Electrospray tandem mass spectrometry analysis of methylenedioxy chalcones, flavanones and flavones

Menezes, José C. J. M. D. S.; Cavaleiro, José A. S.; Kamat, Shrivallabh P.; Barros, Cristina; Domingues, Rosário M.

doi:10.1002/rcm.6577

Cited by 9 publications

(9 citation statements)

References 18 publications

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“…The mass difference of 27.9950 matches the exact mass of CO (Fig S3). The loss of CO has been already described in compounds contacting carbonyl group [24, 25]. The proposed identity and fragmentation mechanisms for the products ions are presented in Supplementary material (Fig S7 and S8).…”

Section: Resultsmentioning

confidence: 78%

LC–UV/MS methods for the analysis of prochelator—Boronyl salicylaldehyde isonicotinoyl hydrazone (BSIH) and its active chelator salicylaldehyde isonicotinoyl hydrazone (SIH)

Bureš

Jansová

Stariat

et al. 2015

Journal of Pharmaceutical and Biomedical Analysis

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Salicylaldehyde isonicotinoyl hydrazone (SIH) is an intracellular iron chelator with well documented potential to protect against oxidative injury both in vitro and in vivo. However, it suffers from short biological half-life caused by fast hydrolysis of the hydrazone bond. Recently, a concept of boronate prochelators has been introduced as a strategy that might overcome these limitations. This study presents two complementary analytical methods for detecting the prochelator BSIH (boronyl salicylaldehyde isonicotinoyl hydrazone) along with its active metal-binding chelator SIH in different solution matrices and concentration ranges. An LC-UV method for determination of BSIH and SIH in buffer and cell culture medium was validated over concentrations of 7 – 115 and 4 – 115 μM, respectively, and applied to BSIH activation experiments in vitro. An LC-MS assay was validated for quantification of BSIH and SIH in plasma over the concentration range of 0.06 – 23 and 0.24 – 23 μM, respectively, and applied to stability studies in plasma in vitro as well as analysis of plasma taken after i.v. administration of BSIH to rats. A Zorbax-RP bonus column and mobile phases containing either phosphate buffer with EDTA or ammonium formate and methanol/acetonitrile mixture provided suitable conditions for the LC-UV and LC-MS analysis, respectively. Samples were diluted or precipitated with methanol prior to analysis. These separative analytical techniques establish the first validated protocols to investigate BSIH activation by hydrogen peroxide in multiple matrices, directly compare the stabilities of the prochelator and chelator in plasma, and provide the first basic pharmacokinetic data of this prochelator. Experiments reveal that BSIH is stable in all media tested and is partially converted to SIH by H2O2. The observed integrity of BSIH in plasma samples from the in vivo study suggest that the concept of prochelation might be a promising strategy for further development of aroylhydrazone cytoprotective agents.

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Section: Resultsmentioning

confidence: 78%

LC–UV/MS methods for the analysis of prochelator—Boronyl salicylaldehyde isonicotinoyl hydrazone (BSIH) and its active chelator salicylaldehyde isonicotinoyl hydrazone (SIH)

Bureš

Jansová

Stariat

et al. 2015

Journal of Pharmaceutical and Biomedical Analysis

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“…However, many radical product ions are formed by homolytic cleavage in the analysis of natural products using ESI-MS/MS, in contradiction to the even-electron rule. Homolytic cleavage was reported for the even-electron molecular ions generated from various flavonoids (Hvattum & Ekeberg, 2003;Cuyckens & Claeys, 2004;March, Miao, & Metcalfe, 2004a;March et al, 2004bMarch et al, , 2006Parejo et al, 2004;Liu et al, 2005Liu et al, , 2009Shahat et al, 2005;Ablajan et al, 2006;Kang, Hick, & Price, 2007;Davis & Brodbelt, 2008;Zhao et al, 2008;Kite & Veitch, 2009;Vessecchi et al, 2011;Menezes et al, 2013;Xia et al, 2013), carotenoids (van Breemen, Dong, & Pajkovic, 2012Rivera, Christou, & Canela-Garayoa, 2014), alkaloids (Fabre et al, 2000;Joly et al, 2005Joly et al, , 2007Zhang et al, 2008;Deevanhxay et al, 2009;Aguiar et al, 2010), aryl a-primary amino ketones (Fornal, 2013), feruloyl quinic acids (Kuhnert et al, 2010), benzofuran derivatives (Wu et al, 2010a), cipadesin limonoids , glyceollins (Quadri et al, 2013). It seemed that the loss of a methyl radical occurs readily from methoxy groups attached to aromatic rings.…”

Section: Other Fragmentation Reactions In the Mass Spectra Of Natumentioning

confidence: 99%

Recent (2000–2015) developments in the analysis of minor unknown natural products based on characteristic fragment information using LC–MS

Cai

Guo

et al. 2016

Mass Spectrometry Reviews

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Liquid chromatography-Mass Spectrometry (LC-MS) has been widely used in natural product analysis. Global detection and identification of nontargeted components are desirable in natural product research, for example, in quality control of Chinese herbal medicine. Nontargeted components analysis continues to expand to exciting life science application domains such as metabonomics. With this background, the present review summarizes recent developments in the analysis of minor unknown natural products using LC-MS and mainly focuses on the determination of the molecular formulae, selection of precursor ions, and characteristic fragmentation patterns of the known compounds. This review consists of three parts. Firstly, the methods used to determine unique molecular formula of unknown compounds such as accurate mass measurements, MS spectra, or relative isotopic abundance information, are introduced. Secondly, the methods improving signal-to-noise ratio of MS/MS spectra by manual-MS/MS or workflow targeting-only signals were elucidated; pure precursor ions can be selected by changing the precursor ion isolated window. Lastly, characteristic fragmentation patterns such as Retro-Diels-Alder (RDA), McLafferty rearrangements, "internal residue loss," and so on, occurring in the molecular ions of natural products are summarized. Classical application of characteristic fragmentation patterns in identifying unknown compounds in extracts and relevant fragmentation mechanisms are presented (RDA reactions occurring readily in the molecular ions of flavanones or isoflavanones, McLafferty-type fragmentation reactions of some natural products such as epipolythiodioxopiperazines; fragmentation by "internal residue loss" possibly involving ion-neutral complex intermediates). © 2016 Wiley Periodicals, Inc. Mass Spec Rev 37:202-216, 2018.

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“…[22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] Most of these previouss tudies relied on two [23-26, 28, 29, 31, 34, 35, 38] (MS 2 )o rt hree [22,27,36] (MS 3 )s tages of mass spectrometry,t hat is, only the fragment ions of the deprotonated molecules and their fragment ions were examined. [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] Most of these previouss tudies relied on two [23-26, 28, 29, 31, 34, 35, 38] (MS 2 )o rt hree [22,27,36] (MS 3 )s tages of mass spectrometry,t hat is, only the fragment ions of the deprotonated molecules and their fragment ions were examined.…”

Section: Introductionmentioning

confidence: 99%

A Fundamental Tandem Mass Spectrometry Study of the Collision‐Activated Dissociation of Small Deprotonated Molecules Related to Lignin

et al. 2016

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The collision-activated fragmentation pathways and reaction mechanisms of 34 deprotonated model compounds representative of lignin degradation products were explored experimentally and computationally. The compounds were evaporated and ionized by using negative-ion mode electrospray ionization doped with NaOH to produce abundant deprotonated molecules. The ions were isolated and subjected to collision-activated dissociation (CAD). Their fragment ions were then isolated and also subjected to CAD. This was repeated until no further fragmentation was observed (up to MS ). This approach enabled the identification of characteristic reaction pathways and delineation of reasonable fragmentation mechanisms for deprotonated molecules containing various functional groups. The varying fragmentation patterns observed for different types of compounds allow for the identification of the functionalities in these compounds. This information was utilized to identify the presence of specific functionalities and their combinations in molecules in an organosolv lignin sample.

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Electrospray tandem mass spectrometry analysis of methylenedioxy chalcones, flavanones and flavones

Cited by 9 publications

References 18 publications

LC–UV/MS methods for the analysis of prochelator—Boronyl salicylaldehyde isonicotinoyl hydrazone (BSIH) and its active chelator salicylaldehyde isonicotinoyl hydrazone (SIH)

LC–UV/MS methods for the analysis of prochelator—Boronyl salicylaldehyde isonicotinoyl hydrazone (BSIH) and its active chelator salicylaldehyde isonicotinoyl hydrazone (SIH)

Recent (2000–2015) developments in the analysis of minor unknown natural products based on characteristic fragment information using LC–MS

A Fundamental Tandem Mass Spectrometry Study of the Collision‐Activated Dissociation of Small Deprotonated Molecules Related to Lignin

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