Feldkamp Michael D, Gakhar Lokesh, Pandey Nisha, Shea Madeline A
Department of Biochemistry, Roy J. and Lucille A. Carver College of Medicine, University of Iowa, Iowa City, Iowa, 52242-1109.
Proteins. 2015 May;83(5):989-96. doi: 10.1002/prot.24781. Epub 2015 Mar 25.
The anti-psychotic drug trifluoperazine (TFP) is an antagonist observed to bind to calcium-saturated calmodulin ((Ca(2+) )4 -CaM) at ratios of 1:1 (1CTR), 2:1 (1A29), and 4:1 (1LIN). Each structure contains one TFP bound in the hydrophobic cleft of the C-domain of CaM. However, the orientation of the trifluoromethyl (CF3 ) moiety differs among them: it is buried in the C-domain cleft of 1A29 and 1LIN, but protrudes from 1CTR. We report a 2.0 Å resolution crystallographic structure (4RJD) of TFP bound to the (Ca(2+) )-saturated C-domain of CaM (CaMC ). The asymmetric unit contains two molecules of (Ca(2+) )2 -CaMC . Chain backbones were nearly identical, but the orientation of TFP in the cleft of Chain A matched 1A29/1LIN, while TFP bound to Chain B matched 1CTR. This was accommodated by a flip of the M144 sidechain and small changes in sidechains of M109 and M145. Docking simulations suggested that the rotamer conformation of M144 determined the orientation of TFP within the cleft of (Ca(2+) )2 -CaMC . Chains A and B show that the open cleft of (Ca(2+) )2 -CaMC is promiscuous in accepting TFP in reversed directions under the same crystallization conditions. Observing multiple orientations of an antagonist bound to a single protein highlights the challenge of designing highly specific pharmaceuticals, and may have importance for QSAR of other CF3 -containing drugs such as fluoxetine (anti-depressant) or efavirenz (reverse transcriptase inhibitor). This study emphasizes that a single structure of a complex represents an energetically accessible state, but does not necessarily show the full range of energetically equivalent states.
抗精神病药物三氟拉嗪(TFP)是一种拮抗剂,已观察到它能以1:1(1CTR)、2:1(1A29)和4:1(1LIN)的比例与钙饱和钙调蛋白((Ca(2+))4 -CaM)结合。每个结构都包含一个结合在CaM C结构域疏水裂缝中的TFP。然而,三氟甲基(CF3)部分的取向在它们之间有所不同:它埋在1A29和1LIN的C结构域裂缝中,但从1CTR中突出。我们报告了TFP与CaM(CaMC)的(Ca(2+))饱和C结构域结合的分辨率为2.0 Å的晶体结构(4RJD)。不对称单元包含两个(Ca(2+))2 -CaMC分子。链骨架几乎相同,但A链裂缝中TFP的取向与1A29/1LIN匹配,而与B链结合的TFP与1CTR匹配。这是通过M144侧链的翻转以及M109和M145侧链的微小变化来实现的。对接模拟表明,M144的旋转异构体构象决定了TFP在(Ca(2+))2 -CaMC裂缝中的取向。A链和B链表明,在相同的结晶条件下,(Ca(2+))2 -CaMC的开放裂缝在以相反方向接受TFP方面具有混杂性。观察到一种拮抗剂与单一蛋白质结合的多种取向突出了设计高度特异性药物的挑战,并且可能对其他含CF3的药物(如氟西汀(抗抑郁药)或依非韦伦(逆转录酶抑制剂))的定量构效关系具有重要意义。这项研究强调,复合物的单一结构代表一种能量上可及的状态,但不一定显示出所有能量上等效的状态。