Isolation, characterization, and synthesis of trans-pilosine stereoisomers occurring in nature. Circular dichroism and mass spectral studies

Tedeschi, E.; Kamionsky, Julia; ZEIDER, D.; Fackler, S.; Sarel, Shalom; Usieli, Varda; Deutsch, Joseph

doi:10.1021/jo00927a017

Cited by 11 publications

(8 citation statements)

References 2 publications

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“…This diagnostic ion is seen in all product ion spectra of the protonated alkaloids extracted from pilocarpine that contain this group. The m/z 95 ion is also observed as the main product ion in the dissociation of epiisopilosine (an isomer of pilosine), as reported by Tedeschi et al 12. Other important product ions in Fig.…”

Section: Resultssupporting

confidence: 70%

“…Jaborandi leaves also contain other imidazole alkaloids, such as pilosine, pilosinine, pilocarpidine, anhydropilosine and 13‐nor‐8(11)‐dihydropilocarpine, whose pharmacological and physiological properties are still unknown 7–10. The presence of pilocarpine and pilosine in jaborandi was first described by Felter and Lloyd in 1898,11 although their complete configuration was determined many years later 7, 8, 12. Brochmann‐Hanssen et al 13.…”

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confidence: 99%

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Characterization of the variation in the imidazole alkaloid profile of Pilocarpus microphyllus in different seasons and parts of the plant by electrospray ionization mass spectrometry fingerprinting and identification of novel alkaloids by tandem mass spectrometry

Abreu

Mazzafera

Eberlin

et al. 2007

Rapid Comm Mass Spectrometry

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Pilocarpus microphyllus (Rutaceae), popularly known as jaborandi, is the only commercial source of an imidazole alkaloid named pilocarpine. In the present study, the variation in the profile of imidazole alkaloids in different seasons and in different parts of the P. microphyllus plant during the summer was analyzed by electrospray ionization mass spectrometry in the positive ion mode [ESI(+)-MS]. The fingerprints of these extracts repeatedly presented similar ions which were mass-selected and studied by tandem mass spectrometry (ESI-MS/MS and ESI-MS/MS/MS) and high-resolution mass spectrometry, resulting in the characterization of eight imidazole alkaloids. The data from the ESI(+)-MS fingerprints were analyzed by principal component analysis (PCA), showing that pilocarpine was present mainly in the summer, whereas in the autumn mainly pilosine and winter anhydropilosine were found. Three alkaloids, reported for the first time in extracts of P. microphyllus, were found. Analysis of the distribution of alkaloids in different parts of the plant during the summer showed that, although pilocarpine was present throughout the plant, 13-nor-8(11)-dihydropilocarpine was found mainly in the stem, pilosine and anhydropilosine were present mainly in the intermediary leaves, and the three new alkaloids were mainly found in the leaflets and petioles. Based on the dissociation patterns of these alkaloids, we observed that there were three structurally related groups of alkaloids differing in their distribution in the plant tissues and responding differently to seasonal variations. These results also indicate that these three groups of alkaloids could belong to intermediate, parallel or competitive pathways for pilocarpine formation biosynthesis.

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Section: Resultssupporting

confidence: 70%

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confidence: 99%

Characterization of the variation in the imidazole alkaloid profile of Pilocarpus microphyllus in different seasons and parts of the plant by electrospray ionization mass spectrometry fingerprinting and identification of novel alkaloids by tandem mass spectrometry

Abreu

Mazzafera

Eberlin

et al. 2007

Rapid Comm Mass Spectrometry

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“…These compounds have slightly different ESI-MS/MS allowing them to be distinguished, and are presented for the first time in literature in Figure 2 (F, G, H, I and J). We have found references to five isomers of molecular formula C 16 H 18 N 2 O 3 found in species P. microphyllus and P. jaborandi : pilosine (2 R ,3 R ,6 S ), isopilosine (2 S ,3 R ,6 R ) and epiisopilosine (2 S ,3 R ,6 S ) [ 15 ], as well as piloturin and epiisopiloturin [ 16 ] in which the imidazole ring is linked at the C 4 (rather than at the C 5 as in pilosine). At the present moment we are able to identify just one of these isomers, that is, pilosine ( 5 ).…”

Section: Resultsmentioning

confidence: 99%

HPLC-ESI-MS/MS of Imidazole Alkaloids in Pilocarpus microphyllus

et al. 2008

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Pilocarpine, an important imidazole alkaloid, is extracted from the leaves of Pilocarpus microphyllus (Rutaceae), known in Brazil as jaborandi and used mainly for the treatment of glaucoma. Jaborandi leaves also contain other imidazole alkaloids, whose pharmacological and physiological properties are unknown, and whose biosynthetic pathways are under investigation. In the present study, a HPLC method coupled with ESI-MSn was developed for their qualitative and quantitative analysis. This method permits the chromatographic separation of the imidazole alkaloids found in extracts of jaborandi, as well as the MS/MS analysis of the individual compounds. Thus two samples: leaves of P. microphyllus and a paste that is left over after the industrial extraction of pilocarpine; were compared. The paste was found to contain significant amounts of pilocarpine and other imidazole alkaloids, but had a slightly different alkaloid profile than the leaf extract. The method is suitable for the routine analysis of samples containing these alkaloids, as well as for the separation and identification of known and novel alkaloids from this family, and may be applied to further studies of the biosynthetic pathway of pilocarpine in P. microphyllus.

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“…The next four peaks in the sample of P. microphyllus from Maranhão state (7, 9, 10 and 12) have the same mass and molecular formula and are isomers of pilosine, found in a previous study (Sawaya et al 2008), with slight differences in their ESI-MS/MS. Several epimers and isomers have been reported (Tedeschi et al 1974;Voigtländer et al 1978) with the same molecular formula. Of these isomers; pilosine has been reported in P. microphyllus and pilosine, isopilosine, epiisopilosine and epiisopiloturine in P. jaborandi (Santos and Moreno 2004).…”

Section: Alkaloid Profile In Different Speciesmentioning

confidence: 98%

Screening species of Pilocarpus (Rutaceae) as sources of pilocarpine and other imidazole alkaloids

Sawaya

Vaz

Eberlin

et al. 2011

Genet Resour Crop Evol

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Plants of the Pilocarpus genus (Rutaceae) are popularly known as jaborandi and are the only source of pilocarpine, an imidazole alkaloid used in eye-drops for the treatment of glaucoma as well as for the stimulation of sweat and lachrymal glands. Alkaloid extracts from leaf samples of seven species of Pilocarpus, from the states of São Paulo and Maranhão in Brazil, were analyzed using HPLC-ESI-MS/MS. The samples contained between 0.88 ± 0.04 and 1.00 ± 0.14% of alkaloids in relation to the dry weight of their leaves, with significant differences in results (P B 0.05) found only between Pilocarpus microphyllus planted in the state of Maranhão and Pilocarpus spicatus, Pilocarpus trachyllophus, Pilocarpus pennatifolius and Pilocarpus jaborandi; as well as between Pilocarpus spicatus and Pilocarpus racemosus. Pilocarpine was not found in P. spicatus, whereas in the other species it ranged from 2.6 ± 0.1 to 70.8 ± 1.2% of total alkaloids. P. microphyllus planted in the state of Maranhão for pilocarpine extraction had the highest total alkaloid content, but it had only 35% of pilocarpine in relation to total alkaloids. Three other species contained more pilocarpine in relation to total alkaloids: P. jaborandi (70.8%), P. racemosus (45.6%) and P. trachyllophus (38.7%); and could be candidates for pilocarpine extraction. Differences in alkaloid content were significant for all these samples (P B 0.05). Imidazole alkaloids were observed and partially characterized based on their retention times and high resolution mass. The seven species analyzed had different imidazole alkaloid profiles, but only one did not present quantifiable pilocarpine contents in its leaves. The Pilocarpus genus shows potential for the prospection of novel alkaloids.

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Isolation, characterization, and synthesis of trans-pilosine stereoisomers occurring in nature. Circular dichroism and mass spectral studies

Cited by 11 publications

References 2 publications

Characterization of the variation in the imidazole alkaloid profile of Pilocarpus microphyllus in different seasons and parts of the plant by electrospray ionization mass spectrometry fingerprinting and identification of novel alkaloids by tandem mass spectrometry

Characterization of the variation in the imidazole alkaloid profile of Pilocarpus microphyllus in different seasons and parts of the plant by electrospray ionization mass spectrometry fingerprinting and identification of novel alkaloids by tandem mass spectrometry

HPLC-ESI-MS/MS of Imidazole Alkaloids in Pilocarpus microphyllus

Screening species of Pilocarpus (Rutaceae) as sources of pilocarpine and other imidazole alkaloids

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