉柏烯或α-石竹烯中的至少一种。
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