Ultrasensitive high-performance liquid chromatography determination of tetracycline antibiotics and their 4-epimer derivatives based on dual effect of methanesulfonic acid
Ultrasensitive high-performance liquid chromatography determination of tetracycline antibiotics and their 4-epimer derivatives based on dual effect of methanesulfonic acid
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基于甲磺酸双重作用的超灵敏高效液相色谱法测定四环素类抗生素及其4-差向异构体衍生物
DOI：
10.1002/jssc.201900618
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发表时间：
2019-11-05
影响因子：
3.1
通讯作者：
Cheng, Xianglei
中科院分区：
文献类型：
--
作者：
Lai, Xiaojing;Liu, Jing;Cheng, Xianglei
在反相液相色谱中，四环素类抗生素产生宽且不对称的峰，这是由于它们与二氧化硅基固定相（通常用C18基团衍生化）中存在的阴离子游离硅烷醇基团和金属离子的离子相互作用。采用甲磺酸作为洗脱液添加剂，利用其双重作用，彻底消除了这些常见的困难。研究表明，甲磺酸的性能，以尽量减少“硅烷醇效应”，主要是通过直接中和的阴离子硅烷醇网站和静电吸引与分析物解释。基于这些双重作用机理，成功地建立了同时测定四环素类抗生素及其衍生物的超灵敏方法（米诺环素，土霉素，四环素，金霉素，美他环素，多西环素，4-表四环素，和4-表金霉素）在牛乳中，方便的紫外检测在15分钟内。在1 ~ 200 ng/mL范围内，所有分析物的标准曲线均呈良好的线性关系（r（2）> 0.999），仪器检测限低至0.3 ng/mL。该研究为分析碱性化合物提供了合适的添加剂，具有与MS检测良好兼容性的优点。
In reversed-phase liquid chromatography, tetracycline antibiotics yield broad and asymmetrical peaks, as a result of their ionic interaction with the anionic free silanol groups and metal ion present in the silica-based stationary phases (commonly derivatized with C18 groups). These frequently encountered difficulties were absolutely eliminated based on dual effect when methanesulfonic acid was employed as an eluent additive. The study revealed that the performance of methanesulfonic acid to minimize the "silanol effect" is mainly explained by both direct neutralization of the anionic silanol sites and electrostatic attraction with analytes. Based on these dual action mechanisms, an ultrasensitive method has been successfully developed for the simultaneous determination of tetracycline antibiotics and their derivatives (minocycline, oxytetracycline, tetracycline, chlortetracycline, metacycline, doxycycline, 4-epitetracycline, and 4-epichlortetracycline) in bovine milk with convenient ultraviolet detection within 15 min. Under the optimal conditions, the calibration curves showed good linearity (r(2) > 0.999) for all analytes in the range of 1 similar to 200 ng/mL with the instrument limits of detection as low as 0.3 ng/mL. The study sheds new light on suitable additives to analyze basic compounds with the advantage of good compatibility with MS detection.