Combining HPLC-PDA-MS-SPE-NMR with Circular Dichroism for Complete Natural Product Characterization in Crude Extracts: Levorotatory Gossypol in<i>Thespesia danis</i>

Sprogøe, Kennett; Stærk, Dan; Ziegler, Hanne L.; Jensen, Thomas Høgh; Holm-Møller, Søren B.; Jaroszewski, Jerzy W.

doi:10.1021/np800010r

Cited by 53 publications

(39 citation statements)

References 56 publications

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“…Fifteen micrograms (∼52 nmol) of oxypeucedanin (22 μg of oxypeucedanin hydrate, ∼72 nmol) in the 1.5 μL detection cell were sufficient to obtain an unambiguous 1 H NMR spectrum in about 2 min 20 s. This technique reduces the required sample quantity by a factor of up to 15 in comparison to a 5 mm tube in a conventional commercial probe. It is for this reason that the microcoil 1 H NMR technique proves useful with mass-limited samples and as a detector in capillary separations, as often demonstrated by our group [27][28][29][30] and several other very active European groups [31][32][33][34][35][36]. Moreover, our results confirmed that disk diffusion is a reliable, easy and inexpensive semi-quantitative susceptibility testing method that is sufficiently sensitive and ideally suited for preliminary investigations on the nano-to microscale.…”

Section: Resultssupporting

confidence: 80%

An efficient approach for the isolation, identification and evaluation of antimicrobial plant components on an analytical scale, demonstrated by the example of Radix imperatoriae

et al. 2010

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Using Radix imperatoriae (the root of masterwort) as an example, we describe an efficient approach for the isolation, identification and evaluation of bioactive plant components on an analytical scale. The extraction of Radix imperatoriae with ethyl acetate was enhanced by the application of ultrasound oscillations. This rhizome extract was applied to three pathogenic bacteria (Bacillus cereus, Escherichia coli, and Staphylococcus aureus) to determine its antimicrobial activity. Disk diffusion was utilized to determine susceptibility. The extract components were separated using a series of chromatography approaches (semi-preparative RP-HPLC, or RP-HPLC on an analytical scale), followed by testing. All fractions were analyzed by LC-UV-ESI-MS and 600 MHz microcoil 1 H NMR spectroscopy. Among other findings, in the fraction with the highest antibacterial activity we were able to identify oxypeucedanin and oxypeucedanin hydrate. Subsequent analysis revealed that only oxypeucedanin hydrate had antibacterial activity, whereas oxypeucedanin itself was inactive at the concentrations applied. Furthermore, oxypeucedanin hydrate appears to be largely, or exclusively, a by-product of sample preparation, since it is either not synthesized by the plant as a second metabolite or is produced by it in only very small quantities.

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Section: Resultssupporting

confidence: 80%

An efficient approach for the isolation, identification and evaluation of antimicrobial plant components on an analytical scale, demonstrated by the example of Radix imperatoriae

et al. 2010

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“…HPLC-PDA-MS-SPE-NMR experiments were performed on a system consisting of an Agilent 1100 LC system, a Knauer K100 Wellchrom pump, a Prospekt 2 solid-phase extraction device, an EsquireLC ion-trap mass spectrometer, and the above-mentioned Bruker Avance spectrometer equipped with a 30 μl 1 H{ 13 C} flow-probe, as described in details elsewhere (Schmidt et al 2008; Sprogøe et al 2008). NMR experiments were controlled with Bruker XWINNMR version 3.1 software, whereas all other operations were controlled with Bruker HyStar version 2.3 or 3.2 software.…”

Section: Methodsmentioning

confidence: 99%

1H NMR-based metabolomics combined with HPLC-PDA-MS-SPE-NMR for investigation of standardized Ginkgo biloba preparations

et al. 2010

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Commercial preparations of Ginkgo biloba are very complex mixtures prepared from raw leaf extracts by a series of extraction and prepurification steps. The pharmacological activity is attributed to a number of flavonoid glycosides and unique terpene trilactones (TTLs), with largely uncharacterized pharmacological profiles on targets involved in neurological disorders. It is therefore important to complement existing targeted analytical methods for analysis of Ginkgo biloba preparations with alternative technology platforms for their comprehensive and global characterization. In this work, 1H NMR-based metabolomics and hyphenation of high-performance liquid chromatography, photo-diode array detection, mass spectrometry, solid-phase extraction, and nuclear magnetic resonance spectroscopy (HPLC-PDA-MS-SPE-NMR) were used for investigation of 16 commercially available preparations of Ginkgo biloba. The standardized extracts originated from Denmark, Italy, Sweden, and United Kingdom, and the results show that 1H NMR spectra allow simultaneous assessment of the content as well as identity of flavonoid glycosides and TTLs based on a very simple sample-preparation procedure consisting of extraction, evaporation and reconstitution in acetone-d6. Unexpected or unwanted extract constituents were also easily identified in the 1H NMR spectra, which contrasts traditional methods that depend on UV absorption or MS ionizability and usually require availability of reference standards. Automated integration of 1H NMR spectral segments (buckets or bins of 0.02 ppm width) provides relative distribution plots of TTLs based on their H-12 resonances. The present study shows that 1H NMR-based metabolomics is an attractive method for non-selective and comprehensive analysis of Ginkgo extracts.Electronic supplementary materialThe online version of this article (doi:10.1007/s11306-009-0195-x) contains supplementary material, which is available to authorized users.

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“…Even though this is a classic example of natural product biaryl atropisomerism, it has only recently been shown that the active atropisomer of gossypol is that of the (M)-(-) enantiomer. 7 This atropisomeric configuration is an order of magnitude more potent than the (P)-(+) enantiomer, hence current studies are focussed on identifying plant species which preferentially produce (M) over (P) with a high enantiomeric excess in an attempt to reduce systemic toxicity. Thus far, the highest observed production was by the Thespia danis Oliv.…”

Section: Natural Atropisomerism In Medicinal Chemistrymentioning

confidence: 99%

A twist of nature – the significance of atropisomers in biological systems

2015

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. (2015). A twist of nature-the significance of atropisomers in biological systems. Natural Product Reports: a journal of current development in bioorganic chemistry, 32 (11), 1562-1583. A twist of nature-the significance of atropisomers in biological systems AbstractRecently identified natural atropisomeric compounds with potential medicinal applications are presented. The ability of natural receptors to possess differential binding between atropisomers is an important factor when considering active and inactive atropisomeric drugs, and has required the development of new techniques for atropselective synthesis of desired targets. Advances in this field therefore have significant relevance to modern pharmaceutical and medicinal chemistry. The atropisomeric natural products discussed include hibarimicinone, flavomannins, talaromannins, viriditoxin, rugulotrosin A, abyssomicin C, marinopyrroles, dixiamycins, streptorubin B, ustiloxins A-F, haouamine A, bisnicalaterines, and tedarene B, all of which show significant potential as leads in antibiotic, antiviral and anticancer studies. The importance for the development of common practices regarding atropisomer recognition and classification is also emphasized. AbstractRecently identified natural atropisomeric compounds with potential medicinal applications are presented. The ability of natural receptors to possess differential binding between atropisomers is an important factor when considering active and inactive atropisomeric drugs, and has required the development of new techniques for atropselective synthesis of desired targets. Advances in this field therefore have significant relevance to modern pharmaceutical and medicinal chemistry. The atropisomeric natural products discussed include hibarimicinone, flavomannins, talaromannins, viriditoxin, rugulotrosin A, abyssomicin C, marinopyrroles, dixiamycins, streptorubin B, ustiloxins A-F, haouamine A, bisnicalaterines, and tedarene B, all of which show significant potential as leads in antibiotic, antiviral and anticancer studies. The importance for the development of common practices regarding atropisomer recognition and classification is also emphasized.

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Combining HPLC-PDA-MS-SPE-NMR with Circular Dichroism for Complete Natural Product Characterization in Crude Extracts: Levorotatory Gossypol inThespesia danis

Cited by 53 publications

References 56 publications

An efficient approach for the isolation, identification and evaluation of antimicrobial plant components on an analytical scale, demonstrated by the example of Radix imperatoriae

An efficient approach for the isolation, identification and evaluation of antimicrobial plant components on an analytical scale, demonstrated by the example of Radix imperatoriae

1H NMR-based metabolomics combined with HPLC-PDA-MS-SPE-NMR for investigation of standardized Ginkgo biloba preparations

A twist of nature – the significance of atropisomers in biological systems

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