Trinuclear copper(II) complex showing high selectivity for the hydrolysis of 2′-5′ over 3′-5′ for UpU and 3′-5′ over 2′-5′ for ApA ribonucleotides

Makoto Komiyama, Shinichiro Kina, Kazunari Matsumura, Jun Sumaoka, Suzanne Tobey, Vincent M. Lynch, Eric Anslyn

Research output: Contribution to journalArticle

72 Citations (Scopus)

Abstract

The cooperative action of multiple Cu(II) nuclear centers is shown to be effective and selective in the hydrolysis of 2′-5′ and 3′-5′ ribonucleotides. Reported herein is the specific catalysis by two trinuclear Cu(II) complexes of L3A and L3B. Pseudo first-order kinetic studies reveal that the L3A trinuclear Cu(II) complex effects hydrolysis of Up(2′-5′)U with a rate constant of 28 × 10-4 min-1 and Up(3′-5′)U with a rate constant of 0.5 × 10-4 min-1. The hydrolyses of Ap(3′-5′)A and Ap(2′-5′)A proceed with rate constants of 24 × 10-4 min-1 and 0.5 × 10-4 min-1 respectively. The L3A trinuclear Cu(II) complex demonstrates high specificity for Up(2′-5′)U and Ap(3′-5′)A. Similar studies with the more rigid L3B trinuclear Cu(II) complex shows no selectivity and yields lower rate constants for hydrolysis. The selectivity observed with the L3A ligand is attributed to the geometry of the ligand-bound diribonucleotide which ultimately dictates the proximity of the attacking hydroxyl and the phosphoester to a Cu(II) center for activation and subsequent hydrolysis.

Original languageEnglish
Pages (from-to)13731-13736
Number of pages6
JournalJournal of the American Chemical Society
Volume124
Issue number46
DOIs
Publication statusPublished - 2002 Nov 20
Externally publishedYes

Fingerprint

Ribonucleotides
Copper
Hydrolysis
Rate constants
Ligands
Hydroxyl Radical
Catalysis
Chemical activation
uridine monophosphate-uridine
Kinetics
Geometry

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Trinuclear copper(II) complex showing high selectivity for the hydrolysis of 2′-5′ over 3′-5′ for UpU and 3′-5′ over 2′-5′ for ApA ribonucleotides. / Komiyama, Makoto; Kina, Shinichiro; Matsumura, Kazunari; Sumaoka, Jun; Tobey, Suzanne; Lynch, Vincent M.; Anslyn, Eric.

In: Journal of the American Chemical Society, Vol. 124, No. 46, 20.11.2002, p. 13731-13736.

Research output: Contribution to journalArticle

Komiyama, Makoto ; Kina, Shinichiro ; Matsumura, Kazunari ; Sumaoka, Jun ; Tobey, Suzanne ; Lynch, Vincent M. ; Anslyn, Eric. / Trinuclear copper(II) complex showing high selectivity for the hydrolysis of 2′-5′ over 3′-5′ for UpU and 3′-5′ over 2′-5′ for ApA ribonucleotides. In: Journal of the American Chemical Society. 2002 ; Vol. 124, No. 46. pp. 13731-13736.
@article{98db0298524145cdb335e53ae258d988,
title = "Trinuclear copper(II) complex showing high selectivity for the hydrolysis of 2′-5′ over 3′-5′ for UpU and 3′-5′ over 2′-5′ for ApA ribonucleotides",
abstract = "The cooperative action of multiple Cu(II) nuclear centers is shown to be effective and selective in the hydrolysis of 2′-5′ and 3′-5′ ribonucleotides. Reported herein is the specific catalysis by two trinuclear Cu(II) complexes of L3A and L3B. Pseudo first-order kinetic studies reveal that the L3A trinuclear Cu(II) complex effects hydrolysis of Up(2′-5′)U with a rate constant of 28 × 10-4 min-1 and Up(3′-5′)U with a rate constant of 0.5 × 10-4 min-1. The hydrolyses of Ap(3′-5′)A and Ap(2′-5′)A proceed with rate constants of 24 × 10-4 min-1 and 0.5 × 10-4 min-1 respectively. The L3A trinuclear Cu(II) complex demonstrates high specificity for Up(2′-5′)U and Ap(3′-5′)A. Similar studies with the more rigid L3B trinuclear Cu(II) complex shows no selectivity and yields lower rate constants for hydrolysis. The selectivity observed with the L3A ligand is attributed to the geometry of the ligand-bound diribonucleotide which ultimately dictates the proximity of the attacking hydroxyl and the phosphoester to a Cu(II) center for activation and subsequent hydrolysis.",
author = "Makoto Komiyama and Shinichiro Kina and Kazunari Matsumura and Jun Sumaoka and Suzanne Tobey and Lynch, {Vincent M.} and Eric Anslyn",
year = "2002",
month = "11",
day = "20",
doi = "10.1021/ja020877t",
language = "English",
volume = "124",
pages = "13731--13736",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "46",

}

TY - JOUR

T1 - Trinuclear copper(II) complex showing high selectivity for the hydrolysis of 2′-5′ over 3′-5′ for UpU and 3′-5′ over 2′-5′ for ApA ribonucleotides

AU - Komiyama, Makoto

AU - Kina, Shinichiro

AU - Matsumura, Kazunari

AU - Sumaoka, Jun

AU - Tobey, Suzanne

AU - Lynch, Vincent M.

AU - Anslyn, Eric

PY - 2002/11/20

Y1 - 2002/11/20

N2 - The cooperative action of multiple Cu(II) nuclear centers is shown to be effective and selective in the hydrolysis of 2′-5′ and 3′-5′ ribonucleotides. Reported herein is the specific catalysis by two trinuclear Cu(II) complexes of L3A and L3B. Pseudo first-order kinetic studies reveal that the L3A trinuclear Cu(II) complex effects hydrolysis of Up(2′-5′)U with a rate constant of 28 × 10-4 min-1 and Up(3′-5′)U with a rate constant of 0.5 × 10-4 min-1. The hydrolyses of Ap(3′-5′)A and Ap(2′-5′)A proceed with rate constants of 24 × 10-4 min-1 and 0.5 × 10-4 min-1 respectively. The L3A trinuclear Cu(II) complex demonstrates high specificity for Up(2′-5′)U and Ap(3′-5′)A. Similar studies with the more rigid L3B trinuclear Cu(II) complex shows no selectivity and yields lower rate constants for hydrolysis. The selectivity observed with the L3A ligand is attributed to the geometry of the ligand-bound diribonucleotide which ultimately dictates the proximity of the attacking hydroxyl and the phosphoester to a Cu(II) center for activation and subsequent hydrolysis.

AB - The cooperative action of multiple Cu(II) nuclear centers is shown to be effective and selective in the hydrolysis of 2′-5′ and 3′-5′ ribonucleotides. Reported herein is the specific catalysis by two trinuclear Cu(II) complexes of L3A and L3B. Pseudo first-order kinetic studies reveal that the L3A trinuclear Cu(II) complex effects hydrolysis of Up(2′-5′)U with a rate constant of 28 × 10-4 min-1 and Up(3′-5′)U with a rate constant of 0.5 × 10-4 min-1. The hydrolyses of Ap(3′-5′)A and Ap(2′-5′)A proceed with rate constants of 24 × 10-4 min-1 and 0.5 × 10-4 min-1 respectively. The L3A trinuclear Cu(II) complex demonstrates high specificity for Up(2′-5′)U and Ap(3′-5′)A. Similar studies with the more rigid L3B trinuclear Cu(II) complex shows no selectivity and yields lower rate constants for hydrolysis. The selectivity observed with the L3A ligand is attributed to the geometry of the ligand-bound diribonucleotide which ultimately dictates the proximity of the attacking hydroxyl and the phosphoester to a Cu(II) center for activation and subsequent hydrolysis.

UR - http://www.scopus.com/inward/record.url?scp=0037146077&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037146077&partnerID=8YFLogxK

U2 - 10.1021/ja020877t

DO - 10.1021/ja020877t

M3 - Article

C2 - 12431103

AN - SCOPUS:0037146077

VL - 124

SP - 13731

EP - 13736

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 46

ER -