Isolation and quantification of tuliposides and tulipalins in tulips (Tulipa) by high‐performance liquid chromatography

Abstract

The content of tuliposides and tulipalins were determined in Tulipa species and cultivars by reversed-phase high-performance liquid chromatography (RP-HPLC), using a water:methanol gradient as mobile phase. The compounds were detected by a diode array detector employed at 208 nm. The investigation revealed, in addition to 1- and 6-tuliposide A, tuliposide D and the lactonized aglycones tulipalin A and (-)-tulipalin B, the new tuliposide F and 6-tuliposide B, the latter being a new acyl derivative of the known 1-tuliposide B. All compounds were isolated by preparative RP-HPLC and identified by NMR and mass spectroscopy. The predominant compounds were 6-tuliposide A and B present in amounts up to 1.5% and 1.3% of fresh weight, respectively. 6-Tuliposide A and tulipalin A seem to be the major allergens in tulips, although tuliposide D and F may also contribute to the allergenic properties. Tulipalin A and (-)-tulipalin B occur in intact tulips and are not only produced in response to fungal attack or after excision of the plants. A few species were found to have very low allergen content and a relatively high level of tuliposide B, indicating it should be possible to breed non-allergenic and disease-resistant tulips.

A Novel Lactone-Forming Carboxylesterase: Molecular Identification of a Tuliposide A-Converting Enzyme in Tulip

“…All parts of tulip plants, such as bulbs, roots, stems, leaves, petals, stamens, and pistils, accumulate large amounts (approximately 0.2%-2% [w/fresh weight]) of tuliposides, whereas tulipalins are far less abundant than tuliposides and sometimes barely detectable (Beijersbergen and Lemmers, 1972;Christensen and Kristiansen, 1999). This fact suggests that inactive tuliposides are stably stored in intact plants and that the conversion of tuliposides into active tulipalins occurs upon infection and wounding.…”

“…They have been found in the genera Tulipa, Erythronium, and Gagea in the family Liliaceae and the genera Alstroemeria and Bomarea in Alstroemeriaceae (Slob et al, 1975) as well as in the genus Spiraea in Rosaceae (Kim et al, 1998(Kim et al, , 1999. Thus far, seven analogs have been identified: 1-tuliposides A and B, 6-tuliposides A and B, and tuliposides D, E, and F (Tschesche et al, 1968(Tschesche et al, , 1969Christensen, 1995aChristensen, , 1995bChristensen, , 1999Kristiansen, 1995, 1999), with 6-tuliposides A and B the predominant tuliposides produced in tulip cultivars (Christensen and Kristiansen, 1999;Shoji et al, 2005). Because of their chemical lability, 6-tuliposides A and B are spontaneously converted to their lactonized aglycons, tulipalins A and B, respectively, under neutral to basic conditions (Tschesche et al, 1969;Beijersbergen and Lemmers, 1972;van Rossum et al, 1998).…”

“…Tuliposides are representative secondary metabolites in the tulip (Tulipa gesneriana; Bergman and Beijersbergen, 1968;Tschesche et al, 1968Tschesche et al, , 1969Slob and Varekamp, 1977;Christensen and Kristiansen, 1999). Tuliposides are sugar esters composed of D-Glc and 49-hydroxy-29-methylenebutanoyl and/or (39S)-39,49-dihydroxy-29-methylenebutanoyl side chains (Fig.…”

Molecular Diversity of Tuliposide A-Converting Enzyme in the Tulip

“…1), are far less abundant than tuliposides. 5,6) Tulipalins show antimicrobial activities against a broad range of strains of bacteria and fungi, in which tulipalin A functions as an antifungal agent rather than an antibacterial, while tulipalin B functions in the opposite manner. [1][2][3][6][7][8][9][10][11][12][13] In addition, tulipalin A has been reported to exhibit high insecticidal activity.…”

“…1). [1][2][3][4][5] Tulip tissues accumulate large amounts (about 2% wt/fr. wt) of tuliposides, and tulipalins A and B, the lactonized aglycons of 6-tuliposides A and B respectively ( Fig.…”