Enantiomeric two-armed lanthanide-binding tags for complementary effects in paramagnetic NMR spectroscopy

Michael D Lee, Matthew L Dennis, James D Swarbrick, Bim Graham

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The synthesis and characterization of three new bis(1,4,7-triazacyclononane) ligands, L1, L2and L3, featuring a bridging guanidinium group between two macrocyclic units, is reported. The corresponding binuclear copper(II) complexes have been studied as agents to accelerate the cleavage of P–O bonds within two model phosphodiesters, namely bis(p-nitrophenyl)phosphate (BNPP) and 2-hydroxypropyl-p-nitrophenylphosphate (HPNPP). The results of a comparative study of cleavage rates, using the mononuclear copper(II)–tacn complexes bearing single alkylguanidinium groups as a reference, revealed that the binuclear copper(II) complexes are generally less effective cleavage agents, which may be related to a tendency to form hydrolytically inactive hydroxo-bridged species at near-neutral pH and above. However, at pH 7, these complexes produced 4–18-fold increases in the rate of BNPP hydrolysis compared to the parent complex, [Cu(tacn)(OH2)2]2+. Likewise, at pH 6, the complexes cleaved HPNP 5–130-fold faster than [Cu(tacn)(OH2)2]2+, suggesting some degree of cooperative interplay between the two proximal copper(II) centers and the protonated guanidinium bridging group in promoting phosphodiester hydrolysis under these conditions.

Original languageEnglish
Pages (from-to)7954-7957
Number of pages4
JournalChemical Communications
Volume52
Issue number51
DOIs
Publication statusPublished - 2016

Cite this

Lee, Michael D ; Dennis, Matthew L ; Swarbrick, James D ; Graham, Bim. / Enantiomeric two-armed lanthanide-binding tags for complementary effects in paramagnetic NMR spectroscopy. In: Chemical Communications. 2016 ; Vol. 52, No. 51. pp. 7954-7957.
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abstract = "The synthesis and characterization of three new bis(1,4,7-triazacyclononane) ligands, L1, L2and L3, featuring a bridging guanidinium group between two macrocyclic units, is reported. The corresponding binuclear copper(II) complexes have been studied as agents to accelerate the cleavage of P–O bonds within two model phosphodiesters, namely bis(p-nitrophenyl)phosphate (BNPP) and 2-hydroxypropyl-p-nitrophenylphosphate (HPNPP). The results of a comparative study of cleavage rates, using the mononuclear copper(II)–tacn complexes bearing single alkylguanidinium groups as a reference, revealed that the binuclear copper(II) complexes are generally less effective cleavage agents, which may be related to a tendency to form hydrolytically inactive hydroxo-bridged species at near-neutral pH and above. However, at pH 7, these complexes produced 4–18-fold increases in the rate of BNPP hydrolysis compared to the parent complex, [Cu(tacn)(OH2)2]2+. Likewise, at pH 6, the complexes cleaved HPNP 5–130-fold faster than [Cu(tacn)(OH2)2]2+, suggesting some degree of cooperative interplay between the two proximal copper(II) centers and the protonated guanidinium bridging group in promoting phosphodiester hydrolysis under these conditions.",
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Enantiomeric two-armed lanthanide-binding tags for complementary effects in paramagnetic NMR spectroscopy. / Lee, Michael D; Dennis, Matthew L; Swarbrick, James D; Graham, Bim.

In: Chemical Communications, Vol. 52, No. 51, 2016, p. 7954-7957.

Research output: Contribution to journalArticleResearchpeer-review

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