漆酚酯键合硅胶液相色谱固定相的制备与应用

以甲基丙烯酸漆酚酯为色谱配体，制备了一种新型色谱固定相。首先以漆酚和甲基丙烯酰氯为原料制备得到甲基丙烯酸漆酚酯，并通过物理吸附涂覆到由3-（甲基丙烯酰氧）丙基三甲氧基硅烷化学修饰的硅胶上，再通过自由基引发与硅烷化硅胶的双键聚合制得漆酚酯键合硅胶固定相（USP）。对固定相进行傅里叶红外光谱（FT-IR）、热重分析（TGA）、扫描电子显微镜（SEM）和元素分析（EA）表征，结果表明通过共聚反应成功地将漆酚酯固定在硅烷化硅胶上，且制备出的固定相具有良好的单分散性。采用匀浆法装柱，以乙腈-0.05%磷酸溶液（3：97，v/v）为流动相，流速为0.4 mL/min，检测波长为220 nm，考察固定相对天麻浸膏的分离性能。以乙腈-水（50：50，v/v）为流动相，流速为0.5 mL/min，检测波长为290 nm，考察固定相对吴茱萸浸膏的分离性能。结果表明该固定相对天麻浸膏和吴茱萸浸膏均具有良好的分离性能，从天麻浸膏中分离出5个色谱峰，从吴茱萸浸膏中分离出2个色谱峰。与商品化C₁₈ 柱相比，USP柱可以从天麻浸膏中分离出更多的有效组分并实现基线分离，分离吴茱萸浸膏的色谱条件更为环保和安全。采用低流速对天麻浸膏和吴茱萸浸膏进行分离，减少了流动相的使用量，分离结果令人满意。以天然产物漆酚制备色谱固定相，既为分离纯化天麻素和吴茱萸碱提供了一种新的方法，又为液相色谱固定相制备提供了新的思路，还拓展了生漆在色谱分离材料方面的应用。

Preparation and application of urushiol methacrylate-bonded silica liquid chromatographic stationary phase

A novel stationary phase for high performance liquid chromatography was prepared using urushiol methacrylate as the chromatographic ligand. The mixed urushiol methacrylate was prepared using urushiol and methacryloyl chloride via a substitution reaction and then coated onto the surface of spherical silica by physical adsorption. The spherical silica was chemically modified with 3-methacryloyloxypropyl trimethoxysilane. Then, the urushiol methacrylate-bonded silica stationary phase (USP) was synthesized via the surface radical polymerization of urushiol methacrylate and the pendant vinyl groups onto the surface of the spherical silica. The stationary phase was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and elemental analysis. The results revealed that the urushiol methacrylate was successfully immobilized on the spherical silica surface after the surface polymerization reaction, and that it had excellent monodispersity. The stationary phases were packed in a stainless-steel hollow column by the slurry packing method, with methanol as the slurry solvent and absolute ethanol as the propelling solvent. The chromatographic performance of the stationary phases were investigated for the separation of Gastrodia elata extract. Acetonitrile-0.05% phosphoric acid solution (3:97, v/v) was employed as the mobile phase at a flow rate of 0.4 mL/min, with the detection wavelength of 220 nm. The separation performance for Fructus evodia extract was also studied, using acetonitrile-water (50:50, v/v) as the mobile phase at a flow rate of 0.5 mL/min, and the detection wavelength was 290 nm. This column showed good separation performance for both these extracts. Out of the five peaks observed for the Gastrodia elata extract, one was attributed to gastrodin, but the other four peaks need to be further verified. Two peaks assignable to evodiamine and rutaecarpine were observed for the Fructus evodia extract. Compared with C₁₈ column, the USP column allowed for more effective separation of the components from the Gastrodia elata extract, with baseline separation; on the other hand, the chromatographic conditions for the separation of the components of the Fructus evodia extract were more environmentally friendly and safer. Because of the low flow rates adopted for the separation of the Gastrodia elata and Fructus evodia extracts, the amount of mobile phase used could be reduced. This study provides not only a new method for the separation and purification of gastrodin and evodiamine in real samples, but also a new strategy for the preparation of chromatographic stationary phases. It expanded the application of raw lacquer in chromatographic separation materials.