Characterization of secondary metabolites from the raphides of calcium oxalate contained in three
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Z. Liang et al., Eur. J. Mass Spectrom. 19, 195–210 (2013) Received: 5 July 2013 n Accepted: 16 July 2013 n Publication: 5 August 2013
195
EUROPEAN JOURNAL OF MASS SPECTROMETRY
Introduction
There are more than 3500 species of plants in the Araceae family in the world.1 Many species are used as Chinese herbal materials. For example, the dried stem tuber of Pinellia ternata (Thunb.) Breit. is the source of the herbal medicinal Banxia which is recorded in the Chinese Pharmacopoeia.2 In addition, P. pedatisecta Schott and Typhonium flagelliforme (Lodd.) Blume from the Araceae family are also used as Chinese herbal materials, namely Zhangye Banxia and Shui Banxia, respectively.3 In the ancient book “Collection of Commentaries on the Classic of the Materia Medica (Ben Cao Jing Ji Zhu)” written in about AD 480–498, it was recorded that Banxia has a strong irritating effect on the throat.4 Therefore, traditionally, Banxia was processed for medicinal use. There were three methods of processing: (1) with alum, to produce “Qingbanxia”; (2) with both ginger and alum, to produce “Jiangbanxia”; or (3) with calcium oxide and licorice (Glycyrrhizae Radix & rhizoma) to produce “Fabanxia”. These methods of processing can reduce the irritation of Banxia.5–7 Modern pharmacological studies have also found that Banxia irritates many kinds of mucosa.5–8 Many studies have been done to determine which components of Banxia cause the irritation.9–11 At the end of the 1950s, Japanese scholars thought homogentisic acid and its glucoside were the irritative constituents. 9 In 1969, the gluocoside of protocatechu aldehyde was reported as the irritative substance.10 However, these two views have not been confirmed by pharmacological data. In 1999, it was reported that raphides of calcium oxalate contained in Banxia induced the irritative effects.11,12 Further studies found that the raphides of calcium oxalate were mainly composed of calcium oxalate and proteins, with trace polysaccharides.13 Comparing the calcium oxalate of Banxia and its processed products, it can be seen that the shape of the raphides changes and the content of calcium oxalate decreases greatly after processing.14 However, in those studies on raphides of calcium oxalate contained in Banxia, the sample processing involved complicated procedures including grinding, extraction with various organic solvents, centrifuging force and precipitation, which would damage or result in the loss of chemicals contained in raphides of calcium oxalate. Besides, both the stem tubers from P . pedatisecta and T. flagelliforme also exhibit strong effects of irritation.12,15 Actually, many plants belonging to the Araceae family can cause irritation, such as Alocasia , Arisaema , Caladium , Colocasia, Dieffenbachia and Philodendron plants. They all contain calcium oxalate crystals in the form of raphides. The raphides of calcium oxalate are thought to mechanically damage cells in the mouth during ingestion and may allow toxins to enter and create cellular havoc.16–19 Although the raphides of calcium oxalate have been found to attribute to strong irritation, any other possible toxic chemicals involving them are unknown. Many studies have demonstrated that the stem tubers of P. ternata, P. pedatisecta and T. flagelliforme contain essential oils, amino acids, alkaloids and a large amount of unsaturated
Zhitao Liang,a,†,* Jian Zhang,†,a,b Lailai Wong,a Tao Yi,a Hubiao Chena and Zhongzhen Zhaoa,*
a School of Chinese Medicine, Hong Kong Baptist University, Kowloon, Hong Kong Special Administrative Region, P.R. China. E-mail: lzt23@hkbu.edu.hk; zzzhao@hkbu.edu.hk b
Characterization of secondary metabolites from the raphides of calcium oxalate contained in three Araceae family plants using laser miHale Waihona Puke Baidurodissection and ultrahigh performance liquid chromatographyquadrupole/time of flight-mass spectrometry
†
These authors contributed equally to this work
© IM Publications LLP 2013 All rights reserved
ISSN: 1469-0667 doi: 10.1255/ejms.1224
196
Characterization of Secondary Metabolites from Raphides of Calcium Oxylate in Three Araceae Plants
College of Pharmaceutical Science, Soochow University, 215123 Suzhou, PR China
The dried stem tubers of Pinellia ternata (Thunb.) Breit, P. pedatisecta Schott and Typhonium flagelliforme (Lodd.) Blume from the Araceae family are used as Chinese medicines, namely Banxia, Zhangye Banxia and Shui Banxia, respectively. They have been reported to have a strong irritative effect on mucosa. Previous studies have indicated that the pure raphides of calcium oxalate contained in the stem tubers of three plants have attributed to this strong irritation. However, the processed products of the stem tubers of P. ternata, including Fabanxia, Qingbanxia and Jiangbanxia, have been found to have no irritative effects on mucosa. Currently, the secondary metabolites from the raphides of calcium oxalate contained in the stem tubers of P. ternata with its processed products, P. pedatisecta and T. flagelliforme were analyzed by means of laser microdissection and ultra-high performance liquid chromatography-quadrupole/ time of flight-mass spectrometry. The results indicate that the stem tubers of P. ternata P. pedatisecta and T. flagelliforme mainly contain amino acids, fatty acids, cyclic dipeptides and alkaloids. The secondary metabolite profile of the stem tuber of P. ternata was different from those of its processed products, Fabanxia, Qingbanxia and Jiangbanxia. However, the secondary metabolites from their raphides of calcium oxalate all contained beta-sitosterol, sitosterol palmitate, trigonelline, octadecenoic acid, pedatisectine A and thymidine. The raphides of calcium oxalate from P. ternata, P. pedatisecta and T. flagelliforme do not include any specific irritants. The results indicated that the irritation induced by raphides of calcium oxalate of three Araceae family plants is not relevant to the secondary metabolites but relates to the special needle shape. Keywords: Araceae, Pinellia ternata, Pinellia pedatisecta, Typhonium flagelliforme, raphides of calcium oxalate, UHPLC-QTOF-MS, laser microdissection
195
EUROPEAN JOURNAL OF MASS SPECTROMETRY
Introduction
There are more than 3500 species of plants in the Araceae family in the world.1 Many species are used as Chinese herbal materials. For example, the dried stem tuber of Pinellia ternata (Thunb.) Breit. is the source of the herbal medicinal Banxia which is recorded in the Chinese Pharmacopoeia.2 In addition, P. pedatisecta Schott and Typhonium flagelliforme (Lodd.) Blume from the Araceae family are also used as Chinese herbal materials, namely Zhangye Banxia and Shui Banxia, respectively.3 In the ancient book “Collection of Commentaries on the Classic of the Materia Medica (Ben Cao Jing Ji Zhu)” written in about AD 480–498, it was recorded that Banxia has a strong irritating effect on the throat.4 Therefore, traditionally, Banxia was processed for medicinal use. There were three methods of processing: (1) with alum, to produce “Qingbanxia”; (2) with both ginger and alum, to produce “Jiangbanxia”; or (3) with calcium oxide and licorice (Glycyrrhizae Radix & rhizoma) to produce “Fabanxia”. These methods of processing can reduce the irritation of Banxia.5–7 Modern pharmacological studies have also found that Banxia irritates many kinds of mucosa.5–8 Many studies have been done to determine which components of Banxia cause the irritation.9–11 At the end of the 1950s, Japanese scholars thought homogentisic acid and its glucoside were the irritative constituents. 9 In 1969, the gluocoside of protocatechu aldehyde was reported as the irritative substance.10 However, these two views have not been confirmed by pharmacological data. In 1999, it was reported that raphides of calcium oxalate contained in Banxia induced the irritative effects.11,12 Further studies found that the raphides of calcium oxalate were mainly composed of calcium oxalate and proteins, with trace polysaccharides.13 Comparing the calcium oxalate of Banxia and its processed products, it can be seen that the shape of the raphides changes and the content of calcium oxalate decreases greatly after processing.14 However, in those studies on raphides of calcium oxalate contained in Banxia, the sample processing involved complicated procedures including grinding, extraction with various organic solvents, centrifuging force and precipitation, which would damage or result in the loss of chemicals contained in raphides of calcium oxalate. Besides, both the stem tubers from P . pedatisecta and T. flagelliforme also exhibit strong effects of irritation.12,15 Actually, many plants belonging to the Araceae family can cause irritation, such as Alocasia , Arisaema , Caladium , Colocasia, Dieffenbachia and Philodendron plants. They all contain calcium oxalate crystals in the form of raphides. The raphides of calcium oxalate are thought to mechanically damage cells in the mouth during ingestion and may allow toxins to enter and create cellular havoc.16–19 Although the raphides of calcium oxalate have been found to attribute to strong irritation, any other possible toxic chemicals involving them are unknown. Many studies have demonstrated that the stem tubers of P. ternata, P. pedatisecta and T. flagelliforme contain essential oils, amino acids, alkaloids and a large amount of unsaturated
Zhitao Liang,a,†,* Jian Zhang,†,a,b Lailai Wong,a Tao Yi,a Hubiao Chena and Zhongzhen Zhaoa,*
a School of Chinese Medicine, Hong Kong Baptist University, Kowloon, Hong Kong Special Administrative Region, P.R. China. E-mail: lzt23@hkbu.edu.hk; zzzhao@hkbu.edu.hk b
Characterization of secondary metabolites from the raphides of calcium oxalate contained in three Araceae family plants using laser miHale Waihona Puke Baidurodissection and ultrahigh performance liquid chromatographyquadrupole/time of flight-mass spectrometry
†
These authors contributed equally to this work
© IM Publications LLP 2013 All rights reserved
ISSN: 1469-0667 doi: 10.1255/ejms.1224
196
Characterization of Secondary Metabolites from Raphides of Calcium Oxylate in Three Araceae Plants
College of Pharmaceutical Science, Soochow University, 215123 Suzhou, PR China
The dried stem tubers of Pinellia ternata (Thunb.) Breit, P. pedatisecta Schott and Typhonium flagelliforme (Lodd.) Blume from the Araceae family are used as Chinese medicines, namely Banxia, Zhangye Banxia and Shui Banxia, respectively. They have been reported to have a strong irritative effect on mucosa. Previous studies have indicated that the pure raphides of calcium oxalate contained in the stem tubers of three plants have attributed to this strong irritation. However, the processed products of the stem tubers of P. ternata, including Fabanxia, Qingbanxia and Jiangbanxia, have been found to have no irritative effects on mucosa. Currently, the secondary metabolites from the raphides of calcium oxalate contained in the stem tubers of P. ternata with its processed products, P. pedatisecta and T. flagelliforme were analyzed by means of laser microdissection and ultra-high performance liquid chromatography-quadrupole/ time of flight-mass spectrometry. The results indicate that the stem tubers of P. ternata P. pedatisecta and T. flagelliforme mainly contain amino acids, fatty acids, cyclic dipeptides and alkaloids. The secondary metabolite profile of the stem tuber of P. ternata was different from those of its processed products, Fabanxia, Qingbanxia and Jiangbanxia. However, the secondary metabolites from their raphides of calcium oxalate all contained beta-sitosterol, sitosterol palmitate, trigonelline, octadecenoic acid, pedatisectine A and thymidine. The raphides of calcium oxalate from P. ternata, P. pedatisecta and T. flagelliforme do not include any specific irritants. The results indicated that the irritation induced by raphides of calcium oxalate of three Araceae family plants is not relevant to the secondary metabolites but relates to the special needle shape. Keywords: Araceae, Pinellia ternata, Pinellia pedatisecta, Typhonium flagelliforme, raphides of calcium oxalate, UHPLC-QTOF-MS, laser microdissection