title: MALDI-TOF mass spectrometry and reversed-phase HPLC-ELSD chromatography for structural and quantitative studies of major steroid saponins in commercial extracts of Yucca schidigera Roezl.
abstract: This paper describes a new, improved systematic qualitative analysis of yucca saponins in commercial products by combined use of high-pressure liquid chromatography (HPLC) coupled to an evaporative light scattering detector (ELSD) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry (MS). Three groups with four saponins in each were completely resolved by HPLC-ELSD under C18 reversed-phase conditions using a linear gradient composed of methanol and water. The selectivity of the described HPLC-ELSD method is given by the sapogenin differences at C12 (carbonyl group) and at C2 (hydroxyl group), followed by the presence or absence of an exomethylene group at C25, and the composition and length of the oligosaccharidic chain at C3 in the sapogenins. The saponins were identified by chemical and spectroscopic methods including MALDI-TOF MS(1) and MS(2), high resolution MS, and one and bi-dimensional nuclear magnetic resonance (NMR) experiments. Among the twelve saponins identified, eleven were previously reported, and one is reported for the first time in Yucca schidigera. An identification flowchart procedure based on the analysis of the sodium adducts of intact saponins [M+Na](+) and the oligosaccharidic chain ions obtained in the MALDI-TOF MS(1) and the MS(2) spectrums, was developed for the analysis of Y. schidigera saponins. Two intact isomeric saponins were differentiated by this method, which could also be applied to the structural assignment of other steroid and triterpenic saponins. Using the four-major saponins as reference standards, a C18 reversed-phase HPLC-ELSD method was validated for their specific analysis in commercial extracts of Y. schidigera. Finally, the applicability of the HPLC-ELSD method for the relative quantification of yucca saponins is discussed.
authors.affiliation: Departamento de Ingeniería Química y Bioprocesos, Escuela de Ingeniería, Pontificia Universidad Católica de Chile (PUC). Av. Vicuña Mackenna 4860, Santiago de Chile 7820436, Chile. Electronic address: fsastre@uc.cl.
authors.forename: F
authors.initials: F
authors.lastname: Sastre
authors.affiliation: Departamento de Química Orgánica, Facultad de Química, Universidad de la Republica (UDELAR). Montevideo, Uruguay. Av. Alfredo Navarro 3051, Montevideo 11600, Uruguay.
authors.forename: F
authors.initials: F
authors.lastname: Ferreira
authors.affiliation: Departamento de Ingeniería Química y Bioprocesos, Escuela de Ingeniería, Pontificia Universidad Católica de Chile (PUC). Av. Vicuña Mackenna 4860, Santiago de Chile 7820436, Chile.
authors.forename: F
authors.initials: F
authors.lastname: Pedreschi
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods; D010840:Phytosterols / Q000032:analysis* / Q000737:chemistry; D010936:Plant Extracts / Q000032:analysis* / Q000737:chemistry; D012503:Saponins / Q000032:analysis* / Q000737:chemistry; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods*; D027623:Yucca
chemical_list: D010840:Phytosterols; D010936:Plant Extracts; D012503:Saponins
keywords: HPLC-ELSD; MALDI-TOF; Qualitative analysis; Quantitative analysis; Steroid saponins; Yucca schidigera