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dc.contributor.authorRuhayel, Rasha
dc.contributor.authorZgani, Ibrahim
dc.contributor.authorBerners-Price, Sue
dc.contributor.authorFarrell, Nicholas
dc.date.accessioned2017-09-25T00:34:38Z
dc.date.available2017-09-25T00:34:38Z
dc.date.issued2011
dc.date.modified2012-02-15T04:44:47Z
dc.identifier.issn1477-9226en_US
dc.identifier.doi10.1039/c1dt00001ben_US
dc.identifier.urihttp://hdl.handle.net/10072/42678
dc.description.abstractThe aquation profiles of two novel dinuclear polyamine-linked, platinum-based antitumour complexes [{trans-PtCl(15NH3)2}2{μ-(15NH2(CH2)615NH2(CH2)615NH2)}]3+ (BBR3007, 1,1/t,t-6,6, 1) and [{trans-PtCl(15NH3)2}2{μ-(15NH2(CH2)615NH2(CH2)215NH2(CH2)615NH2)}]4+ (BBR3610, 1,1/t,t-6,2,6, 1′) have been probed using 2D [1H, 15N] HSQC NMR spectroscopy. Reported herein are the rate constants for the hydrolysis of 1 and 1′, as well as the acid dissociation constants of the coordinated aqua ligands in their aquated derivatives. The aquation and anation rate constants for the single step aquation model in 15 mM NaClO4 (pH 5.4) at 298 K are, for 1, k1 = 7.2 ± 0.1 ×10−5s−1, k−1 = 0.096 ± 0.002 M−1s−1 and, for 1′, k1 = 4.0 ± 0.2 × 10−5s−1, k−1 = 1.4 ± 0.1 M−1s−1. The effect of the linker backbone (Pt(tetra(m)mine vs.polyamine) was evaluated by comparison with previous data for the trinuclear complex [{trans-PtCl(NH3)2}2(μ-trans-Pt(NH3)2{NH2(CH2)6NH2}2)]4+ (1,0,1/t,t,t or BBR3464). The pK1 for 1,0,1/t,t,t (3.44) is closest to that of 1 (3.12), while the pronounced difference for 1′ (4.54), means that 1′ is the least aquated of the three complexes at equilibrium. pKa values of 5.92 were calculated for the aquated forms of both 1 and 1′, which are 0.3 pK units higher than for either 1,0,1/t,t,t, or the dinuclear 1,1/t,t. The higher pKa values for both polyamine-linked compounds may be attributed to the formation of macrochelates between the central NH2 groups and the {PtN3O} coordination sphere of the aquated species.en_US
dc.description.peerreviewedYesen_US
dc.description.publicationstatusYesen_US
dc.languageEnglishen_US
dc.publisherRoyal Society of Chemistryen_US
dc.publisher.placeUnited Kingdomen_US
dc.relation.ispartofstudentpublicationNen_US
dc.relation.ispartofpagefrom4147en_US
dc.relation.ispartofpageto4154en_US
dc.relation.ispartofissue16en_US
dc.relation.ispartofjournalDalton Transactionsen_US
dc.relation.ispartofvolume40en_US
dc.rights.retentionYen_US
dc.subject.fieldofresearchBioinorganic Chemistryen_US
dc.subject.fieldofresearchcode030201en_US
dc.titleSolution studies of dinuclear polyamine-linked platinum-based antitumour complexesen_US
dc.typeJournal articleen_US
dc.type.descriptionC1 - Peer Reviewed (HERDC)en_US
dc.type.codeC - Journal Articlesen_US
gro.date.issued2011
gro.hasfulltextNo Full Text


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