【摘要】 氨基酸是手性小分子,其选择和固定化的方法,有助于开发新的"刷型"手性固定相(CSP)。分别以L-缬氨酸和L-丙氨酸为原料制备了10种新型氨基酸衍生物手性固定相(CSPs),包括8种氨基酸三嗪衍生物CSPs(CSP-1~CSP-8)和两种对甲基苯甲酰氨基酸CSPs(CSP-9~CSP-10),在正相色谱条件下,考察了所合成的CSPs对邻、间和对硝基苯酚位置异构体以及萘普生乙酯、丙环唑、苯醚甲环唑、戊唑醇、己唑醇和联萘酚6种外消旋样品的分离能力。结果表明,硝基苯酚的3种位置异构体在CSP-1~CSP-3和CSP-6~CSP-8上获得较好分离。相同条件下,由丙氨酸制得的CSPs对外消旋样品表现出更好的手性识别能力,萘普生乙酯在CSP-6上获得基线分离。由化学软件Gaussian 09计算出的L-丙氨酸三取代三嗪衍生物CSP-Ⅵ与萘普生乙酯的两个光学异构体之间相互作用的结合能分别为52.51和133.9 k J/mol,也说明了手性选择子与R、S形成的非对映配合物的稳定性不同,Gaussian 09所给出的结合构型图显示手性选择子与样品之间有明显的氢键作用。Gaussian 09的计算结果有助于认识CSPs的手性识别机理。更多还原

【Abstract】 Ten novel amino acid derived chiral stationary phases( CSPs),including eight amino acid modified triazine derived CSPs( CSP-1 ~ CSP-8) and two N-p-methylbenzoyl L-amino acid CSPs( CSP-9 ~ CSP-10),were prepared from L-valine and L-alanine. The chiral recognition ability of these CSPs was evaluated for regioisomers of o-, m-, p-nitrophenol and six racemates of naproxen ethyl ester, propiconazole,difenoconazole,tebuconazole,hexaconazole,1,1’-bi-2-naphthol,under normal phase mode. The results show that CSP-1 ~ CSP-3 and CSP-6 ~ CSP-8 exhibit good selectivity for three regioisomers of nitrophenol. The CSPs obtained from L-alanine show better enantioselective recognition toward the racemates,which leads to a baseline separation of naproxen ethyl ester on CSP-6. Meanwhile,the binding mode and association energy of L-alanine three-substituted triazine derivative CSP Ⅵ with R or S naproxen ethyl ester were investigated by computational simulation with Gaussian 09 software,and hydrogen bonding was found to be a significant factor on the enantioselective recognition.更多还原