Boletín Latinoamericano y del Caribe de Plantas Medicinales y Aromáticas ISSN: 0717-7917 [email protected] Universidad de Santiago de Chile Chile Rodríguez-Hernández, Diego; Demuner, Antonio J.; Montanari, Ricardo M.; Barbosa, Luiz C.A. Cyanolipids from Sapindus saponaria L. seeds oil Boletín Latinoamericano y del Caribe de Plantas Medicinales y Aromáticas, vol. 15, núm. 6, 2016, pp. 364-372 Universidad de Santiago de Chile Santiago, Chile Available in: http://www.redalyc.org/articulo.oa?id=85648040001 How to cite Complete issue Scientific Information System More information about this article Network of Scientific Journals from Latin America, the Caribbean, Spain and Portugal Journal's homepage in redalyc.org Non-profit academic project, developed under the open access initiative © 2016 Boletín Latinoamericano y del Caribe de Plantas Medicinales y Aromáticas 15 (6): 364 - 372 ISSN 0717 7917 www.blacpma.usach.cl Artículo Original | Original Article Cyanolipids from Sapindus saponaria L. seeds oil [Cianolípidos en las semillas de Sapindus saponaria L] Diego Rodríguez-Hernández1,2, Antonio J. Demuner1, Ricardo M. Montanari1 & Luiz C.A. Barbosa1,2 1Department of Chemistry, Universidade Federal de Viçosa, Viçosa, MG, Brazil 2Department of Chemistry, Universidade Federal de Minas Gerais, Campus Pampulha, Belo Horizonte, MG, Brazil Contactos | Contacts: Diego RODRÍGUEZ-HERNÁNDEZ - E-mail address: [email protected] Abstract: The chemical composition of the oil extracted from the seeds of Sapindus saponaria L., (Sapindaceae), was investigated. Cyanolipids constituted 5% hexane extract of the seeds, whereas triacylglycerols (TAG) accounted for 90%. The oil contains type III cyanolipids (CL) 1-cyano-2-hydroxymethylprop-1-en-3-ol-diesters. Structural investigation of the oil components was accomplished by chemical, chromatographic (TLC, CC, GC-MS), and spectroscopic (IR, NMR) means. GC-MS analysis showed that fatty acids were dominant in the CL components of the oil from S. saponaria L., with cis-11-eicosenoic acid, cis-11-octadecenoic acid and eicosanoic acid as the only esterified fatty acyl chains respectively. This being the first report of this kind of natural products (CL), located in the seeds of this plant.. Keywords: Cyanolipids, Sapindus saponaria, Sapindaceae, Fatty acids. Resumen: La composición química del aceite de las semillas de Sapindus saponaria L., (Sapindaceae), fue investigada. Cianolípidos (CL) constituyen el 5% del extracto hexanico de las semillas, mientras que los triacilgliceroles (TAG) representaron el 90%. La fracción cianolipídica estaba compuesta por el CL tipo III, el diester de 1-ciano-2-hidroximetilprop-3-en-1-ol. La investigación estructural de los componentes del aceite se logró mediante técnicas cromatografícas, (CCF, CC, GC-MS), y espectroscópicas (IR, RMN). El análisis por GC- MS mostró que los ácidos grasos tales como: ácidos cis-11-eicosenoico, cis-11-octadecanoico y eicosanoico fueron los únicos ácidos grasos esterificados ubicados en el extracto rico en CL tipo III. Siendo este el primer reporte de esta clase de productos naturales (CL) ubicados en las semilla de esta planta. Palabras clave: Cianolípidos, Sapindus saponaria, Sapindaceae, Ácidos grasos.. Recibido | Received: January 12, 2016 Aceptado | Accepted: May 22, 2016 Aceptado en versión corregida | Accepted in revised form: June 27, 2016 Publicado en línea | Published online: October 30, 2016 Declaración de intereses | Declaration of interests: We are grateful to the following Brazilian agencies: Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) for research fellowships (AJD, LCAB), Fundação de Amparo à Pesquisa de Minas Gerais (FAPEMIG) for financial support and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) for research fellowships (DRH). Este artículo puede ser citado como / This article must be cited as: D Rodríguez-Hernández, AJ Demuner, RM Montanari, LCA Barbosa. 2016. Cyanolipids from Sapindus saponaria L. seeds oil. Bol Latinoam Caribe Plant Med Aromat 15 (6): 364 – 372. 364 Rodríguez-Hernández et al. Cyanolipids from Sapindus saponaria L. sedes oil INTRODUCTION The cyanolipids (CL), derived from amino acid 1970b); types I and IV CL are cyanogenic. metabolism (Møller & Seigler, 1999) are present, Composition studies have shown that cyanolipid along with acylglycerols (AG) and triacilglicerides isolates from Sapindaceae plants posses a high (TAG), in seed oils of plants belonging to the family content of cis-11-eicosenoic acid, eicosanoic acid Sapindaceae (Mikolajczak, 1977). Four types of CL (arachidic acid) and cis-11-octadecenoic acid structures (Figure. 1; I–IV), with fatty acid esterified (vaccenic acid), constituents with these acid, account (FA) to a mono or a dihydroxynitrile moiety, have for up to 50% of total cyanolips in some of species been reported as occurring in this plant family this family (Hopkins & Swingle, 1967; Spitzer, 1995; (Mikolajczak et al., 1970a; Mikolajczak et al., Spitzer, 1996; Lago et al., 2000). Figure 1 Chemical structures of cyanolipids I–IV The physiological role of CL in plants is still not food poisoning. completely understood. These phytochemicals may The species Sapindus saponaria L., serve in vivo as a major nitrogen source for (Sapindaceae) is popularly known in Brazil as developing seedlings (Selmar et al., 1990). “saboneteira”. This medium sized tropical tree found Nevertheless, their co-occurrence with hydroxynitrile in South America and India, produces great quantities glycosides in some species (Bjarnholt & Møller, of small fruits where a sap is accumulated (Saha et 2008), has suggested that they represent a al., 2010). In the tropics these fruits are mainly used biosynthetic variation of hydroxynitrile glycosides as a soap substitute. However, they are also used in with esterification to lipids possibly, serving specific the folk medicine for treating skin lesions, functions related to storage and transport (Tava & inflammation and ulcers (Saha et al., 2010). In a Avato, 2014). recent work our group have isolated from the fruits Many species belonging to Sapindaceae pericarp a large quantities of a triterpene called family, are used commercially as food besides, are hederagenin and produced several derivatives used in the folk medicine. For instance, the arils of endowed with anti-tumor activity (Rodríguez- Nephelium lappaceum which are a part of the seeds, Hernández et al., 2015; Rodríguez-Hernández et al., are well known and eaten fresh or cooked (Almeyada 2016). Since there is no report on the chemistry of et al., 1979). In addition, other parts of the seeds are cyanolipids in the seeds of S. saponaria, in this work, also eaten roasted. The arils of Paullinia cupana we report the preliminary results of re-investigated of (guarana) contain caffeine and are used to prepare chemical composition of its seed oils. Chemical data soft drinks and to relieve fatigue (Avato et al., 2003; and structural elucidation of the TAG and CL Hamerski et al., 2013). Fruits from some Allophylus constituents of the seed oils from S. saponaria are species are considered edible and added to traditional reported and discussed in this work. beverages (Reitz et al., 1988; Aichholz et al., 1997). Moreover, As a consequence, identification and MATERIALS AND METHODS quantification of cyanolipids in food and forage Plant Material. plants containing this natural product is of Fruits of Sapindus saponaria were collected in the importance, to possibly allow their removal and avoid municipality Tocantins (21°10’30”S and Boletín Latinoamericano y del Caribe de Plantas Medicinales y Aromáticas/365 Rodríguez-Hernández et al. Cyanolipids from Sapindus saponaria L. sedes oil 43°01’04”W), Minas Gerais State, Brazil. Voucher temperature was 200° C; 5.00 min solvent cut time. specimens were dried and placed in the collection of The compounds were identified by comparison with the VIC Herbarium of the Plant Biology Department the data held in the Wiley 7.0 and NIST libraries. of Viçosa Federal University (UFV), under the register numbers VIC 35.403. FTIR Infrared spectra were recorded on a Varian 660-IR, Oil extraction and purification. equipped with GladiATR scanning from 4000 to 500 The seeds broken and kernels were separated from cm-1. shells. A yellow mass (30 g) was macerated in hexane with stirring for 24 hours, obtaining, after NMR removal of the solvent, 10 g of yellow oil (33%). The 1H, 13C NMR and two-dimensional (COSY) Composition of the oil was first investigated spectra were recorded on a Varian Mercury 300 by TLC eluting with hexane/Et2O (9:1, v/v). The oil instrument at 300 MHz and 75 MHz, respectively, components were visualized with phosphomolybdic using CDCl3 as a solvent and TMS as internal acid reagent (10% EtOH; Vetec, Sigma Brazil) reference. followed by heating the plates at 110° C. After of the study by TLC, the composition RESULTS AND DISCUSSION of the oil was separated by column chromatography General (CC) (silica gel 60-230 mesh) eluted by gradient Lipid extracts obtained from the seeds of S. elution with hexane/ Et2O. Then, the fractions saponaria were first investigated by TLC. Inspection obtained according to TLC analysis were grouped of the extract by TLC elution in hexane/Et2O (9:1, into 4 main fractions. Fraction 2 was composed of v/v) showed the presence of three components at Rf = TAG and the fraction 3 showed CL 0.75 (TAG), 0.57 (CL), 0.51 and 0.25 (Others). The TLC data readily suggested the presence of types of Transesterification