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Mechanistic information on the reaction of cis- and trans-[RuCl2(DMSO)(4)] with d(T(2)GGT(2)) derived from MALDI-TOF and HPLC studies

Brindell, M; Elmroth, Sofi LU and Stochel, G (2004) In Journal of Inorganic Biochemistry 98(8). p.1367-1377
Abstract
Reactions of trans and cis isomers of the Ru-II complex [RuCl2(DMSO)(4)] with single-stranded hexanucleotide d(T(2)GGT(2)) were studied in aqueous solutions in the absence and presence of excess chloride by high performance liquid chromatography (HPLC) and matrix-assisted laser desorption/ionisation time of flight mass spectrometry (MALDI-TOF MS). Despite the different reactive species formed from the two isomers in aqueous solution, similar reaction products are obtained in their interaction with d(T(2)GGT(2)). Both [RuCl2(DMSO)(4)] isomers bind to the oligonucleotide in the bidentate mode to form thermodynamically stable bis-guanosine adducts, Ru(G-N7)(2), Significant differences were observed in the reaction rates, however the reaction... (More)
Reactions of trans and cis isomers of the Ru-II complex [RuCl2(DMSO)(4)] with single-stranded hexanucleotide d(T(2)GGT(2)) were studied in aqueous solutions in the absence and presence of excess chloride by high performance liquid chromatography (HPLC) and matrix-assisted laser desorption/ionisation time of flight mass spectrometry (MALDI-TOF MS). Despite the different reactive species formed from the two isomers in aqueous solution, similar reaction products are obtained in their interaction with d(T(2)GGT(2)). Both [RuCl2(DMSO)(4)] isomers bind to the oligonucleotide in the bidentate mode to form thermodynamically stable bis-guanosine adducts, Ru(G-N7)(2), Significant differences were observed in the reaction rates, however the reaction with trans[RuCl2(DMSO)(4)] is ca. 5-10 times faster in comparison to that observed for the cis analogue. This difference is interpreted in terms of different rate-limiting steps for the trans and cis complexes, respectively. It is suggested that the rate of the reaction with the trans isomer is controlled by dissociation of a Cl- ligand from the initially formed trans, cis, cis-[RuCl2(DMSO)(2)(H2O)(2)]. In the contrast, release of a dimethyl sulfoxide molecule from the reactive species cis,fac-[RuCl2(DMSO)(3)(H2O)] is likely to be rate limiting for the cis analogue. Significant influence of electrostatic interactions on the reaction rate was observed for the trans isomer. Mechanistic interpretation of the observed reactivity trends based on data obtained from UV-Vis spectroscopy, HPLC and MALDI-TOF MS studies is presented and discussed within the paper. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
oligonucleotide, ruthenium complexes, bidentate binding mode, MALDI-TOF, HPLC
in
Journal of Inorganic Biochemistry
volume
98
issue
8
pages
1367 - 1377
publisher
Elsevier
external identifiers
  • pmid:15271513
  • wos:000223383600014
  • scopus:3242731538
ISSN
1873-3344
DOI
10.1016/j.jinorgbio.2004.04.015
language
English
LU publication?
yes
id
514c83b4-0b6a-4b93-8bad-3e6a0d4f0f8d (old id 269527)
date added to LUP
2007-10-17 12:42:18
date last changed
2017-01-01 06:53:45
@article{514c83b4-0b6a-4b93-8bad-3e6a0d4f0f8d,
  abstract     = {Reactions of trans and cis isomers of the Ru-II complex [RuCl2(DMSO)(4)] with single-stranded hexanucleotide d(T(2)GGT(2)) were studied in aqueous solutions in the absence and presence of excess chloride by high performance liquid chromatography (HPLC) and matrix-assisted laser desorption/ionisation time of flight mass spectrometry (MALDI-TOF MS). Despite the different reactive species formed from the two isomers in aqueous solution, similar reaction products are obtained in their interaction with d(T(2)GGT(2)). Both [RuCl2(DMSO)(4)] isomers bind to the oligonucleotide in the bidentate mode to form thermodynamically stable bis-guanosine adducts, Ru(G-N7)(2), Significant differences were observed in the reaction rates, however the reaction with trans[RuCl2(DMSO)(4)] is ca. 5-10 times faster in comparison to that observed for the cis analogue. This difference is interpreted in terms of different rate-limiting steps for the trans and cis complexes, respectively. It is suggested that the rate of the reaction with the trans isomer is controlled by dissociation of a Cl- ligand from the initially formed trans, cis, cis-[RuCl2(DMSO)(2)(H2O)(2)]. In the contrast, release of a dimethyl sulfoxide molecule from the reactive species cis,fac-[RuCl2(DMSO)(3)(H2O)] is likely to be rate limiting for the cis analogue. Significant influence of electrostatic interactions on the reaction rate was observed for the trans isomer. Mechanistic interpretation of the observed reactivity trends based on data obtained from UV-Vis spectroscopy, HPLC and MALDI-TOF MS studies is presented and discussed within the paper.},
  author       = {Brindell, M and Elmroth, Sofi and Stochel, G},
  issn         = {1873-3344},
  keyword      = {oligonucleotide,ruthenium complexes,bidentate binding mode,MALDI-TOF,HPLC},
  language     = {eng},
  number       = {8},
  pages        = {1367--1377},
  publisher    = {Elsevier},
  series       = {Journal of Inorganic Biochemistry},
  title        = {Mechanistic information on the reaction of cis- and trans-[RuCl2(DMSO)(4)] with d(T(2)GGT(2)) derived from MALDI-TOF and HPLC studies},
  url          = {http://dx.doi.org/10.1016/j.jinorgbio.2004.04.015},
  volume       = {98},
  year         = {2004},
}