CN110143942B - 一种有机酸水解淫羊藿苷制备淫羊藿素及鼠李糖糖浆的方法 - Google Patents
一种有机酸水解淫羊藿苷制备淫羊藿素及鼠李糖糖浆的方法 Download PDFInfo
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Abstract
本发明属于医药技术领域,具体涉及一种有机酸水解淫羊藿苷制备淫羊藿素及鼠李糖糖浆的方法。本发明首次采用中等酸度的柠檬酸作为催化剂水解淫羊藿苷制备淫羊藿素,水解条件温和;水解物可通过醇水溶液纯化即可制备出高纯度淫羊藿素;制备过程中可获得白利糖度值为60%‑65%的焦糖色的鼠李糖葡萄糖复合糖液,且品质稳定;另外,柠檬酸最终转化为了易于分离的联产物柠檬酸钙。本发明水解工艺温和,能够获得高纯度的淫羊藿素,另外可以获得高白利糖度值的复合糖,最后本发明联产副产物柠檬酸钙的获得能够在一定程度上降低生产成本。
Description
技术领域
本发明属于医药技术领域,具体涉及一种有机酸水解淫羊藿苷制备淫羊藿素及鼠李糖糖浆的方法。
背景技术
淫羊藿(Epimedium brevicomu Maxim)为小檗科淫羊藿属植物,最早记载见于《神农本草经》,具有补肾壮阳、祛风除湿等功效,现代中医将淫羊藿用于治疗乳房肿块、高血压等疾病。现代中医将淫羊藿用于治疗乳房肿块、高血压等疾病。现代研究表明,淫羊藿具有增强人体免疫功能、延缓衰老、防治神经性疾病等作用。淫羊藿苷(Icariin,ICA)是淫羊藿的主要活性单体成分,口服吸收率低,生物利用度只有12%,其效应主要是通过代谢成淫羊藿素(Icaritin,ICT)后起作用。
而淫羊藿素在原植物中含量很低,难以直接分离纯化得到,因此可以通过水解淫羊藿苷中糖苷键的方法制备淫羊藿苷元。已报道的水解糖苷键的方法有:(1)化学方法,如酸、碱水解法。酸水解法多用盐酸、硫酸或硝酸,碱水解法多用氢氧化钠或氢氧化钾。此法多采用水解淫羊藿苷3-鼠李糖糖苷键和7-葡萄糖糖苷键从而获得淫羊藿苷元,这些研究以淫羊藿苷为反应底物,而淫羊藿苷本身成本较高,且化学方法反应条件剧烈,容易破坏产物,往往得不到完整的苷元,要获取纯度较高得淫羊藿素则需要一定得纯化步骤。(2)生物转化法,如以淫羊藿为细菌、霉菌、酵母菌的发酵产酶诱导物,制备含霉菌液,再用此菌液将淫羊藿黄酮苷类化合物转化为低糖苷或苷元(公开号:CN 1473938A酶法水解淫羊藿甙糖基制备低糖淫羊藿甙或甙元的方法),由于淫羊藿黄酮苷类化合物种类很多,其糖苷键结构十分复杂,主要由α-L-鼠李糖糖苷键、β-D-葡萄糖糖苷键、β-D-木糖糖苷键等单糖糖苷键以及由他们组成的二糖糖苷键构成,加上酶催化水解的高度专一性,这些含酶菌液无法彻底将糖苷键脱去,因此无法得到纯度较高的淫羊藿苷元。另外,此法操作复杂,耗时多,目的性不强,多得到低糖苷,难以得到苷元,且转化率低,分离纯化难,不利于工业化生产。因此仅为了获取单一得淫羊藿素,使用前两种制备方法不具备商业应用前景。
发明内容
本发明的目的是克服现有技术中的不足,提供一种有机酸水解淫羊藿苷制备淫羊藿素及鼠李糖糖浆的方法。
本发明是通过如下技术方案实现上述目的的,一种有机酸水解淫羊藿苷制备淫羊藿素及鼠李糖糖浆的方法,包括如下步骤:
1)淫羊藿苷酸解工序
将淫羊藿苷加入到柠檬酸水溶液中,在高温高压下进行水解;水解结束后过滤得滤饼和水解滤液;
2)淫羊藿素的纯化工序
将步骤1)所得滤饼加入到含有活性炭的醇水溶液中加热脱色,然后过滤、浓缩、降温析晶得淫羊藿素;
3)复合糖液的制备工序
将步骤1)所得水解滤液采用氢氧化钙调pH至近中性,析出柠檬酸钙;过滤、分离出柠檬酸钙得二次滤液;向二次滤液中加入硅藻土搅拌,过滤,浓缩得到焦糖香气的焦糖色的鼠李糖葡萄糖复合糖液。
优选的,所述步骤1)中柠檬酸水溶液的浓度为1.5-2.5mol/L;按照重量比计算,淫羊藿苷∶柠檬酸水溶液=1∶8-12;所述高温高压是指温度为140-150℃、压力为0.26-0.38MPa;所述水解的时间为20-40min;
优选的,步骤2)所述浓缩的浓缩终点为浓缩后的体积为浓缩前体积的1/3-1/2;所述降温析晶的析晶温度为3-5℃,如4℃;
优选的,步骤3)所述近中性是指pH=6.5-7.0;所述鼠李糖葡萄糖复合糖液的白利糖度值(brix)为60%-65%;本发明意外的发现,所得鼠李糖葡萄糖复合糖液的白利糖度值(brix)可高达60%-65%,品质稳定,常温保存的情况下不会析出。由一种或者多种纯的糖来复配制备复合糖液,往往brix都达不到60%就会析出了。
本发明使用柠檬酸水解淫羊藿苷,在高温高压下,耗时短,水解彻底,在获得高纯度淫羊藿素得同时,还得到两个副产品,一个是高Brix含量,且性质稳定,不易析晶的具有浓郁的焦糖香味的焦糖色复合鼠李糖和葡萄糖糖液,可以直接作为复配甜味剂或者风味香料添加于各类食品中。以及副产品柠檬酸钙,可作为食品添加剂使用。扩充了产出,增加了该产品线的综合价值,具有良好的工业化前景。
与现有技术相比,本发明具有如下优点:
1)本发明首次采用中等强度酸柠檬酸作为催化剂水解淫羊藿苷制备淫羊藿素,水解条件温和不破坏产物结构;经过简单纯化即得到高纯度淫羊藿素;
2)本发明首次获得白利糖度值为60%-65%的复合糖,且品质稳定,常温保存的情况下不会析出;
3)本发明采用的柠檬酸在工艺过程中转化为了联产产物柠檬酸钙,在后续制备复合糖液时能够顺便分离出来,在一定程度上降低了生产成本。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明了,下面结合具体实施方式,对本发明进一步详细说明。应该理解,这些描述只是示例性的,而并非要限制本发明的范围。
原料淫羊藿苷:市售,纯度≥95%(HPLC)。
淫羊藿苷及淫羊藿素液相检测方法:液相色谱仪Agilent 1260 HPLC,色谱柱Agilent XDB C-18(4.6mm×150mm,5μm),流动相流速:1mL/min,柱温30℃,流动相为甲醇-0.2%磷酸水溶液(50∶50);检测波长288nm,进样量10μL。
糖液液相检测方法:液相检测条件为:Agilent 1260 HPLC+ELSD检测器,色谱柱:GRACE Prevail Carbohydrate ES分析柱(250mm×4.6mm,5μm)流动相采用V(乙腈)∶V(水)=70∶30,流速为1.0mL/min;柱温为30℃,进样量20μL;ELSD的漂移管温度为80℃,氮气作载气,流速2.0mL/min。
实施例1
将1kg淫羊藿苷加入2.0mol/L的柠檬酸水溶液10L,于高压釜中(压力0.26-0.27MPa)加热至140℃水解40min,水解结束后的水解液冷却至室温,过滤水解液,水解滤液备用;
所得滤饼用含有活性炭(滤饼重量的6wt%)的75V%乙醇水溶液溶解(乙醇水溶液的重量为滤饼重量的8-10倍),85℃搅拌20min,趁热过滤,之后滤液50℃减压浓缩至体积为浓缩前的1/2,4℃静置12小时,析出晶体即为淫羊藿素,经液相检测含量为95.2%。
将前述水解滤液在室温条件下用氢氧化钙调pH为6.5-7.0之间,过滤,滤饼经过纯水淋洗两次,得柠檬酸钙;滤液加入重量比为1%的硅藻土,搅拌20min,过滤,将滤液浓缩至brix为60%即得到焦糖香气浓郁的焦糖色的鼠李糖葡萄糖复合糖液,稳定,不易析出结晶。
实施例2
将1kg淫羊藿苷加入2.5mol/L的柠檬酸水溶液8L,于高压釜中(压力0.30-0.32MPa)加热至145℃水解30min,水解结束后的水解液冷却至室温,过滤水解液,水解滤液备用;
所得滤饼用含有活性炭(滤饼重量的8wt%)的80V%乙醇水溶液溶解(乙醇水溶液的重量为滤饼重量的8-10倍),75℃搅拌20min,趁热过滤,之后滤液50℃减压浓缩至体积为浓缩前的2/5,4℃静置12小时,析出晶体即为淫羊藿素,经液相检测含量为96.5%。
将前述水解滤液在室温条件下用氢氧化钙调pH为6.5-7.0之间,过滤,滤饼经过纯水淋洗两次,得柠檬酸钙。滤液加入重量比为1.5%的硅藻土,搅拌20min,过滤,将滤液浓缩至brix为63%即得到焦糖香气浓郁的焦糖色的鼠李糖葡萄糖复合糖液,且稳定,不易析出结晶。
实施例3
将1kg淫羊藿苷加入1.5mol/L的柠檬酸水溶液12L,于高压釜中(压力0.37-0.38MPa)加热至150℃水解20min,水解结束后的水解液冷却至室温,过滤水解液,水解滤液备用;
所得滤饼用含有活性炭(滤饼重量的4wt%)的85V%乙醇水溶液溶解(乙醇水溶液的重量为滤饼重量的8-10倍),70℃搅拌20min,趁热过滤,之后滤液50℃减压浓缩至体积为浓缩前的1/3,4℃静置12小时,析出晶体即为淫羊藿素,经液相检测含量为95.1%。
将前述水解滤液在室温条件下用氢氧化钙调pH为6.5-7.0之间,过滤,滤饼经过纯水淋洗两次,得柠檬酸钙。滤液加入重量比为0.8%的硅藻土,搅拌20min,过滤,将滤液浓缩至brix为65%即得到焦糖香气浓郁的焦糖色的鼠李糖葡萄糖复合糖液,且稳定,不易析出结晶。
对比例1
将1kg淫羊藿苷加入0.4mol/L的硫酸水溶液10L,于高压釜中(压力0.26-0.27MPa)加热至140℃水解40min,水解结束后的水解液冷却至室温,过滤水解液,水解滤液备用;
所得滤饼用含有活性炭(滤饼重量的6wt%)的75V%乙醇水溶液溶解(乙醇水溶液的重量为滤饼重量的8-10倍),80℃搅拌20min,趁热过滤,之后滤液50℃减压浓缩至体积为浓缩前的1/2,4℃静置12小时,析出晶体即为淫羊藿素,经液相检测含量为83.2%。
将前述水解滤液在室温条件下用氢氧化钙调pH为6.5-7.0之间,过滤,滤饼为硫酸钙;滤液加入重量比为1%的硅藻土,搅拌20min,过滤,将滤液浓缩至brix为60%即得到焦糖香气浓郁的焦糖色的鼠李糖葡萄糖复合糖液。
对比例采用强酸硫酸虽然能够实现水解淫羊藿苷制备淫羊藿素的目的,但是该方法较本发明方法制备出的淫羊藿素纯度低。
尽管已经详细描述了本发明的实施方式,但是应该理解的是,在不偏离本发明的精神和范围的情况下,可以对本发明的实施方式做出各种改变、替换和变更。
Claims (5)
1.一种有机酸水解淫羊藿苷制备淫羊藿素及鼠李糖糖浆的方法,包括如下步骤:
1)淫羊藿苷酸解工序
将淫羊藿苷加入到柠檬酸水溶液中,在高温高压下进行水解;水解结束后过滤得滤饼和水解滤液;
所述高温高压是指温度为140-150℃、压力为0.26-0.38MPa;
2)淫羊藿素的纯化工序
将步骤1)所得滤饼加入到含有活性炭的醇水溶液中加热脱色,然后过滤、浓缩、降温析晶得淫羊藿素;
3)复合糖液的制备工序
将步骤1)所得水解滤液采用氢氧化钙调pH至6.5-7.0,析出柠檬酸钙;过滤、分离出柠檬酸钙得二次滤液;向二次滤液中加入硅藻土搅拌,过滤,浓缩得到焦糖香气的焦糖色的鼠李糖葡萄糖复合糖液。
2.根据权利要求1所述的方法,其特征在于:步骤3)所述鼠李糖葡萄糖复合糖液的白利糖度值为60%-65%。
3.根据权利要求1或2所述的方法,其特征在于:所述步骤1)中柠檬酸水溶液的浓度为1.5-2.5mol/L;按照重量比计算,淫羊藿苷:柠檬酸水溶液=1:8-12。
4.根据权利要求1或2所述的方法,其特征在于:步骤1)所述水解的时间为20-40min。
5.根据权利要求1或2所述的方法,其特征在于:步骤2)所述浓缩的浓缩终点为浓缩后的体积为浓缩前体积的1/3-1/2;所述降温析晶的析晶温度为3-5℃。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101284000A (zh) * | 2007-04-10 | 2008-10-15 | 殷正丰 | 一种肥胖症或脂肪肝治疗药物 |
CN101302548A (zh) * | 2007-05-09 | 2008-11-12 | 北京珅奥基医药科技有限公司 | 淫羊藿素的制备方法 |
CN101502540A (zh) * | 2008-02-04 | 2009-08-12 | 北京凯瑞创新医药科技有限公司 | 一种以苷元为有效成分的高效药物组合物及其制备方法 |
CN105585551A (zh) * | 2016-03-01 | 2016-05-18 | 苏州禾研生物技术有限公司 | 一种落新妇苷的水解方法 |
-
2019
- 2019-05-30 CN CN201910466537.XA patent/CN110143942B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101284000A (zh) * | 2007-04-10 | 2008-10-15 | 殷正丰 | 一种肥胖症或脂肪肝治疗药物 |
CN101302548A (zh) * | 2007-05-09 | 2008-11-12 | 北京珅奥基医药科技有限公司 | 淫羊藿素的制备方法 |
CN101502540A (zh) * | 2008-02-04 | 2009-08-12 | 北京凯瑞创新医药科技有限公司 | 一种以苷元为有效成分的高效药物组合物及其制备方法 |
CN105585551A (zh) * | 2016-03-01 | 2016-05-18 | 苏州禾研生物技术有限公司 | 一种落新妇苷的水解方法 |
Non-Patent Citations (2)
Title |
---|
柠檬酸催化大豆异黄酮糖苷水解苷元的工艺研究;于丽颖 等;《江苏农业科学》;20141231;第42卷(第11期);第294页左栏第2段,右栏第2段 * |
淫羊藿黄酮水解产物化学成分的研究;李丹凤;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20150415(第04期);B016-453 * |
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