{"title":"Unveiling Flavonoid Reactivity: A High-Resolution Mass Spectrometry Journey Through the Silylation of Quercetin","authors":"Thabang Bernette Ncongwane, Ntakadzeni Edwin Madala, Derek Tantoh Ndinteh, Elize Smit","doi":"10.1002/rcm.10101","DOIUrl":null,"url":null,"abstract":"<div>\n \n \n <section>\n \n <h3> Rationale</h3>\n \n <p>Quercetin is an example of a pentahydroxylated flavonol compound studied extensively due to its excellent biological activity (e.g., antioxidant, antiviral, and antimicrobial). The antioxidant properties of flavonoids are influenced by the arrangement of the substituents around the molecule, a phenomenon known as the structure–activity relationship (SAR). SAR studies the relationship between compounds' structural characteristics and their biological activity in drug design.</p>\n </section>\n \n <section>\n \n <h3> Methods</h3>\n \n <p>Quercetin was silylated with MTBSTFA using a semiautomated flow system, and the order in which hydroxyl groups were silylated was used to derive the sequential reactivity of quercetin.</p>\n </section>\n \n <section>\n \n <h3> Results</h3>\n \n <p>The collision-induced dissociation MS/MS fragmentation of the precursor ion of quercetin is influenced by the electrospray ionization (+ and − modes) and an increase in collision energy (<span>CE</span>). Structure elucidation with in-depth high-resolution tandem mass spectrometric analysis revealed that silylation primarily occurs at A7 and is sequentially followed by B3′, B4′, C3, and A5.</p>\n </section>\n \n <section>\n \n <h3> Conclusions</h3>\n \n <p>Retro-Dials Alder cleavage of the C-ring plays a significant role in the MS/MS fragmentations of silylated quercetin, maintaining the integrity of the fragment ions and subsequently allowing tracking of the position of the silyl group.</p>\n </section>\n </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"39 20","pages":""},"PeriodicalIF":1.8000,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/rcm.10101","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Rapid Communications in Mass Spectrometry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/rcm.10101","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"BIOCHEMICAL RESEARCH METHODS","Score":null,"Total":0}
引用次数: 0
Abstract
Rationale
Quercetin is an example of a pentahydroxylated flavonol compound studied extensively due to its excellent biological activity (e.g., antioxidant, antiviral, and antimicrobial). The antioxidant properties of flavonoids are influenced by the arrangement of the substituents around the molecule, a phenomenon known as the structure–activity relationship (SAR). SAR studies the relationship between compounds' structural characteristics and their biological activity in drug design.
Methods
Quercetin was silylated with MTBSTFA using a semiautomated flow system, and the order in which hydroxyl groups were silylated was used to derive the sequential reactivity of quercetin.
Results
The collision-induced dissociation MS/MS fragmentation of the precursor ion of quercetin is influenced by the electrospray ionization (+ and − modes) and an increase in collision energy (CE). Structure elucidation with in-depth high-resolution tandem mass spectrometric analysis revealed that silylation primarily occurs at A7 and is sequentially followed by B3′, B4′, C3, and A5.
Conclusions
Retro-Dials Alder cleavage of the C-ring plays a significant role in the MS/MS fragmentations of silylated quercetin, maintaining the integrity of the fragment ions and subsequently allowing tracking of the position of the silyl group.
期刊介绍:
Rapid Communications in Mass Spectrometry is a journal whose aim is the rapid publication of original research results and ideas on all aspects of the science of gas-phase ions; it covers all the associated scientific disciplines. There is no formal limit on paper length ("rapid" is not synonymous with "brief"), but papers should be of a length that is commensurate with the importance and complexity of the results being reported. Contributions may be theoretical or practical in nature; they may deal with methods, techniques and applications, or with the interpretation of results; they may cover any area in science that depends directly on measurements made upon gaseous ions or that is associated with such measurements.