Connolly D T, Witherbee B J, Melton M A, Durley R C, Grapperhaus M L, McKinnis B R, Vernier W F, Babler M A, Shieh J J, Smith M E, Sikorski J A
Pharmacia Discovery Research, 800 North Lindbergh Boulevard, St. Louis, Missouri 63167, USA.
Biochemistry. 2000 Nov 14;39(45):13870-9. doi: 10.1021/bi001356q.
Chiral N,N-disubstituted trifluoro-3-amino-2-propanols represent a recently discovered class of compounds that inhibit the neutral lipid transfer activity of cholesteryl ester transfer protein (CETP). These compounds all contain a single chiral center that is essential for inhibitory activity. (R,S)SC-744, which is composed of a mixture of the two enantiomers, inhibits CETP-mediated transfer of [(3)H]cholesteryl ester ([(3)H]CE) from HDL donor particles to LDL acceptor particles with an IC(50) = 200 nM when assayed using a reconstituted system in buffer and with an IC(50) = 6 microM when assayed in plasma. Upon isolation of the enantiomers, it was found that the (R,+) enantiomer, SC-795, was about 10-fold more potent than the mixture, and that the (S,-) enantiomer, SC-794, did not have significant inhibitory activity (IC(50) > 0.8 microM). All of the activity of the (S,-)SC-794 enantiomer could be accounted for by contamination of this sample with a residual 2% of the highly potent (R,+) enantiomer, SC-795. The IC(50) of (R,+)SC-795, 20 nM, approached the concentration of CETP (8 nM) in the buffer assay. These chiral N,N-disubstituted trifluoro-3-amino-2-propanols were found to associate with both LDL and HDL, but did not disrupt overall lipoprotein structure. They did not affect the on or off rates of CETP binding to HDL disk particles. Inhibition was highly specific since the activities of phospholipid transfer protein and lecithin cholesterol acyl transferase were not affected. Competition experiments showed that the more potent enantiomer (R)SC-795 prevented cholesteryl ester binding to CETP, and direct binding experiments demonstrated that this inhibitor bound to CETP with high affinity and specificity. It is estimated, based on the relative concentrations of inhibitor and lipid in the transfer assay, that (R)SC-795 binds approximately 5000-fold more efficiently to CETP than the natural ligand, cholesteryl ester. We conclude that these chiral N,N-disubstituted trifluoro-3-amino-2-propanol compounds do not affect lipoprotein structure or CETP-lipoprotein recognition, but inhibit lipid transfer by binding to CETP reversibly and stereospecifically at a site that competes with neutral lipid binding.
手性N,N-二取代三氟-3-氨基-2-丙醇是最近发现的一类化合物,可抑制胆固醇酯转移蛋白(CETP)的中性脂质转移活性。这些化合物均含有一个对抑制活性至关重要的单一手性中心。(R,S)SC-744由两种对映体的混合物组成,在缓冲液中使用重组系统进行测定时,其抑制CETP介导的[(3)H]胆固醇酯([(3)H]CE)从高密度脂蛋白(HDL)供体颗粒向低密度脂蛋白(LDL)受体颗粒转移的IC(50) = 200 nM,而在血浆中测定时IC(50) = 6 μM。分离对映体后发现,(R,+)对映体SC-795的效力比混合物高约10倍,而(S,-)对映体SC-794没有显著抑制活性(IC(50) > 0.8 μM)。(S,-)SC-794对映体的所有活性都可归因于该样品被残留2%的高效(R,+)对映体SC-795污染。(R,+)SC-795的IC(50)为20 nM,接近缓冲液测定中CETP的浓度(8 nM)。发现这些手性N,N-二取代三氟-3-氨基-2-丙醇与LDL和HDL都有关联,但不会破坏整体脂蛋白结构。它们不影响CETP与HDL盘状颗粒结合的结合或解离速率。抑制作用具有高度特异性,因为磷脂转移蛋白和卵磷脂胆固醇酰基转移酶的活性不受影响。竞争实验表明,效力更强的对映体(R)SC-795可阻止胆固醇酯与CETP结合,直接结合实验表明该抑制剂以高亲和力和特异性与CETP结合。根据转移测定中抑制剂和脂质的相对浓度估计,(R)SC-795与CETP的结合效率比天然配体胆固醇酯高约5000倍。我们得出结论,这些手性N,N-二取代三氟-3-氨基-2-丙醇化合物不影响脂蛋白结构或CETP-脂蛋白识别,但通过在与中性脂质结合竞争的位点可逆且立体特异性地结合CETP来抑制脂质转移。