Unveiling Flavonoid Reactivity: A High-Resolution Mass Spectrometry Journey Through the Silylation of Quercetin

IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS
Thabang Bernette Ncongwane, Ntakadzeni Edwin Madala, Derek Tantoh Ndinteh, Elize Smit
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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.

Abstract Image

揭示类黄酮反应性:槲皮素硅基化的高分辨率质谱之旅
槲皮素是五羟基化黄酮醇化合物的一个例子,由于其优异的生物活性(例如,抗氧化,抗病毒和抗菌)而被广泛研究。黄酮类化合物的抗氧化性能受分子周围取代基排列的影响,这种现象被称为构效关系(SAR)。SAR在药物设计中研究化合物的结构特征与生物活性之间的关系。方法采用半自动化流动系统对槲皮素进行甲基化反应,并根据羟基被硅化的顺序推导槲皮素的顺序反应性。结果槲皮素前体离子的碰撞诱导解离MS/MS碎裂受电喷雾电离(+和-模式)和碰撞能量(CE)增加的影响。高分辨率串联质谱分析表明,硅基化主要发生在A7位点,其次是B3′、B4′、C3和A5位点。结论c环的retrodial Alder切割在硅基化槲皮素的MS/MS片段中起着重要作用,维持了片段离子的完整性,从而可以跟踪硅基的位置。
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来源期刊
CiteScore
4.10
自引率
5.00%
发文量
219
审稿时长
2.6 months
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.
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