Mononucleotide recognition by cyclic trinuclear palladium(II) complexes containing 4,7-phenanthroline N,N bridges
Mononucleotide recognition by cyclic trinuclear palladium(II) complexes containing 4,7-phenanthroline N,N bridges
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DOI：
10.1039/b402602k
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发表时间：
2004-01-01
影响因子：
4
通讯作者：
Quirós, M
中科院分区：
文献类型：
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作者：
Galindo, MA;Navarro, JAR;Quirós, M
[(Dach)Pd(NO3)(2)]实体(dach=(R，R)-1，2-二氨基环己烷，(S，S)-1，2-二氨基环己烷)和4，7-二氮杂菲(Phen)分别提供90和120度的键角，反应导致两个新的带正电的同手性环状三核金属杯[3]芳烃物种[((R，R)-1，2-二氨基环己烷)Pd(Phen)](3)(NO3)(6)(2a)和[(S，S)-1，2-二氨基环己烷)Pd(Phen)](3)(NO3)(6)(2b)。用H-1NMR和X射线衍射法(2b)对这些物种进行了表征，表明它们具有适合超分子识别过程的可进入的空穴。我们确实从H-1核磁共振研究中证明了水溶液中的三核物种[(乙二胺基)Pd(Phen)](3)(6+)(1)、[((R，R)-1，2-二氨基环己烷)Pd(Phen)](3)(6+)(2a)和[((S，S)-1，2-二氨基环己烷)Pd(Phen)](3)(6+)(2b)在水溶液中包含单核苷酸。[(乙二胺)Pd(Phen)](3)(6+)与一磷酸腺苷相互作用的缔合常数(K-ASS)为85+/-6M-1，[(1，2-二氨基环己烷)Pd(Phen)](3)(6+)与胸腺嘧啶核苷相互作用为37+/-4M-1。我们引用静电、阴离子-pi和pi-pi相互作用的协同效应来解释金属杯[3]芳烃腔内单核苷酸的识别。
Reaction of [(dach) Pd(NO3)(2)] entities (dach = (R, R)-1,2- diaminocyclohexane, (S, S)-1,2-diaminocyclohexane) and 4,7-phenanthroline phen) providing, respectively, 90 and 120degrees bond angles, leads to the formation of two novel positively charged homochiral cyclic trinuclear metallacalix[3] arene species [((R, R)-1,2-diaminocyclohexane)Pd( phen)](3)(NO3)(6) (2a) and [((S, S)-1,2-diaminocyclohexane) Pd(phen)](3)(NO3)(6) (2b). These species have been characterised by H-1 NMR and X-ray diffraction methods (2b), showing that they possess accessible cavities suited for supramolecular recognition processes. We prove, indeed, from H-1 NMR studies the inclusion of mononucleotides inside the cavity of the trinuclear species [(ethylenediamino) Pd(phen)](3)(6+) (1), [((R, R)-1,2-diaminocyclohexane)Pd( phen)](3)(6+) (2a) and [((S, S)-1,2-diaminocyclohexane) Pd(phen)](3)(6+) (2b) in aqueous solution. Association constants (K-ass) range from 85 +/- 6 M-1 for the interaction between [( ethylenediamine) Pd(phen)](3)(6+) and adenosine monophosphate to 37 +/- 4 M-1 for the interaction between [(1,2-diaminocyclohexane) Pd(phen)](3)(6+) and thymidine monophosphate. We invoke the synergy of electrostatic, anion - pi and pi-pi interactions to explain the recognition of mononucleotides inside the cavity of the metallacalix[3] arenes.