Hydrolysis Reaction of N-Phosphoryl-α-, β- and γ-amino Acids Studied by HPLC

The hydrolysis reactions of N-（O,O＇diisopropyl）phosphoryl-L-α-alanine （DIPP-L-α-Ala）, N-（O,O＇diisopropyl）- phosphoryl-D-α-alanine （DIPP-D-α-Ala）, N-（O,O＇-diisopropyl）phosphoryl-β-alanine （DIPP-β-Ala） and N-（O,O＇-diisopropyl）phosphoryl-γ-amino butyric acid （DIPP-γ-Aba）, were studied by HPLC and their hydrolysis reaction kinetic equations were obtained. Under acid conditions, the reaction rate of DIPP-L-α-Ala was close to that of DIPP-D-α-Ala and the same rule was true between DIPP-β-Ala and DIPP-γ-Aba. Meantime, the reaction rate of DIPP-L/D-α-Ala was as 10 times as that of DIPP-β-Ala or DIPP-γ-Aba. Under basic conditions, the hydrolysis reactions of DIPP-β-Ala and DIPP-γ-Aba almost did not take place and the reaction rate of DIPP-L/D-α-Ala was about 1/10 of that under acid conditions. Moreover, theoretical calculation further illuminated the differences of the hydrolysis rate from the view of energy. The results would provide some helpful clues to why nature chose a-amino acids but not other kinds of analogs as protein backbones.

β-环糊精催化磷酰化氨基酸水解反应的电喷雾电离质谱研究

利用电喷雾离子阱质谱对 β-环糊精和 N-二异丙氧磷酰化氨基酸的相互作用进行了探讨。结果发现 :β-环糊精能够催化 N-二异丙氧磷酰化氨基酸的水解反应 ,并对 β-环糊精对 N-二异丙氧磷酰化氨基酸的水解反应机制进行了推测。而且还对β-环糊精和 N -二异丙氧磷酰化氨基酸以及氨基酸形成的复合物进行了碰撞诱导裂解 ( CID)研究 。