Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan, 430072, Hubei, China.
Kaifeng Inspection Center for Agricultural Products Safety and Quality, Kaifeng, 475000, Henan, China.
Anal Bioanal Chem. 2018 Jun;410(16):3731-3742. doi: 10.1007/s00216-018-1037-3. Epub 2018 Apr 13.
In this study, a ternary mixed-mode silica sorbent (TMSS) with octamethylene, carboxyl, and amino groups was prepared via Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click reaction and a subsequent reduction of azide to primary amine. While used in solid-phase extraction (SPE), the retention behavior of TMSS towards a total of nine kinds of basic, neutral, and acidic drugs was investigated in detail. The results revealed that hydrophobic, ion-exchange interaction, and electrostatic repulsion between TMSS and the analytes were closely related to the retention behavior of TMSS. Besides, the log K value of the analyte was also a factor influencing the retention behavior of analytes on TMSS. The nine analytes could be retained by TMSS simultaneously and then, were eluted into two fractions according to the acid-base property of the analytes for further determinations. The acidic and neutral analytes were in one fraction, and the basic ones in the other fraction. When used to treat the human serum spiked with the nine drugs, TMSS offered higher recoveries than BakerBond CBA and comparable recoveries to Oasis WCX. It should be noted TMSS had better purifying capability for human serum than Oasis WCX. Under the optimized SPE conditions, a method of SPE hyphenated to high-performance liquid chromatography-ultraviolet detection (HPLC-UV) for determination of the basic, neutral, and acidic drugs spiked in human serum was established. For the nine drugs, the linear ranges were all between 5.0 and 1000 μg L with correlation coefficients (R) above 0.9990, and the limits of detection (LODs) were in the range of 0.8-2.3 μg L. The intra-day and inter-day relative standard deviations (RSDs) were less than 5.3 and 8.8%, respectively. Graphical abstract Treating drugs in human serum by SPE with ternary mixed-mode silica sorbent.
在这项研究中，通过铜（I）催化的叠氮-炔环加成（CuAAC）点击反应和随后将叠氮化物还原为伯胺，制备了一种具有辛二烯、羧基和氨基的三元混合模式硅胶固定相（TMSS）。在固相萃取（SPE）中，详细研究了 TMSS 对总共 9 种碱性、中性和酸性药物的保留行为。结果表明，TMSS 与分析物之间的疏水性、离子交换相互作用和静电排斥与 TMSS 的保留行为密切相关。此外，分析物的 log K 值也是影响分析物在 TMSS 上保留行为的一个因素。这 9 种分析物可以同时被 TMSS 保留，然后根据分析物的酸碱性质分为两部分进行进一步测定。酸性和中性分析物在一个部分，碱性分析物在另一个部分。当用于处理人血清中加入的 9 种药物时，TMSS 提供的回收率高于 BakerBond CBA，与 Oasis WCX 的回收率相当。值得注意的是，TMSS 对人血清的净化能力优于 Oasis WCX。在优化的 SPE 条件下，建立了 SPE 与高效液相色谱-紫外检测（HPLC-UV）联用测定人血清中加入的碱性、中性和酸性药物的方法。对于这 9 种药物，线性范围均在 5.0-1000μg/L 之间，相关系数（R）均大于 0.9990，检出限（LODs）在 0.8-2.3μg/L 范围内。日内和日间相对标准偏差（RSD）分别小于 5.3%和 8.8%。
