CN112341418A - 一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法 - Google Patents
一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法 Download PDFInfo
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Abstract
本发明公开了一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,该方法采用蒸汽爆破法,于压力0.5‑3.0MPa下维压30‑180s,使杭白菊中的酚酸化合物中的同分异构体之间相互转化。本发明采用蒸汽爆破法便于实现杭白菊黄酮苷水解和明确酚酸化合物之间的转化规律,改变目前黄酮类化合物难水解、污染大的问题,该蒸汽爆破法通过改变压力和维压时间促使酚酸类化合物转化的量和黄酮苷降解的量出现转变。
Description
技术领域
本发明涉及一种咖啡酰奎宁酸转化及黄酮糖苷水解的方法,具体涉及一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法。
背景技术
杭白菊为菊科菊属植物菊(Chrysanthemum morifolium Ramat.)的干燥头状花序,又名小汤黄、小白菊,主产于我国浙江桐乡,具有散风清热、平肝明目、清热解毒之功效,常用于治疗风热感冒、头痛眩晕、目赤肿痛、眼目昏花、疮痈肿毒。它具有心血管保护、降血脂、抗氧化,保肝、神经保护等作用。至今,从杭白菊中分得的化学成分主要包括黄酮类、挥发油、三萜类、甾体类、酚酸类、多糖及其他物质等。
蒸汽爆破(简称“汽爆”)预处理是近年来发展迅速的一种预处理方法。原料用蒸汽加热至180-235℃,维压一段时间,在突然释压喷放时,产生二次蒸汽,体积猛增,在机械力的作用下,将固体物料结构破坏。蒸汽爆破技术最早用于纸浆生产,现正广泛用于生物质能转换的预处理技术,目前国内外尚未开展蒸汽爆破杭白菊的研究,但从蒸汽爆破技术的原理及作用特点来看,由于在处理过程中只需高温蒸气,不添加任何化学物质,即可造成物料发生多种化学物理变化。已知目前研究发现汽爆过程中存在类似酸水解、热降解、类机械断裂、氧键破坏和结构重排等协同作用,原料物理结构和化学成分在加工过程中发生较大的变化。杭白菊的咖啡酰奎宁酸化合物中新绿原酸(3-CQA),隐绿原酸(4-CQA),绿原酸(5-CQA)是同分异构体,异绿原酸A(3,5-CQA),异绿原酸C(3,4-CQA),异绿原酸B(4,5-CQA)是同分异构体,在一定条件下会发生互相转化。在探究其单一物质转化的过程中通常对其进行温度,压力,溶剂,pH的改变,模拟体系实验较为繁琐且动力学还尚未证明。而黄酮类化合物的开发利用一直是中药领域的研究热点。从植物中将黄酮类化合物有效地提取出来是实现其药用价值的关键环节,目前国内外对黄酮类化合物提取的方法众多,包括传统的提取方法如浸渍法、煎煮法、回流法、索氏提取法等,传统提取方法工艺简单、成本低,在中药制药产业中发挥着重要的作用。但传统提取方法存在着明显的缺陷,如提取率低、周期长、溶剂消耗大、纯度低等问题,在中药有效成分提取中应用新技术、新工艺可有效弥补传统提取方法的不足。
发明内容
针对现有技术中存在的问题,本发明设计的目的在于提供一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,该方法通过对杭白菊进行蒸汽爆破处理,从而影响杭白菊黄酮类,咖啡酰奎宁酸类物质以及挥发油成分的含量,便于探索同分异构体之间的物量转化,同时对杭白菊中黄酮类化合物起到降解作用。
本发明通过以下技术方案加以实现:
所述的一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,其特征在于该方法采用蒸汽爆破法,于压力0.5-3.0MPa下维压30-180s,使杭白菊中的酚酸化合物中的同分异构体之间相互转化。
所述的一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,其特征在于该方法的具体步骤为:
1)蒸汽爆破仪提前开水阀,加水注满;
2)打开总电源,煤气瓶进行烧水;
3)达到预设压力时,将新鲜干燥过的杭白菊加入汽爆仓中,合上盖后,将高温饱和蒸汽通入气爆仓中使内压力及维压时间均达到权利要求1设定的范围内;
4)阀门打开时间为瞬间泄压的同时完成物料的爆破,收集腔内喷出的物料即为蒸汽爆破后的固液混合物;
5)汽爆后的杭白菊混合物于烘箱低温烘干或者冷冻干燥,磨粉,过筛备用;
6)后续进行样品抗氧化,高效色谱检测。
所述的一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,其特征在于步骤5)中烘箱温度为40-60℃。
所述的一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,其特征在于步骤5)中过筛为过10-120目筛。
本发明采用蒸汽爆破法便于实现杭白菊黄酮苷水解和明确酚酸化合物之间的转化规律,实现咖啡酰奎宁酸同分异构体之间的含量相对均衡,达到协同增效的作用,改变目前黄酮类化合物难水解、污染大的问题,该蒸汽爆破法通过改变压力和维压时间促使酚酸类化合物转化的量和黄酮苷降解的量出现转变。
附图说明
图1为本发明原理框图;
图2为12种对照品的HPLC图(12种对照品分别为1.新绿原酸;2.绿原酸;3.隐绿原酸;4.木犀草素-7-葡萄糖;5.异绿原酸B;6.异绿原酸A;7.芹菜素-7-葡萄糖;8.异绿原酸C;9.蒙花苷;10.木犀草素;11.芹菜素;12.金合欢素);
图3为未气爆的杭白菊样品HPLC图;
图4为0.5MPa,60s条件爆破的杭白菊HPLC色谱图;
图5为1.5MPa,90s条件爆破的杭白菊HPLC色谱图;
图6为1.5MPa,30s条件爆破的杭白菊HPLC色谱图;
图7为2.0MPa,90s条件爆破的杭白菊HPLC色谱图。
具体实施方式
以下结合说明书附图对本发明做进一步详细描述,并给出具体实施例。
本发明一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,该方法采用蒸汽爆破法,具体步骤为:1)蒸汽爆破仪提前开水阀,加水注满;2)打开总电源,煤气瓶进行烧水;3)达到预设压力时,将新鲜干燥过的杭白菊加入汽爆仓中,合上盖后,将高温饱和蒸汽通入气爆仓中,使内压力达到0.5-3.0MPa下维压30-180s;4)阀门打开时间为瞬间泄压的同时完成物料的爆破,收集腔内喷出的物料即为蒸汽爆破后的固液混合物;5)汽爆后的杭白菊混合物于烘箱40-60℃低温烘干或者冷冻干燥,磨粉,过10-120目筛备用;6)后续进行样品活性成分高效色谱检测。其原理框图见图1。
其中,其中,新绿原酸;绿原酸;隐绿原酸;木犀草素-7-葡萄糖;异绿原酸B;异绿原酸A;芹菜素-7-葡萄糖;异绿原酸C;蒙花苷;木犀草素;芹菜素;金合欢素12种对照品的HPLC图见图2,未气爆的杭白菊的高效液相色谱图见图3。
该发明方法蒸汽爆破由于改变压力,温度也随着饱和蒸压的增大而上升,温度区间在150-215 ℃之间,而由于温度和压力的双因素影响,变化的差异非常显著。蒸汽爆破技术可以提高酚酸含量已经被大量学者证实,但是高温处理也能导致酚酸的降解,汽爆后的杭白菊黄酮和酚酸化合物有所减少,未汽爆杭白菊中总黄酮为74.99 mg/g,显著高于汽爆样品中的含量。其中,总黄酮含量随着汽爆压力的增加,含量不断上升,从0.5 Mpa下的35.58上升至2.5 Mpa下的65.23,增加了83.33%。总酚含量也随着汽爆压力的增加,含量不断上升,从56.19 mg/g(0.5 MPa)上升至82.93 mg/g(2.5 Mpa),增加了47.59%,接近于未汽爆的杭白菊样品。
实施例1
1)汽爆仪器提前开水阀,加水注满;
2)打开总电源,煤气瓶进行烧水;
3)达到预设压力时,将新鲜干燥过的杭白菊加入汽爆仓中,合上盖后,将高温饱和蒸汽通入汽爆使内压力至设定压力0.5 MPa并保持一定的时间,维压60 s结束后打开气动阀门;
4)阀门打开时间为瞬间泄压的同时完成物料的爆破,收集腔内喷出的物料即为蒸汽爆破后的固液混合物;
5)汽爆后的杭白菊混合物在45℃烘箱低温烘干,磨粉,过65目筛备用;
6)高效色谱检测,色谱条件如下:Luna-C18色谱柱(250 mm ×4.6 mm, 5um);以乙腈为流动相A,以0.1%磷酸溶液为流动相B。梯度洗脱如下,流速:0.8 mL/min,检测波长330nm,进样量:10μL,柱温35℃。0~11 min,A 10~18%,11~32 min A 18%,32-40 min A 18-30%,40-48min A 30-35%,48-50 min,A 35-40%,50-55min,A40%,55-60 min,A 40-70%,60-70min,A70-10%。其HPLC色谱图见图4。
检测结果:在此压力点下,和未汽爆样品相比,总酚酸和黄酮含量分别下降52.55%和33.29%;咖啡酰奎宁酸中,新绿原酸(3-CQA)增加7.5%,隐绿原酸(4-CQA)增加7.0%,绿原酸(5-CQA)降低54.66%,异绿原酸A(3,5-CQA)降低78.49%,异绿原酸C(3,4-CQA)降低8.83%,异绿原酸B(4,5-CQA)降低30.87%,黄酮类化合物中,木犀草苷增加64.9%,芹菜素-7-葡萄糖苷增加32.7%,蒙花苷下降30%,木犀草素从未检测到增加到3.64 mg/g,芹菜素降低19.4%。
实施例2
1)汽爆仪器提前开水阀,加水注满;
2)打开总电源,煤气瓶进行烧水;
3)达到预设压力时,将新鲜干燥过的杭白菊加入汽爆仓中,合上盖后,将高温饱和蒸汽通入汽爆使内压力至设定压力1.0 MPa并保持一定的时间,维压90 s结束后打开气动阀门;
4)阀门打开时间为瞬间泄压的同时完成物料的爆破,收集腔内喷出的物料即为蒸汽爆破后的固液混合物。
5)汽爆后的杭白菊混合物在50 ℃烘箱低温烘干,磨粉,过120目筛备用。
6)高效色谱检测,HPLC色谱图见图5。
检测与结果:在此压力点下,和未汽爆样品相比,总酚酸和黄酮含量分别下降24.24%%和14.02%,新绿原酸(3-CQA)增加131.15%,隐绿原酸(4-CQA)增加94.37 %,绿原酸(5-CQA)降低51.88%,异绿原酸A(3,5-CQA)降低86.28%,异绿原酸C(3,4-CQA)降低27.45%,异绿原酸B(4,5-CQA)降低4.55%,黄酮类化合物中,木犀草苷增加64.9%,芹菜素-7-葡萄糖苷增加24.33%,蒙花苷下降37.9%,木犀草素从未检测到增加到8.03mg/g,芹菜素增加111.3%,金合欢素从未检测增加到0.41 mg/g。
实施例3
1)汽爆仪器提前开水阀,加水注满;
2)打开总电源,煤气瓶进行烧水;
3)达到预设压力时,将新鲜干燥过的杭白菊加入汽爆仓中,合上盖后,将高温饱和蒸汽通入汽爆使内压力至设定压力1.5 MPa并保持一定的时间,维压30s结束后打开气动阀门;
4)阀门打开时间为瞬间泄压的同时完成物料的爆破,收集腔内喷出的物料即为蒸汽爆破后的固液混合物;
5)汽爆后的杭白菊混合物在60℃烘箱低温烘干,磨粉,过60目筛备用;
6)高效色谱检测,HPLC色谱图见图6。
检测与结果:在此压力点下,和未汽爆样品相比,总酚酸和黄酮含量分别下降31.36%和29.47%;咖啡酰奎宁酸中,新绿原酸(3-CQA)增加45.90%,隐绿原酸(4-CQA)增加39.44%,绿原酸(5-CQA)降低51.66%,异绿原酸A(3,5-CQA)降低83.14%,异绿原酸C(3,4-CQA)降低21.47%,异绿原酸B(4,5-CQA)降低20.91%,黄酮类化合物中,木犀草苷增加60%,芹菜素-7-葡萄糖苷增加9.5%,蒙花苷下降25.88%,木犀草素从未检测到增加到6.67mg/g,芹菜素降低19.4%,金合欢素从未检测增加到0.28mg/g。
实施例4
1)汽爆仪器提前开水阀,加水注满
2)打开总电源,煤气瓶进行烧水
3)达到预设压力时,将新鲜干燥过的杭白菊加入汽爆仓中,合上盖后,将高温饱和蒸汽通入汽爆使内压力至设定压力2.5 MPa并保持一定的时间,维压180 s结束后打开气动阀门
4)阀门打开时间为瞬间泄压的同时完成物料的爆破,收集腔内喷出的物料即为蒸汽爆破后的固液混合物。
5)汽爆后的杭白菊混合物在冷冻烘干,磨粉,过10目筛备用。
6)高效色谱检测,HPLC色谱图见图7。
检测与结果:在此压力点下,和未汽爆样品相比,总酚酸和黄酮含量分别下降13.01%和1.54%;咖啡酰奎宁酸中,新绿原酸(3-CQA)增加162.3%,隐绿原酸(4-CQA)增加1.15%,绿原酸(5-CQA)降低56.91%,异绿原酸A(3,5-CQA)降低88.67%,异绿原酸C(3,4-CQA)降低42.08%,异绿原酸B(4,5-CQA)降低5.69%;黄酮类化合物中,木犀草苷增加40.3%,芹菜素-7-葡萄糖苷增加6.9%,蒙花苷下降52.9%,木犀草素从未检测到增加到9.20mg/g,芹菜素增加250%,金合欢素从未检测增加到0.87mg/g。
12种标准品线性关系考察
以峰面积为纵坐标,以对照品浓度(μg/ml)为横坐标,绘制标准曲线,得到回归方程、相关系数和线性范围,见表1。
表1 12种被测成分的线性方程、相关系数和线性范围
Claims (4)
1.一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,其特征在于该方法采用蒸汽爆破法,于压力0.5-3.0MPa下维压30-180s,使杭白菊中的酚酸化合物中的同分异构体之间相互转化,同时黄酮糖苷水解产生黄酮苷元。
2.如权利要求1所述的一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,其特征在于该方法的具体步骤为:
1)蒸汽爆破仪提前开水阀,加水注满;
2)打开总电源,煤气瓶进行烧水;
3)达到预设压力时,将新鲜干燥过的杭白菊加入汽爆仓中,合上盖后,将高温饱和蒸汽通入气爆仓中使内压力及维压时间均达到权利要求1设定的范围内;
4)阀门打开时间为瞬间泄压的同时完成物料的爆破,收集腔内喷出的物料即为蒸汽爆破后的固液混合物;
5)汽爆后的杭白菊混合物于烘箱低温烘干或者冷冻干燥,磨粉,过筛备用;
6)后续进行样品高效色谱检测各个活性成分含量。
3.如权利要求2所述的一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,其特征在于步骤5)中烘箱温度为40-60℃。
4.如权利要求2所述的一种促进杭白菊中咖啡酰奎宁酸转化和黄酮糖苷水解产生黄酮苷元的方法,其特征在于步骤5)中过筛为过10-120目筛。
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