Simulation Strategies for Characterizing Phosphodiesterase-5 Inhibitors in Botanical Dietary Supplements
Simulation Strategies for Characterizing Phosphodiesterase-5 Inhibitors in Botanical Dietary Supplements
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DOI：
10.1021/acs.analchem.8b01609
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发表时间：
2018-09-18
影响因子：
7.4
通讯作者：
Lu, Feng
中科院分区：
文献类型：
--
作者：
Lv, Diya;Cao, Yan;Lu, Feng
提出了一种新的“预测和确认”（PC）策略，用于现场检测植物性膳食补充剂（bds）中磷酸二酯酶-5抑制剂（PDE-5）衍生物。“预测”步骤使用了Discovery Studio （DS）和密度泛函理论（DFT）计算，以便在不合成衍生物的情况下估计PDE-5衍生物的结构和理论拉曼位移。通过DS获得11个具有潜在生物活性的西地那非衍生物后，通过DFT获得32个共同计算的拉曼位移。优化了主要波段的平均绝对波数偏差（delta，峰程）和与计算出的共移相匹配的拉曼光谱峰的最小峰数（tau），从而合理地得出未知样品的阳性结果。在本研究中，优化后的delta设为+/- 10 cm(-1)，相应的tau设为4-5。表面等离子体共振（SPR）生物传感器和表面增强拉曼散射（SERS）检测分别是验证DS和DFT在“预测”步骤中的可靠性和准确性的“确认”步骤。将优化后的delta和tau标准作为现场SERS检测指标，对6个实际样品进行薄层色谱（TLC）分离，其中1个样品初步确定为“疑似阳性样品”。该策略允许快速测定掺入西地那非或其衍生物的bds，独立于任何标准材料。
A novel "Prediction and Confirmation" (PC) strategy was proposed for characterizing phosphodiesterase-5 inhibitor (PDE-5) derivatives in botanical dietary supplements (BDSs) for on-site detection. Discovery Studio (DS) and density functional theory (DFT) calculations were used for the "Prediction" step in order to estimate PDE-5 derivative structures and theoretical Raman shifts without synthesizing the derivatives. After 11 potentially bioactive sildenafil derivatives were acquired through DS, 32 common calculated Raman shifts were obtained through DFT. The mean absolute wavenumber deviation (delta, peak range) of the major bands and the minimum number (tau) of Raman spectral peaks matching the calculated common shifts were optimized, so that a positive result of an unknown sample could be reasonably produced. In this study, delta was set at +/- 10 cm(-1) and the corresponding tau was set at 4-5 after optimization. Surface plasmon resonance (SPR) biosensor and surface-enhanced Raman scattering (SERS) detection were the "Confirmation" step to validate the reliability and accuracy of DS and DFT in the "Prediction" step, respectively. The optimized delta and tau criteria were used as indexes for on-site SERS detection after thin-layer chromatographic (TLC) separation of six real-world samples, one of which was preliminarily identified as "suspected positive samples." This strategy allows for a quick determination of the BDSs adulterated with sildenafil or its derivatives, independent of any standard materials.