二聚炔雌醇分子钳对氨基酸的对映选择性识别

利用人工受体与适当底物间的分子识别 ,以建立仿生模型的研究已成为生物有机化学前沿富有挑战性的领域之一 1 ] .生物分子多数是手性分子 ,因而手性识别在生命过程中极其重要2 ] .近年来对氨基酸的手性识别引起了广泛的兴趣 .多种大环受体 (如冠醚、环糊精、环番等 )对氨基酸的手性识别有较多的报道 ,然而甾体类大环和甾体分子钳受体对氨基酸的手性识别报道却很少 .我们曾报道了二聚雌二醇分子钳 ( 1 ,2 ,3,4)对氨基酸具有对映选择性识别性能3,4] .这里报道由炔雌醇构筑的分子钳 ( 5 ,6 ,7,8)对氨基酸的手性识别 ,并与雌二醇分子钳的识别…

ENANTIOSELECTIVE RECOGNITION OF AMINO ACID BY CHIRAL MOLECULAR TWEEZERS BASED ON ETHYNYLESTRADIOL DIMER

The molecular recognition ability of the molecular tweezers 5～8 for the aromatic amino acid have been investigated by means of UV～Visible spectrophotometric titrition. The titrition data are analyzed by using the Benesi-Hidebrandequation. The results showed that all these molecular tweezers can form 1:1 supramolecular complexes with the aromatic amino acid and exhibited chiral recognition property. These receptors are favorable for complexation with D-amino acid. The enantioselectivity KD/KL of receptor 8 for Phe-OMe reached to 3.18. The recognition ability of these molecular tweezers come mainly from hydrogen bonding, π-π Stacking between aromatic residues and Van der Waals interaction. The size/shepe-fit and micvoenvion ments complementary between receptor and substrate pley a pivotal role in the inclusion complexation of amino acid methyl esters with these receptors.