Liberles S D, Diver S T, Austin D J, Schreiber S L
Howard Hughes Medical Institute, Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA.
Proc Natl Acad Sci U S A. 1997 Jul 22;94(15):7825-30. doi: 10.1073/pnas.94.15.7825.
The natural product rapamycin has been used to provide temporal and quantitative control of gene expression in animals through its ability to interact with two proteins simultaneously. A shortcoming of this approach is that rapamycin is an inhibitor of cell proliferation, the result of binding to FKBP12-rapamycin-associated protein (FRAP). To overcome this limitation, nontoxic derivatives of rapamycin bearing bulky substituents at its C16-position were synthesized, each in a single step. The isosteric isopropoxy and methallyl substituents with the nonnatural C16-configuration abolish both binding to FRAP and inhibition of T cell proliferation. Binding proteins for these derivatives were identified from libraries of cDNAs encoding mutants of the FKBP12-rapamycin-binding (FRB) domain of FRAP by using a mammalian three-hybrid transcription assay. Targeting of the mutations was guided by the structure of the FKBP12-rapamycin-FRB ternary complex. Three compensatory mutations in the FRB domain, all along one face of an alpha-helix in a rapamycin-binding pocket, were identified that together restore binding of the rapamycin derivatives. Using this mutant FRB domain, one of the nontoxic rapamycin derivatives induced targeted gene expression in Jurkat T cells with an EC50 below 10 nM. Another derivative was used to recruit a cytosolic protein to the plasma membrane, mimicking a process involved in many signaling pathways.
天然产物雷帕霉素已被用于通过其同时与两种蛋白质相互作用的能力,对动物体内的基因表达进行时间和定量控制。这种方法的一个缺点是雷帕霉素是细胞增殖的抑制剂,这是其与FKBP12 - 雷帕霉素相关蛋白(FRAP)结合的结果。为克服这一局限性,合成了在其C16位带有庞大取代基的雷帕霉素无毒衍生物,且均为一步合成。具有非天然C16构型的等排异丙氧基和甲基烯丙基取代基消除了与FRAP的结合以及对T细胞增殖的抑制。通过使用哺乳动物三杂交转录测定法,从编码FRAP的FKBP12 - 雷帕霉素结合(FRB)结构域突变体的cDNA文库中鉴定出这些衍生物的结合蛋白。突变的定位以FKBP12 - 雷帕霉素 - FRB三元复合物的结构为指导。在FRB结构域中鉴定出三个补偿性突变,它们都位于雷帕霉素结合口袋中α - 螺旋的一个面上,这些突变共同恢复了雷帕霉素衍生物的结合。使用这种突变型FRB结构域,其中一种无毒雷帕霉素衍生物在Jurkat T细胞中诱导靶向基因表达,其半数有效浓度(EC50)低于10 nM。另一种衍生物用于将一种胞质蛋白募集到质膜,模拟许多信号通路中涉及的一个过程。