Separation of catechin epimers by complexation using ion mobility mass spectrometry

Troć, Anna; Zimnicka, Magdalena; Danikiewicz, Witold

doi:10.1002/jms.3560

Cited by 19 publications

(10 citation statements)

References 31 publications

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“…In similar experiments with crown ethers, 12C4, 15C5, 18C6, and dibenzo‐30C10 were used by Clemmer in the ESI solution to shift the mobilities of peptide ions to different regions of the mobility spectrum, extending the ability to resolve components before mass spectrometry . Also, overlapping catechin epimers (M) were separated with D‐ and L‐amino acids (AA), chiral crown ethers, tartaric acid, cyclodextrins, and transition metals in the ESI solution by forming [2M + D‐AA + Cu 2+ ‐ 3H] − clusters …”

Section: Applications Of Mobility Shifts Upon Injection Of Buffer Gasmentioning

confidence: 69%

Buffer gas additives (modifiers/shift reagents) in ion mobility spectrometry: Applications, predictions of mobility shifts, and influence of interaction energy and structure

Fernandez‐Maestre

2018

J Mass Spectrom

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Ion mobility spectrometry (IMS) is an analytical technique used for fast and sensitive detection of illegal substances in customs and airports, diagnosis of diseases through detection of metabolites in breath, fundamental studies in physics and chemistry, space exploration, and many more applications. Ion mobility spectrometry separates ions in the gas-phase drifting under an electric field according to their size to charge ratio. Ion mobility spectrometry disadvantages are false positives that delay transportation, compromise patient's health and other negative issues when IMS is used for detection. To prevent false positives, IMS measures the ion mobilities in 2 different conditions, in pure buffer gas or when shift reagents (SRs) are introduced in this gas, providing 2 different characteristic properties of the ion and increasing the chances of right identification. Mobility shifts with the introduction of SRs in the buffer gas are due to clustering of analyte ions with SRs. Effective SRs are polar volatile compounds with free electron pairs with a tendency to form clusters with the analyte ion. Formation of clusters is favored by formation of stable analyte ion-SR hydrogen bonds, high analytes' proton affinity, and low steric hindrance in the ion charge while stabilization of ion charge by resonance may disfavor it. Inductive effects and the number of adduction sites also affect cluster formation. The prediction of IMS separations of overlapping peaks is important because it simplifies a trial and error procedure. Doping experiments to simplify IMS spectra by changing the ion-analyte reactions forming the so-called alternative reactant ions are not considered in this review and techniques other than drift tube IMS are marginally covered.

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Section: Applications Of Mobility Shifts Upon Injection Of Buffer Gasmentioning

confidence: 69%

Buffer gas additives (modifiers/shift reagents) in ion mobility spectrometry: Applications, predictions of mobility shifts, and influence of interaction energy and structure

Fernandez‐Maestre

2018

J Mass Spectrom

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“…Today, saponin characterization takes more and more advantage of the capabilities of mass spectrometry-based methods and LC-MS experiments are very efficient for saponin mixture characterization [6,9], often using accurate mass measurements (high-resolution MS-HRMS) and tandem mass spectrometry experiments (collision-induced dissociation-CID) [6,9,20]. We have reported the use of ion mobility spectrometry (IMS) [21,22] for saponin characterization [23,24]. We shown that isomeric saponins presenting different connectivities between the glycone and the aglycone moieties can be distinguished using IMS [24].…”

Section: Introductionmentioning

confidence: 99%

Enhancing the Membranolytic Activity of Chenopodium quinoa Saponins by Fast Microwave Hydrolysis

et al. 2020

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Saponins are plant secondary metabolites. There are associated with defensive roles due to their cytotoxicity and are active against microorganisms. Saponins are frequently targeted to develop efficient drugs. Plant biomass containing saponins deserves sustained interest to develop high-added value applications. A key issue when considering the use of saponins for human healthcare is their toxicity that must be modulated before envisaging any biomedical application. This can only go through understanding the saponin-membrane interactions. Quinoa is abundantly consumed worldwide, but the quinoa husk is discarded due to its astringent taste associated with its saponin content. Here, we focus on the saponins of the quinoa husk extract (QE). We qualitatively and quantitively characterized the QE saponins using mass spectrometry. They are bidesmosidic molecules, with two oligosaccharidic chains appended on the aglycone with two different linkages; a glycosidic bond and an ester function. The latter can be hydrolyzed to prepare monodesmosidic molecules. The microwave-assisted hydrolysis reaction was optimized to produce monodesmosidic saponins. The membranolytic activity of the saponins was assayed based on their hemolytic activity that was shown to be drastically increased upon hydrolysis. In silico investigations confirmed that the monodesmosidic saponins interact preferentially with a model phospholipid bilayer, explaining the measured increased hemolytic activity.

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“…4,6,9−13,15−18 As a result, it is not surprising that many recent publications on amygdalin analysis do not mention/identify the S-amygdalin, which is always present to some extent depending on the storage conditions, extraction solvents, and analytical procedures. Although in a few specific cases, using advanced instrumentation such as MS-MS that may allow differentiation of epimers, 19,20 ideally it is desired and usually necessary that the epimers are separated chromatographically. Thus, the separation of the natural and its unwanted isomerized amygdalin is best done chromatographically.…”

Section: Journal Of Agricultural and Food Chemistrymentioning

confidence: 99%

Problems and Pitfalls in the Analysis of Amygdalin and Its Epimer

Wahab

Breitbach

Armstrong

et al. 2015

J. Agric. Food Chem.

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α-[(6-O-β-d-Glucopyranosyl-β-d-glucopyranosyl)oxy]-(αR)-benzeneacetonitrile, or R-amygdalin, is the most common cyanogenic glycoside found in seeds and kernels of the Rosaceae family and other plant genera such as Passiflora. Many commercially important seeds are analyzed for amygdalin content. In "alternative medicine", amygdalin has been sold as a treatment for cancer for several decades without any rigorous scientific support for its efficacy. We have found that there are some inconsistencies and possible problems in the published analytical chemistry of amygdalin. It is shown that some analytical approaches do not account for the presence of the S-isomer; therefore, a fast reliable method was developed using a chiral stationary phase and HPLC. This approach allows "real-time" monitoring and complete and highly efficient separations. It is found that the S-amygdalin continuously forms in aqueous solutions. A striking result is that the conversion of amygdalin is glassware dependent. "Clean" vials from various vendors can show drastically different reaction rates of the conversion to the isomer (S-amygdalin, also called neo-amygdalin). The epimerization kinetics are dependent on the solvent, temperature, pH, and the nature of the container. For example, epimerization in water was complete in <15 min in a new glass vial taken from the box, whereas it can take >1 h in specially cleaned glassware. Conversely, epimerization can be significantly delayed at high temperature if high-density polyethylene is used as the container. Hence, inert plastic containers are recommended for storage of aqueous amygdalin solutions. Commercial preparations of R-amygdalin actually contain greater quantities of S-amygdalin and ∼ 5% of other degradation products.

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Separation of catechin epimers by complexation using ion mobility mass spectrometry

Cited by 19 publications

References 31 publications

Buffer gas additives (modifiers/shift reagents) in ion mobility spectrometry: Applications, predictions of mobility shifts, and influence of interaction energy and structure

Buffer gas additives (modifiers/shift reagents) in ion mobility spectrometry: Applications, predictions of mobility shifts, and influence of interaction energy and structure

Enhancing the Membranolytic Activity of Chenopodium quinoa Saponins by Fast Microwave Hydrolysis

Problems and Pitfalls in the Analysis of Amygdalin and Its Epimer

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