The Cannabis sativa L. plant has a complex chemical composition, containing various chemical compounds such as terpenes, sugars, hydrocarbons, steroids, flavonoids, and amino acids. Few works have attempted to identify the constitutional isomers of cannabinoids that are found in the plant. The present study reported the analysis of seven cannabinoid standards: five neutral and two acidic, as well as Cannabis products (hashish and marijuana) and parts of the Cannabis plant (flower and leaf) using mono-dimensional gas chromatography coupled with mass spectrometry (GC-MS) and two-dimensional gas chromatography coupled with quadrupole MS (GC × GC-QMS), ultra performance liquid chromatography coupled with electrospray ionization-quadrupole-time of flight (UPLC-ESI-QTOF)-MS and UPLC-ESI-travelling wave ion mobility (TWIM)-MS. The results of GC-MS demonstrated close retention times (∆tR = 1.303 min) in separation of the five cannabinoid standards, whereas GC × GC-QMS provided a substantially better identification and distinction of constitutional isomers of cannabinoids, where a total of 11 cannabinoids were identified in the hashish sample. UPLC-QTOF-MS and UPLC-TWIM-MS data obtained complete chemical information, in which ESI(+) revealed the presence of seven constitutional isomers of ∆9-tetrahydrocannabinol (∆9-THC), whereas ESI(-) proved the presence of four isomers of ∆9-tetrahydrocannabinolic acid A (∆9-THCA A).

In commemoration of the International Year of Chemistry this article presents the normalization and standardization of key terms used in mass spectrometry in Portuguese Language.

Durante nossos estudos visando a obtenção de microorganismos endofíticos associados a plantas tropicais, um fungo do grupo Xylareaceae foi isolado das partes internas dos frutos de Sapindus saponaria. Os frutos de S. saponaria acumulam grande quantidade de saponinas triterpênicas e sesquiterpênicas. A saponina 3-O-(β-D-xilopiranosil)-(1→3)-α-L-ramnopiranosil-(1→2)-α-L-arabinopiranosil-hederagenina foi isolada por métodos cromatográfios após saponificação do extrato bruto obtido dos frutos de S. saponaria e admistrada junto ao meio de cultivo usado para crescimento do fungo. Após extração dos metabólitos obtidos, uma nova saponina foi purificada por CLAE em escala preparativa e caracterizada como um derivado 22α-hidroxilado. Essa saponina hidroxilada teve sua estrutura molecular elucidada através da interpretação de dados de EM/EM e RMN.

During our screening of tropical plants for endophyte microorganisms, a Xylareaceous fungus was found living on the internal part of Sapindus saponaria fruits. The fruits of S. saponaria accumulate great amounts of triterpenoidal and sesquiterpenoidal saponins. The saponin 3-O-(β-D-xylopyranosyl)-(1→3)-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranosyl-hederagenin was isolated using chromatographic methods, after alkaline hydrolysis of the crude extract obtained from S. saponaria fruits and added to the culture medium used to grows the fungus. A new saponin was isolated from this experiment by preparative scale HPLC and characterized as a 22α-hydroxy derivative. The structure of this hydroxylated saponin was elucidated based on interpretation of MS/MS data and NMR spectra.

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.