八种海参中主要海参皂苷的结构特性研究
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摘要
海参(sea cucumber)是我国一种传统的海洋滋补品,富含多种生理活性成分,具有较高的食用和药用价值。海参皂苷是海参体内最重要的活性成分之一,具有抗肿瘤、抗真菌、免疫调节、细胞毒作用和溶血作用等多种生理活性。本论文对仿刺参中的皂苷组分做了分离鉴定,并采用ESI-MS的方法对其质谱的裂解规律进行了研究,采用HPLC的方法建立了仿刺参皂苷指纹图谱,随后成功将此方法延伸到了其他8种海参的皂苷特征图谱和结构分析中。本论文的研究和结果为海参品质的评价、海参种类的鉴别以及建立海参质量评价标准提供了理论基础和科学依据,对促进海参产业的发展具有重要的理论意义和应用价值。本文主要内容包括以下几个部分:
1.采用大孔树脂、硅胶柱层析和半制备HPLC技术,从仿刺参(Apostichopus japonicus)体壁中分离得到6种海参皂苷化合物,根据化合物的理化性质和波谱数据,共鉴定了3种皂苷化合物的结构,分别为:cladoloside B, holotoxin A1和holotoxin B1。
2.采用电喷雾飞行时间质谱技术(ESI-TOF-MS),在负离子检测方式下,对9种皂苷化合物的质谱裂解途径进行了研究。通过ESI-MS产生的[M-H]-/ [M-Na]-获得了相应化合物的分子质量信息。对[M-H]-/ [M-Na]-进行碰撞诱导解离(CID)获得了相应化合物的裂解途径信息。在二级质谱中,糖链上无硫酸酯基取代的皂苷发生糖苷键的断裂,连续丢失糖链的末端单糖,最后生成苷元的特征碎片离子,这些特征有助于皂苷的结构解析。糖链上有硫酸酯基取代的皂苷不发生糖苷键的断裂,而是发生了苷元的裂解,生成了更加稳定的结构。将其进行脱硫酸化处理后,其脱硫产物的MS/MS图谱中出现糖链上单糖顺序脱落形成的碎片峰。根据已知皂苷的二级质谱裂解规律,对仿刺参体内提取出的3种含量较少,无法进行核磁分析的皂苷单体进行了质谱分析,推测出了3种皂苷的结构。
3.建立了仿刺参(Apostichopus japonicus)皂苷类成分的HPLC指纹图谱,为仿刺参的质量控制提供了新的方法。实验采用固相萃取(SPE)制备供试品溶液,选用Zorbox SB-C18色谱柱(250 mm×4.6 mm, 5μm),以乙腈-0.1%磷酸水溶液为流动相进行梯度洗脱,柱温30℃,流速1.0 mL/min,检测波长为205 nm。分析了不同产地的10批仿刺参样品,采用国家药典委员会推荐的“中药色谱指纹图谱相似度评价系统(2004 A版)”处理谱图,确定了6个共有峰。计算了10个样本间的指纹图谱相似度,所得相似度计算结果均大于0.97。该方法具有良好的稳定性和重现性,可用于仿刺参的质量控制。
4.采用SPE-HPLC方法研究了8种海参的总皂苷特征图谱,比较不同种海参间皂苷的组成及含量差异,为海参的品种鉴定提供依据。使用Zorbax SB-C18(250mm×4.6 mm, 5μm)色谱柱,以乙腈-0.1%的三氟乙酸水溶液为流动相梯度洗脱,柱温30℃,流速1.0 mL/min,检测波长205nm。对不同海参体内皂苷类成分进行HPLC分析,所得图谱特征性强,8种海参的各皂苷成分均得到很好的色谱分离。结果表明不同海参体内的皂苷组成及含量有明显差异,所建立的方法简便、可靠,可用于海参的品种鉴定。
5.采用HPLC-MS/MS联用技术,对8种海参体内主要的皂苷类成分进行了定性鉴定。选用Eclipse XDB-C18色谱柱(150mm×4.6mm, 5μm),以乙腈-0.1%碳酸氢铵水溶液为流动相进行梯度洗脱,通过与电喷雾飞行时间质谱联用获得各皂苷成分的精确分子量和分子式,通过碰撞诱导解离技术(CID)获得各化合物的裂解信息。每种海参选取含量较高具有代表性的几种皂苷作为其特征峰,通过定性鉴定,确认了每种海参独特的皂苷组成,并结合文献对部分已知皂苷化合物的结构进行了初步鉴定。该技术还可用于新皂苷化合物的快速检测,为寻找新颖的皂苷化合物提供快速简便的方法。
Sea cucumber is a traditional costful tonic sea food in China, which contains multi-kinds of bioactive components. It is well known that holothurians are of high nutrition and pharmic values. Triterpene glycosides, one of the most important bioactive compositions of sea cucumbers, are proved to exhibit various biological activities, including anti-tumor, antifungal, immunomodulatory, cytotoxic and hemolytic effects. This thesis make a study on the isolation and identification on triterpene glycosides in sea cucumber Apostichopus japonicus, their fragmentation patterns are investigated using electrospray ionization-mass spectrometry (ESI-MS) method, and finally establish the fingerprint chromatograms of triterpene glycosides in S. japonicus by high performance liquid chromatography (HPLC). This method is successfully used for the characteristic spectrum and structure analyze of eight other different sea cucumbers. The researches will provide some academic and scientific groundwork for the identification of different types of sea cucumbers, also for quality control and nutrition evaluation of sea cucumber. The main researches in this thesis are listed below:
1. To study the constituents and proportion of triterpene glycosides from Apostichopus japonicus, macroporous resin, Si-gel chromatography and semi-preparative HPLC are used. Six triterpene glycosides are found, chemical structures of three compounds are identified. They are cladoloside B, holotoxin A1 and holotoxin B1 based on the chemical evidence and spectral data.
2. The fragment pathways of nine kinds of triterpene glycosides from sea cucumbers has been investigated in negative ion mode by electrospray ionization -time of flight-mass spectrometry (ESI-TOF-MS). The[M-H]-/ [M-Na]-ions are observed by ESI-MS, from which the molecular weights are obtained. The collision induced dissociation (CID) data of the [M - H] - / [M - Na] - ions provide fragmentation pathways of the triterpene glycosides. In the MS/MS spectra, results show that the cleavage of non-sulfated triterpene glycosides is occurred on the sugar chain. Product ions are produced by consecutively losses of monosaccharide residue from sugar chain, and finally yield a signature ion of aglycone. These characteristic fragmentations will be helpful in identifying the structures of triterpene glycosides. The sulfated triterpene glycosides have different fragmentation pattern, the cleavage is occured on the agalycon, generating a more stable structure. After solvolysis, the desufated productions show signature ions by the cleavage of glucosidic bonds again. The fragmentation patterns are used for the structural conjecture of three minor triterpene glycosides from Apostichopus japonicus, and their structures are concluded by the information of MS/MS spectra.
3. The fingerprint chromatograms of triterpene glycosides in S. japonicus are established for its quality control. The samples are prepared by solid phase extraction (SPE). The analysis is performed on a Zorbax SB-C18 column (250 mm×4.6 mm, 5μm) with acetonitrile-water (containing 0.1% phosphoric acid) as mobile phase, gradient elution, at a flow rate of 1.0 mL/min, at a column temperature of 30℃, and the detection wavelength is 205nm. Ten different original samples are analyzed, and 6 peaks are identified as common fingerprint peaks using the similarity evaluation system for chromatographic fingerprint of TCM(Version 2004 A)recommended by State Pharmacopoeia Committee of China. The similarity of the fingerprints is greater than 0.97. The method set up is proved to be stable and repeatable and can be utilized as a quality control for S. japonicus.
4. A SPE-HPLC methord is established for the species identification by comparing the composition of triterpene glycosides among different sea cucumbers. The analysis is performed on a Zorbax SB-C18 column (250mm×4.6 mm, 5μm), use acetonitrile- water (containing 0.1% trifluoroacetic acid) as mobile phase, gradient elution, at a flow rate of 1.0 mL/min, at a column temperature of 30℃, and the detection wavelength is set at 205nm. The HPLC analysis of triterpene glycosides from different sea cucumbers is established for the first time. Among the obtained characteristic spectrums, all the detected peaks are separated effectively. The results show that triterpene glycosides in different sea cucumbers are significant difference. The method established is simple, stable, and can be utilized as a quality control for sea cucumber.
5. A convenient method based on high performance liquid chromatography-mass spectrometry (HPLC-MS/MS) has been developed for analysis and characterization of triterpene saponins in extract of different sea cucumbers. Samples are analyzed on a Eclipse XDB-C18 column ( 150mm×4.6mm, 5μm ) , with acetonitrile-water (containing 0.1% ammonium acid carbonate) as mobile phase, gradient elution. ESI-TOF-MS is used to obtain accurate molecular weight and molecular formula information of triterpene glycosides. Fragmentation behavior is obtained by CID experiment. Several chromatographic peaks are chosen for signature peaks for different sea cucumbers, and their unique compositions are verified. Combined with literature review, some triterpene glycosides are primary identified. This method has the advantages of simple operation, rapid measurement, and it is a powerful tool for identification of new triterpene glycosides.
1.采用大孔树脂、硅胶柱层析和半制备HPLC技术,从仿刺参(Apostichopus japonicus)体壁中分离得到6种海参皂苷化合物,根据化合物的理化性质和波谱数据,共鉴定了3种皂苷化合物的结构,分别为:cladoloside B, holotoxin A1和holotoxin B1。
2.采用电喷雾飞行时间质谱技术(ESI-TOF-MS),在负离子检测方式下,对9种皂苷化合物的质谱裂解途径进行了研究。通过ESI-MS产生的[M-H]-/ [M-Na]-获得了相应化合物的分子质量信息。对[M-H]-/ [M-Na]-进行碰撞诱导解离(CID)获得了相应化合物的裂解途径信息。在二级质谱中,糖链上无硫酸酯基取代的皂苷发生糖苷键的断裂,连续丢失糖链的末端单糖,最后生成苷元的特征碎片离子,这些特征有助于皂苷的结构解析。糖链上有硫酸酯基取代的皂苷不发生糖苷键的断裂,而是发生了苷元的裂解,生成了更加稳定的结构。将其进行脱硫酸化处理后,其脱硫产物的MS/MS图谱中出现糖链上单糖顺序脱落形成的碎片峰。根据已知皂苷的二级质谱裂解规律,对仿刺参体内提取出的3种含量较少,无法进行核磁分析的皂苷单体进行了质谱分析,推测出了3种皂苷的结构。
3.建立了仿刺参(Apostichopus japonicus)皂苷类成分的HPLC指纹图谱,为仿刺参的质量控制提供了新的方法。实验采用固相萃取(SPE)制备供试品溶液,选用Zorbox SB-C18色谱柱(250 mm×4.6 mm, 5μm),以乙腈-0.1%磷酸水溶液为流动相进行梯度洗脱,柱温30℃,流速1.0 mL/min,检测波长为205 nm。分析了不同产地的10批仿刺参样品,采用国家药典委员会推荐的“中药色谱指纹图谱相似度评价系统(2004 A版)”处理谱图,确定了6个共有峰。计算了10个样本间的指纹图谱相似度,所得相似度计算结果均大于0.97。该方法具有良好的稳定性和重现性,可用于仿刺参的质量控制。
4.采用SPE-HPLC方法研究了8种海参的总皂苷特征图谱,比较不同种海参间皂苷的组成及含量差异,为海参的品种鉴定提供依据。使用Zorbax SB-C18(250mm×4.6 mm, 5μm)色谱柱,以乙腈-0.1%的三氟乙酸水溶液为流动相梯度洗脱,柱温30℃,流速1.0 mL/min,检测波长205nm。对不同海参体内皂苷类成分进行HPLC分析,所得图谱特征性强,8种海参的各皂苷成分均得到很好的色谱分离。结果表明不同海参体内的皂苷组成及含量有明显差异,所建立的方法简便、可靠,可用于海参的品种鉴定。
5.采用HPLC-MS/MS联用技术,对8种海参体内主要的皂苷类成分进行了定性鉴定。选用Eclipse XDB-C18色谱柱(150mm×4.6mm, 5μm),以乙腈-0.1%碳酸氢铵水溶液为流动相进行梯度洗脱,通过与电喷雾飞行时间质谱联用获得各皂苷成分的精确分子量和分子式,通过碰撞诱导解离技术(CID)获得各化合物的裂解信息。每种海参选取含量较高具有代表性的几种皂苷作为其特征峰,通过定性鉴定,确认了每种海参独特的皂苷组成,并结合文献对部分已知皂苷化合物的结构进行了初步鉴定。该技术还可用于新皂苷化合物的快速检测,为寻找新颖的皂苷化合物提供快速简便的方法。
Sea cucumber is a traditional costful tonic sea food in China, which contains multi-kinds of bioactive components. It is well known that holothurians are of high nutrition and pharmic values. Triterpene glycosides, one of the most important bioactive compositions of sea cucumbers, are proved to exhibit various biological activities, including anti-tumor, antifungal, immunomodulatory, cytotoxic and hemolytic effects. This thesis make a study on the isolation and identification on triterpene glycosides in sea cucumber Apostichopus japonicus, their fragmentation patterns are investigated using electrospray ionization-mass spectrometry (ESI-MS) method, and finally establish the fingerprint chromatograms of triterpene glycosides in S. japonicus by high performance liquid chromatography (HPLC). This method is successfully used for the characteristic spectrum and structure analyze of eight other different sea cucumbers. The researches will provide some academic and scientific groundwork for the identification of different types of sea cucumbers, also for quality control and nutrition evaluation of sea cucumber. The main researches in this thesis are listed below:
1. To study the constituents and proportion of triterpene glycosides from Apostichopus japonicus, macroporous resin, Si-gel chromatography and semi-preparative HPLC are used. Six triterpene glycosides are found, chemical structures of three compounds are identified. They are cladoloside B, holotoxin A1 and holotoxin B1 based on the chemical evidence and spectral data.
2. The fragment pathways of nine kinds of triterpene glycosides from sea cucumbers has been investigated in negative ion mode by electrospray ionization -time of flight-mass spectrometry (ESI-TOF-MS). The[M-H]-/ [M-Na]-ions are observed by ESI-MS, from which the molecular weights are obtained. The collision induced dissociation (CID) data of the [M - H] - / [M - Na] - ions provide fragmentation pathways of the triterpene glycosides. In the MS/MS spectra, results show that the cleavage of non-sulfated triterpene glycosides is occurred on the sugar chain. Product ions are produced by consecutively losses of monosaccharide residue from sugar chain, and finally yield a signature ion of aglycone. These characteristic fragmentations will be helpful in identifying the structures of triterpene glycosides. The sulfated triterpene glycosides have different fragmentation pattern, the cleavage is occured on the agalycon, generating a more stable structure. After solvolysis, the desufated productions show signature ions by the cleavage of glucosidic bonds again. The fragmentation patterns are used for the structural conjecture of three minor triterpene glycosides from Apostichopus japonicus, and their structures are concluded by the information of MS/MS spectra.
3. The fingerprint chromatograms of triterpene glycosides in S. japonicus are established for its quality control. The samples are prepared by solid phase extraction (SPE). The analysis is performed on a Zorbax SB-C18 column (250 mm×4.6 mm, 5μm) with acetonitrile-water (containing 0.1% phosphoric acid) as mobile phase, gradient elution, at a flow rate of 1.0 mL/min, at a column temperature of 30℃, and the detection wavelength is 205nm. Ten different original samples are analyzed, and 6 peaks are identified as common fingerprint peaks using the similarity evaluation system for chromatographic fingerprint of TCM(Version 2004 A)recommended by State Pharmacopoeia Committee of China. The similarity of the fingerprints is greater than 0.97. The method set up is proved to be stable and repeatable and can be utilized as a quality control for S. japonicus.
4. A SPE-HPLC methord is established for the species identification by comparing the composition of triterpene glycosides among different sea cucumbers. The analysis is performed on a Zorbax SB-C18 column (250mm×4.6 mm, 5μm), use acetonitrile- water (containing 0.1% trifluoroacetic acid) as mobile phase, gradient elution, at a flow rate of 1.0 mL/min, at a column temperature of 30℃, and the detection wavelength is set at 205nm. The HPLC analysis of triterpene glycosides from different sea cucumbers is established for the first time. Among the obtained characteristic spectrums, all the detected peaks are separated effectively. The results show that triterpene glycosides in different sea cucumbers are significant difference. The method established is simple, stable, and can be utilized as a quality control for sea cucumber.
5. A convenient method based on high performance liquid chromatography-mass spectrometry (HPLC-MS/MS) has been developed for analysis and characterization of triterpene saponins in extract of different sea cucumbers. Samples are analyzed on a Eclipse XDB-C18 column ( 150mm×4.6mm, 5μm ) , with acetonitrile-water (containing 0.1% ammonium acid carbonate) as mobile phase, gradient elution. ESI-TOF-MS is used to obtain accurate molecular weight and molecular formula information of triterpene glycosides. Fragmentation behavior is obtained by CID experiment. Several chromatographic peaks are chosen for signature peaks for different sea cucumbers, and their unique compositions are verified. Combined with literature review, some triterpene glycosides are primary identified. This method has the advantages of simple operation, rapid measurement, and it is a powerful tool for identification of new triterpene glycosides.
引文
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