Jiang R T, Shyy Y J, Tsai M D
Biochemistry. 1984 Apr 10;23(8):1661-7. doi: 10.1021/bi00303a013.
Separate diastereomers of 1,2-dipalmitoyl-sn-glycero-3- thiophosphoethanolamine ( DPPsE ) were prepared in 97% diastereomeric purity and characterized by 31P, 13C, and 1H nuclear magnetic resonance (NMR). The isomers hydrolyzed by phospholipases A2 and C specifically were designated as isomer B (31P NMR delta 59.13 in CDCl3 + Et3N ) and isomer A (59.29 ppm), respectively, analogous to the isomers B and A of 1,2-dipalmitoyl-sn-glycero-3- thiophosphocholine ( DPPsC ) [ Bruzik , K., Jiang , R.-T., & Tsai, M.-D. (1983) Biochemistry 22, 2478-2486]. Phospholipase D from cabbage was shown to be specific to isomer A of DPPsC in transphosphatidylation . The product DPPsE was shown to be isomer A. The absolute configuration of chiral DPPsE at phosphorus was elucidated by bromine-mediated desulfurization in H2 18O to give chiral 1,2-dipalmitoyl-sn-glycero-3-[18O]phosphoethanolamine ( [18O]DPPE) followed by 31 P NMR analysis [ Bruzik , K., & Tsai, M.-D. (1984) J. Am. Chem. Soc. 106, 747-754]. The absolute configuration of chiral DPPsC was elucidated by desulfurization in H2 18O mediated by bromine or cyanogen bromide to give chiral 1,2-dipalmitoyl-sn-glycero-3-[18O]phosphocholine ( [18O]DPPC), which was then converted to [18O]DPPE by phospholipase D with retention of configuration [ Bruzik , K., & Tsai, M.-D. (1984) Biochemistry (preceding paper in this issue)]. The results indicate that isomer A of both DPPsE and DPPsC is SP whereas isomer B is RP.
制备了非对映体纯度为97%的1,2 - 二棕榈酰 - sn - 甘油 - 3 - 硫代磷酸乙醇胺（DPPsE）的单一非对映异构体，并通过³¹P、¹³C和¹H核磁共振（NMR）进行了表征。被磷脂酶A2和C特异性水解的异构体分别被指定为异构体B（在CDCl₃ + Et₃N中³¹P NMR δ 59.13）和异构体A（59.29 ppm），类似于1,2 - 二棕榈酰 - sn - 甘油 - 3 - 硫代磷酸胆碱（DPPsC）的异构体B和A [布鲁齐克，K.，江，R.-T.，& 蔡，M.-D.（1983年）《生物化学》22，2478 - 2486]。已证明来自卷心菜的磷脂酶D在转磷脂酰化反应中对DPPsC的异构体A具有特异性。产物DPPsE被证明是异构体A。通过在H₂¹⁸O中溴介导的脱硫反应得到手性1,2 - 二棕榈酰 - sn - 甘油 - 3 - [¹⁸O]磷酸乙醇胺（[¹⁸O]DPPE），然后进行³¹P NMR分析，阐明了手性DPPsE在磷原子处的绝对构型 [布鲁齐克，K.，& 蔡，M.-D.（1984年）《美国化学会志》106，747 - 754]。通过溴或溴化氰介导的H₂¹⁸O中的脱硫反应得到手性1,2 - 二棕榈酰 - sn - 甘油 - 3 - [¹⁸O]磷酸胆碱（[¹⁸O]DPPC），阐明了手性DPPsC的绝对构型，然后通过磷脂酶D将其转化为[¹⁸O]DPPE，构型保持不变 [布鲁齐克，K.，& 蔡，M.-D.（1984年）《生物化学》（本期前一篇论文）]。结果表明，DPPsE和DPPsC的异构体A均为SP型，而异构体B为RP型。
