摘要
多孔有机笼(POCs)是由分立的三维笼状分子通过分子间作用力组装而形成的一类新兴的多孔材料。它们具有良好的溶解性和明确的分子固有内腔,是一种良好的色谱分离介质。本研究以1,3,5-均苯三甲醛和(1R,2R)-环己二胺为原料合成了一种手性POC(CC3-R,C_(72)H_(84)N_(12)),用NaBH4还原制得RCC3-R(C_(72)H_(108)N_(12))。将RCC3-R后修饰引入碳碳双键功能化的连接臂后通过巯基-烯点击反应将其键合到巯基硅胶表面,成功制备了一种高效液相色谱手性固定相(CSP)。在正相(NP)和反相(RP)两种洗脱模式下对手性醇类、酯类、酮类、醛类、胺类、有机酸类等不同类型的外消旋体进行了分离测试,评价了该CSP的手性识别能力。结果表明,该CSP在NP和RP洗脱模式下均表现出较好的手性拆分能力,分别实现了对18种和16种外消旋体的拆分。此外,该CSP填充柱还与两种广泛使用的商品柱(Chiralcel OD-H柱和Chiralpak AD-H柱)具有良好的手性拆分互补性,能够拆分这两种商品柱无法拆分的一些外消旋体。同时,还考察了柱温和进样量对自制的RCC3-R柱手性拆分性能的影响。该自制柱还具有较好的重复性和稳定性,经数百次进样使用后,对外消旋体拆分的保留时间和分离度与柱使用之初无显著变化,相对标准偏差(RSD,n=5)分别≤0.50%和≤1.30%,此外,不同批次制备的RCC3-R手性柱对外消旋体拆分的保留时间和分离度的RSD(n=3)分别≤1.89%和≤4.10%。本研究表明手性POC RCC3-R是一种具有潜在应用价值的高效液相色谱手性分离材料,也对基于手性POCs的新型高效液相色谱CSP的研究具有重要的意义。
Porous organic cages(POCs)are a new class of porous materials formed by the assembly of discrete three-dimensional cage-like molecules through intermolecular forces.They possess good solubility and well-defined intrinsic molecular cavities,making them an extremely attractive medium for chromatographic separation.In this study,a chiral porous organic cage(CC3-R,C_(72)H_(84)N_(12))was synthesized using 1,3,5-triformylbenzene and(1R,2R)-diaminocyclohexane as raw materials,and it was then reduced by NaBH4 to obtain RCC3-R(C_(72)H_(108)N_(12)).After post-modification of RCC3-R with 5-bromo-1-pentene to introduce carbon-carbon double-bond functionalized linker arms,it was successfully bonded to the surface of thiolated silica via thiol-ene click reaction to prepare a chiral stationary phase(CSP)for high performance liquid chromatography(HPLC).The successful synthesis of CC3-R,RCC3-R and CSP was confirmed by various characterization methods such as nuclear magnetic resonance(NMR),Fourier-transform infrared spectroscopy(FT-IR),high resolution mass spectrometry(HRMS),thermogravimetric analysis(TGA),and elemental analysis(EA).The enantioseparation performance of the CSP was evaluated by separating various types of racemic compounds,including alcohols,esters,ketones,aldehydes,amines,and organic acids in both normal-phase(NP)and reversed-phase(RP)elution modes.The results demonstrate that the CSP achieved enantioseparation of 18 and 16 racemates in NP and RP modes,respectively.Among them,12 racemates achieved baseline separation in NP elution mode,while 7 racemates achieved baseline separation in RP elution mode.Moreover,the CSP-packed column exhibited good complementarity in chiral separation with two widely used commercial columns,Chiralcel OD-H and Chiralpak AD-H,enabling the separation of some racemic compounds that cannot be separated on these two commercial columns.In NP elution mode,7 of the 18 tested racemates could not be enantioseparated on Chiralpak AD-H column,and 4 of the 18 tested racemates could not be enantioseparated on Chiralcel OD-H column.In RP elution mode,8 of the 16 tested racemates could not be enantioseparated on Chiralpak AD-H column,and 5 of the 16 tested racemates could not be enantioseparated on Chiralcel OD-H column.The effects of column temperature and injection mass on chiral separation performance of the RCC3-R column were investigated.In addition,the RCC3-R column exhibited excellent repeatability and stability.After hundreds of injections,no significant changes were observed in the retention times and resolution values of the analytes compared to the initial use of the column,with relative standard deviations(RSDs,n=5)of less than 0.50% and 1.30%,respectively.Furthermore,the RSDs(n=3)of retention times and resolution values of the racemates separated on RCC3-R columns prepared in different batches were less than 1.89% and 4.10%,respectively.This study demonstrates that the chiral POC RCC3-R is a potentially valuable chiral separation material for HPLC.It also holds significant importance for the research on novel CSPs for HPLC based on chiral POCs.
作者
吴嘉蕾
俞力琴
王帮进
谢生明
章俊辉
袁黎明
WU Jialei;YU Liqin;WANG Bangjin;XIE Shengming;ZHANG Junhui;YUAN Liming(Yunnan Key Laboratory of Modern Separation Analysis and Substance Transformation,College of Chemistry and Chemical Engineering,Yunnan Normal University,Kunming 650500,China)
出处
《色谱》
北大核心
2025年第12期1314-1326,I0001-I0013,共26页
Chinese Journal of Chromatography
基金
国家自然科学基金项目(22564021,22364022,22174125).
关键词
高效液相色谱
手性分离
手性固定相
多孔有机笼
high performance liquid chromatography(HPLC)
chiral separation
chiral stationary phase(CSP)
porous organic cage(POC)
