Dereplication of glycosides from Sapindus saponaria using liquid chromatography-mass spectrometry

Abstract

Frutos de Sapindus saponaria (Sapindaceae), uma planta amplamente distribuída nos trópicos, foram coletados a cada trinta dias, durante seis meses. Estudos usando cromatografia a líquido com detecção por UV e EM (CLAE/UV/ESI-EM) e fragmentações por EM/EM, mostraram que os principais glicosídeos presentes nesses frutos são saponinas (SAP) derivadas dos triterpenos hederagenina e ácido oleanólico, e oligoglicosídeos de sesquiterpenos acíclicos (ASOGs). Usando esses métodos de análise, foram detectados até trinta SAPs e sessenta e três ASOGs. A planta produz esses compostos como uma mistura complexa de glicosídeos naturalmente acetilados de forma não regiosseletiva. Hidrólise alcalina dos glicosídeos naturais produziu uma mistura, constituída de apenas quatro SAPs e cinco ASOGs. Análise quantitativa dos glicosídeos saponificados mostrou que a quantidade de SAPs acumulada durante a maturação dos frutos permaneceu constante (~110 mg g -1 ) enquanto a quantidade de ASOGs é consideravelmente maior e chega a uma acumulação máxima de 540 mg g -1 aos três meses de idade.Fruits of Sapindus saponaria (Sapindaceae), a widespread tree throughout the tropics, were collected each 30 days during six months. Liquid-chromatography with UV and MS detection (LC/UV/ESI-MS) and MS/MS fragmentation studies showed that the main glycosides present in these fruits are saponins (SAP) derived from the triterpenes hederagenin and oleanolic acid, and acyclic sesquiterpene oligoglycosides (ASOGs). Using these methods of analysis, we detected up to thirty SAPs and sixty-three ASOGs. The plant produces these compounds as a complex mixture of naturally non-regiosselective acetylated glycosides. Alkaline hydrolysis of the natural glycosides produced simplified mixtures of compounds formed of only four SAPs and five ASOGs. Quantitative analysis of the saponificated glycosides showed that the amount of SAPs accumulated during fruit maturation was almost constant at ca. 110 mg g -1 while the quantity of ASOGs are considerably higher and hits a maximum accumulation of ca. 540 mg g -1 at an age of ca. 3 months.Keywords: Sapindus saponaria, saponin, sesquiterpene oligoglycoside, electrospray, HPLC IntroductionSapindus saponaria (Sapindaceae) is a medium size tree distributed all over the tropics and produce yearly small fruits in large amounts. These fruits accumulate in its pericarps great quantity of a sap that foam when shaken in water. Many people in the tropics use this sap as a soap substitute, not only for cleaning procedures itself but also for treatment of skin lesions caused by fungi. Also, fruits of S. saponaria contain molluscicidal saponins and can be used for schistosomiasis control.1 The antigastric ulcer potential of extracts obtained from S. saponaria fruits was recently demonstrated. 2Earlier phytochemical studies using fruits of S. saponaria collected in Brazil 1,3,4 led to the identification of five monodesmosidic saponins derived from hederagenin (23-hydroxyoleanolic acid) ( Table 1). Some of these saponins were acylated with acetic...

Hydroxylation of a hederagenin derived saponin by a Xylareaceous fungus found in fruits of Sapindus saponaria

“…2 Alkaline hydrolysis of these natural glycosides produced simplified mixtures of compounds formed of only four SAPs and five ASOGs. Preparative scale HPLC separation of the SAP fraction let to isolation of pure saponin 1, which was characterized as 3-O-( -D-xylopyranosyl)-(1 3)--L-rhamnopyranosyl-(1 2)--L-arabinopyranosylhederagenin by comparison of both MS and NMR spectra with those published by Grover and co-workers.…”

“…1 Studying the glycoside composition of this soap by means of mass spectrometry coupled with liquid chromatography (LC-MS), it was found that those fruits accumulate on their pericarp huge amounts of monodesmosidic triterpene (SAPs) and bisdesmosidic sesquiterpene (acyclic sesquiterpene oligoglycosides, ASOGs) acetylated saponins. 2 Saponins are usually referred as antifungal and antibacterial compounds, being the monodesmosidic the most active ones. 3,4 These compounds form a group of chemical weapons used by plants in the fight against fungi, and the protection against pathogenic microbes is probably their natural role in plants.…”

A saponin tolerant and glycoside producer xylariaceous fungus isolated from fruits of Sapindus saponaria

“…Hederagenin derived saponins (SAPs) and acyclic sesquiterpene oligoglycosides (ASOGs) used as substrates in these experiments were obtained from the host plant (Murgu and Rodrigues-Filho 2006); oleanolic acid was isolated from flowers of Eugenia triflorida, which produces this compound in great yields; a commercial sweeter (Stevita TM ) containing 3% stevioside on its formula was also used. The fungus was cultivated the same way described above but with the medium containing each of the substrate at a concentration of 5 mg for each 100 ml of liquid medium.…”

“…Studying the glycoside composition of the soap produced by S. saponaria, using mass spectrometry coupled with liquid chromatography, we found that the fruit accumulate on its pericarp huge amounts of monodesmosidic triterpene and bisdesmosidic sesquiterpene saponins (e.g. 1 and 2, respectively) (Murgu and Rodrigues-Filho 2006), which where found as a mixture of naturally non-regiosselective acetylated compounds. Saponins are usually referred as antifungal and antibacterial compounds, being the monodesmosidic ones the most actives (Gruiz 1996;Morrossey et al 1999).…”

Phytotoxic activity of crude aqueous extracts and fractions of young leaves of Sapindus saponaria L. (Sapindaceae)

“…Using these methods of analysis, 30 saponins and 63 acyclic sesquiterpene oligoglycosides have been detected (Murgu & Rodrigues-Filho 2006;Pelegrini et al 2008). Saponins display diverse behaviors, such as molluscicidal, and piscicidal, anti-infl ammatory, analgesic, expectorant, antioxidant, antiviral, antibacterial and antifungal activity (Sparg et al 2004).…”