南葶苈子脂肪油成分的提取、分离和成分鉴定研究
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摘要
南葶苈子来源于十字花科植物播娘篙(Descurainia sophia(L.)Webb.ex Prantl)的干燥成熟种子,又称华东葶苈子。2005年版《中国药典》规定葶苈子来源为十字花科植物独行菜Lepidium apetalum Willd和播娘蒿Descurainiasophia(L.)Webb.ex Prantl的干燥成熟种子,前者称为“北葶苈子”,后者称为“南葶苈子”。目前葶苈子商品药材的主流品种为南葶苈子。南葶苈子含油量高,且油中多不饱和脂肪酸含量高,具有明显的调血脂作用。
通过文献调研得知,国外对南葶苈子的研究主要在其挥发油、脂肪油类成分方面,国内对南葶苈子的研究多集中在药用活性成分及药理作用,而有关南葶苈子脂肪油提取方法和工艺研究及开发利用未见报道。本文对南葶苈子脂肪油作了较为系统的研究,包括油脂的提取方法及提取工艺的研究、以及脂肪酸及不皂化物的分离鉴定。
建立了南葶苈子脂肪油的提取工艺。经过选择4种提取溶剂进行比较,通过实验研究,确定石油醚(30-60℃)为提取南葶苈子脂肪油的最佳溶剂,通过比较几种提取方法:索氏提取法、冷浸提取法、超声提取法、微波提取法对得到的油脂的提取率和理化性质,确定最佳的提取方法为超声提取法,该方法提取速度快(30min-1h),所得油脂理化性质为:相对密度(20/4℃)0.9176,折光指数(n~(20))1.4767,酸值3.43(mgKOH/g),皂化值182.54(mgKOH/g),过氧化值1.65(meq/Kg),碘值153.26(gI_2/100g)。
优化了超声提取工艺,通过单因素和正交实验设计优化超声波辅助提取南葶苈子脂肪油。研究了提取的温度、时间、料液比、粉碎度、提取次数及超声频率、功率对提取率的影响。优化的提取工艺参数为:提取温度30℃、料液比为1:6(g/ml)、提取时间40min、南葶苈子粉碎过55目筛、超声频率和功率分别为45kHz和240W,提取1次,平均出油率可达到31.95%,表明该工艺稳定、可行。
建立了利用气相色谱-质谱联用技术分离、鉴定南葶苈子脂肪油组成的分析方法。将南葶苈子脂肪油的油样经皂化后采用三氟化硼-甲醇进行甲酯化处理,以气相色谱-质谱联用技术分离,共鉴定出29种脂肪酸。南葶苈子脂肪酸的主要组成为:α-亚麻酸26.12%,亚油酸15.68%,芥酸12.34%,11-二十碳烯酸11.34%,油酸10.75%,棕榈酸6.40%,硬脂酸3.03%,其中不饱和脂肪酸总量占86.06%。结果表明,南葶苈子脂肪油含有多种对人体有益的脂肪酸,是一种具有较高开发价值的功能性油脂。
首次采用柱层析结合薄层色谱法对南葶苈子油不皂化物进行了分离,气相色谱-质谱联用对不皂化物各部分进行成分鉴定和含量测定。南葶苈子油不皂化物的主要成分为烃类、4-去甲基甾醇、4-甲基甾醇和三萜醇,另外,还检测出生育酚和环氧角鲨烯。以上鉴定的化合物中,除β-谷甾醇外,其它均为首次从南葶苈子中检出。
This kind of Chinese traditional medicine is the ripe dried seed of Descurainia sophia(L.)Webb ex Prantl, which is the plant of Cruciferae. The pharmacopoeia of P.R.China(2005 revision)specifies Tinglizi as the ripe dried seeds of Descurainia sophia(L.)Webb ex Prantl and Lepidium apetalum Willd. Descurainia sophia(L.) Webb ex Prantl is the main sources of Tinglizi at present. The Descurainia sophia(L.) seed oil contains polyunsaturated fatty acids(PUFAs), which have important functions for human health.
Based on a series of literature investigations, research field of Descurainia sophia(L.) seed abroad was mainly in it's essential oil and fatty oil, while domestic research emphasised on active pharmaceutical ingredients and pharmacological effects of it. But little study on the extraction technology seed oil in Descurainia sophia(L.) was carried over the time. This research attempts to make a systematic research on the seed oil of Descurainia sophia(L.), including chose extration method and optimized the extration technical, the fatty acid composition and unsaponifiable matter constituents were also investigated in this thesis.
The extraction method of Descurainia sophia(L.) seed oil was established. After comparing four extraction solvent, it was found that pertroleum ether can be used as the most suitable solvent to extract fatty oil from the seed oil of Descurainia sophia(L.). Comparison of extraction rate and physiacl-chemiacl porperties of the obtained oil by four extraction methods, it is suggests that ultrasound-assisted extraction is the best one. Specific gavity(20/4℃), rerfactive index(n~(20)), acid value (mgKOH/g), Saponification value(mgKOH/g), peroxide value(meq/Kg), iodine value (gI_2/100g) of Descurainia sophia(L.) seed oil extareted by ultrasound-assisted are 0.9176, 1.4767,3.43, 182.54, 1.65, 153.26, respectively.
Ultrasound-associated extraction technology of Descurainia sophia(L.) seed oil was optimized. The effects of some operating parameters such as appropriate extraction solvent, extraction temperature, extraction time, solvent to solid ratio, and ultrasonic power and frequency on the yield of Descurainia sophia(L.) seed oil have been investigated. The optimal conditions were obtained as follows: the extraction solvent was pertroleum ether, extraction temperature was 30℃, solvent to solid ratio was 1:6(g/ml), extraction time was 40min, size of raw material was 55 mesh, extraction times of 1 time, ultrasonic power and frequency are 45kHz and 240W respectively. The average extraction rate was 31.95%.
The method for analysis and identification fatty acids in Descurainia sophia(L.) seed oil was established. After Saponification and methylated by BF3/methanol the oil was analyzed by GC-MS. 29 components were identified. The analysis results indicate that the main compositions of the fatty acids in Descurainia sophia(L.) seed areα-linolenic acid(26.12%), linoleic acid(15.68%), erucic acid(12.34%), 11 -Eicosenoic acid(11.34%), oleic acid(10.75%), palmi tic acid(6.40%), stearic acid(3.03%).The total content of unsaturated acids is 86.06%, which suggest that Descurainia sophia(L.) seed oil has a developing potential as functional oil.
Column chromatography and thin-layer chromatography were used to separate unsaponifiable matters in Descurainia sophia(L.) seed oil. Each portion of the unsaponifiable matters was analyzed by GC-MS. The main contents of the unsaponifable matters in Descurainia sophia(L.) seed oil are hydrocarbons, sterol,4-methylsteols and triterpene alcohols, 2,3-Oxidosqualene and tocopherol are also detected in the unsaponifable matters. All compounds exceptβ-Sitosterol were determined from Descurainia sophia(L.) seed for the first time.
通过文献调研得知,国外对南葶苈子的研究主要在其挥发油、脂肪油类成分方面,国内对南葶苈子的研究多集中在药用活性成分及药理作用,而有关南葶苈子脂肪油提取方法和工艺研究及开发利用未见报道。本文对南葶苈子脂肪油作了较为系统的研究,包括油脂的提取方法及提取工艺的研究、以及脂肪酸及不皂化物的分离鉴定。
建立了南葶苈子脂肪油的提取工艺。经过选择4种提取溶剂进行比较,通过实验研究,确定石油醚(30-60℃)为提取南葶苈子脂肪油的最佳溶剂,通过比较几种提取方法:索氏提取法、冷浸提取法、超声提取法、微波提取法对得到的油脂的提取率和理化性质,确定最佳的提取方法为超声提取法,该方法提取速度快(30min-1h),所得油脂理化性质为:相对密度(20/4℃)0.9176,折光指数(n~(20))1.4767,酸值3.43(mgKOH/g),皂化值182.54(mgKOH/g),过氧化值1.65(meq/Kg),碘值153.26(gI_2/100g)。
优化了超声提取工艺,通过单因素和正交实验设计优化超声波辅助提取南葶苈子脂肪油。研究了提取的温度、时间、料液比、粉碎度、提取次数及超声频率、功率对提取率的影响。优化的提取工艺参数为:提取温度30℃、料液比为1:6(g/ml)、提取时间40min、南葶苈子粉碎过55目筛、超声频率和功率分别为45kHz和240W,提取1次,平均出油率可达到31.95%,表明该工艺稳定、可行。
建立了利用气相色谱-质谱联用技术分离、鉴定南葶苈子脂肪油组成的分析方法。将南葶苈子脂肪油的油样经皂化后采用三氟化硼-甲醇进行甲酯化处理,以气相色谱-质谱联用技术分离,共鉴定出29种脂肪酸。南葶苈子脂肪酸的主要组成为:α-亚麻酸26.12%,亚油酸15.68%,芥酸12.34%,11-二十碳烯酸11.34%,油酸10.75%,棕榈酸6.40%,硬脂酸3.03%,其中不饱和脂肪酸总量占86.06%。结果表明,南葶苈子脂肪油含有多种对人体有益的脂肪酸,是一种具有较高开发价值的功能性油脂。
首次采用柱层析结合薄层色谱法对南葶苈子油不皂化物进行了分离,气相色谱-质谱联用对不皂化物各部分进行成分鉴定和含量测定。南葶苈子油不皂化物的主要成分为烃类、4-去甲基甾醇、4-甲基甾醇和三萜醇,另外,还检测出生育酚和环氧角鲨烯。以上鉴定的化合物中,除β-谷甾醇外,其它均为首次从南葶苈子中检出。
This kind of Chinese traditional medicine is the ripe dried seed of Descurainia sophia(L.)Webb ex Prantl, which is the plant of Cruciferae. The pharmacopoeia of P.R.China(2005 revision)specifies Tinglizi as the ripe dried seeds of Descurainia sophia(L.)Webb ex Prantl and Lepidium apetalum Willd. Descurainia sophia(L.) Webb ex Prantl is the main sources of Tinglizi at present. The Descurainia sophia(L.) seed oil contains polyunsaturated fatty acids(PUFAs), which have important functions for human health.
Based on a series of literature investigations, research field of Descurainia sophia(L.) seed abroad was mainly in it's essential oil and fatty oil, while domestic research emphasised on active pharmaceutical ingredients and pharmacological effects of it. But little study on the extraction technology seed oil in Descurainia sophia(L.) was carried over the time. This research attempts to make a systematic research on the seed oil of Descurainia sophia(L.), including chose extration method and optimized the extration technical, the fatty acid composition and unsaponifiable matter constituents were also investigated in this thesis.
The extraction method of Descurainia sophia(L.) seed oil was established. After comparing four extraction solvent, it was found that pertroleum ether can be used as the most suitable solvent to extract fatty oil from the seed oil of Descurainia sophia(L.). Comparison of extraction rate and physiacl-chemiacl porperties of the obtained oil by four extraction methods, it is suggests that ultrasound-assisted extraction is the best one. Specific gavity(20/4℃), rerfactive index(n~(20)), acid value (mgKOH/g), Saponification value(mgKOH/g), peroxide value(meq/Kg), iodine value (gI_2/100g) of Descurainia sophia(L.) seed oil extareted by ultrasound-assisted are 0.9176, 1.4767,3.43, 182.54, 1.65, 153.26, respectively.
Ultrasound-associated extraction technology of Descurainia sophia(L.) seed oil was optimized. The effects of some operating parameters such as appropriate extraction solvent, extraction temperature, extraction time, solvent to solid ratio, and ultrasonic power and frequency on the yield of Descurainia sophia(L.) seed oil have been investigated. The optimal conditions were obtained as follows: the extraction solvent was pertroleum ether, extraction temperature was 30℃, solvent to solid ratio was 1:6(g/ml), extraction time was 40min, size of raw material was 55 mesh, extraction times of 1 time, ultrasonic power and frequency are 45kHz and 240W respectively. The average extraction rate was 31.95%.
The method for analysis and identification fatty acids in Descurainia sophia(L.) seed oil was established. After Saponification and methylated by BF3/methanol the oil was analyzed by GC-MS. 29 components were identified. The analysis results indicate that the main compositions of the fatty acids in Descurainia sophia(L.) seed areα-linolenic acid(26.12%), linoleic acid(15.68%), erucic acid(12.34%), 11 -Eicosenoic acid(11.34%), oleic acid(10.75%), palmi tic acid(6.40%), stearic acid(3.03%).The total content of unsaturated acids is 86.06%, which suggest that Descurainia sophia(L.) seed oil has a developing potential as functional oil.
Column chromatography and thin-layer chromatography were used to separate unsaponifiable matters in Descurainia sophia(L.) seed oil. Each portion of the unsaponifiable matters was analyzed by GC-MS. The main contents of the unsaponifable matters in Descurainia sophia(L.) seed oil are hydrocarbons, sterol,4-methylsteols and triterpene alcohols, 2,3-Oxidosqualene and tocopherol are also detected in the unsaponifable matters. All compounds exceptβ-Sitosterol were determined from Descurainia sophia(L.) seed for the first time.
引文
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