Lanthanide ethylenediaminetetra-acetate chelates as aqueous shift reagents: Evidence for effective axial symmetry in bidentate cytidine 5′-monophosphate and alanine complexes

A. Dean Sherry, Cynthia A. Stark, José R. Ascenso, Carlos F G C Geraldes

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

Lanthanide-induced shift (l.i.s.) data are presented for cytidine 5′-monophosphate (cydmp) and L-alanine binding to a series of lanthanide-edta chelates at high pH (edta = ethylenediaminetetra-acetate). Slow exchange of these substrates between their bound and free environments precludes the use of the heavier Ln(edta) chelates at 25 °C. The cydmp proton l.i.s. ratios at 90 °C are independent of the Ln(edta) used, indicative of effective axial symmetry for this substrate. The alanine l.i.s. values contain large contact shift components which once removed yield corrected pseudo-contact shifts which also are adequately described by an effective axial symmetry model. The results indicate that chemically reasonable structures may be determined from l.i.s. data for substrates acting as bidentate chelators of the lanthanide, providing rapid exchange conditions are met and contact shift contributions are extracted from experimental l.i.s. values for nuclei near the co-ordination site(s). Therefore the fact that the substrate acts as a bidentate chelator does not necessarily exclude the possibility that the axially symmetric model for the l.i.s. is a satisfactory model.

Original languageEnglish (US)
Pages (from-to)2078-2082
Number of pages5
JournalJournal of the Chemical Society, Dalton Transactions
Issue number10
DOIs
StatePublished - 1981

Fingerprint

Cytidine
Lanthanoid Series Elements
Alanine
Acetates
Substrates
Chelating Agents
Protons

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{33ebe18c420048b48c0c4f940d06a05a,
title = "Lanthanide ethylenediaminetetra-acetate chelates as aqueous shift reagents: Evidence for effective axial symmetry in bidentate cytidine 5′-monophosphate and alanine complexes",
abstract = "Lanthanide-induced shift (l.i.s.) data are presented for cytidine 5′-monophosphate (cydmp) and L-alanine binding to a series of lanthanide-edta chelates at high pH (edta = ethylenediaminetetra-acetate). Slow exchange of these substrates between their bound and free environments precludes the use of the heavier Ln(edta) chelates at 25 °C. The cydmp proton l.i.s. ratios at 90 °C are independent of the Ln(edta) used, indicative of effective axial symmetry for this substrate. The alanine l.i.s. values contain large contact shift components which once removed yield corrected pseudo-contact shifts which also are adequately described by an effective axial symmetry model. The results indicate that chemically reasonable structures may be determined from l.i.s. data for substrates acting as bidentate chelators of the lanthanide, providing rapid exchange conditions are met and contact shift contributions are extracted from experimental l.i.s. values for nuclei near the co-ordination site(s). Therefore the fact that the substrate acts as a bidentate chelator does not necessarily exclude the possibility that the axially symmetric model for the l.i.s. is a satisfactory model.",
author = "Sherry, {A. Dean} and Stark, {Cynthia A.} and Ascenso, {Jos{\'e} R.} and Geraldes, {Carlos F G C}",
year = "1981",
doi = "10.1039/DT9810002078",
language = "English (US)",
pages = "2078--2082",
journal = "Journal of the Chemical Society. Dalton Transactions",
issn = "1472-7773",
publisher = "Royal Society of Chemistry",
number = "10",

}

TY - JOUR

T1 - Lanthanide ethylenediaminetetra-acetate chelates as aqueous shift reagents

T2 - Evidence for effective axial symmetry in bidentate cytidine 5′-monophosphate and alanine complexes

AU - Sherry, A. Dean

AU - Stark, Cynthia A.

AU - Ascenso, José R.

AU - Geraldes, Carlos F G C

PY - 1981

Y1 - 1981

N2 - Lanthanide-induced shift (l.i.s.) data are presented for cytidine 5′-monophosphate (cydmp) and L-alanine binding to a series of lanthanide-edta chelates at high pH (edta = ethylenediaminetetra-acetate). Slow exchange of these substrates between their bound and free environments precludes the use of the heavier Ln(edta) chelates at 25 °C. The cydmp proton l.i.s. ratios at 90 °C are independent of the Ln(edta) used, indicative of effective axial symmetry for this substrate. The alanine l.i.s. values contain large contact shift components which once removed yield corrected pseudo-contact shifts which also are adequately described by an effective axial symmetry model. The results indicate that chemically reasonable structures may be determined from l.i.s. data for substrates acting as bidentate chelators of the lanthanide, providing rapid exchange conditions are met and contact shift contributions are extracted from experimental l.i.s. values for nuclei near the co-ordination site(s). Therefore the fact that the substrate acts as a bidentate chelator does not necessarily exclude the possibility that the axially symmetric model for the l.i.s. is a satisfactory model.

AB - Lanthanide-induced shift (l.i.s.) data are presented for cytidine 5′-monophosphate (cydmp) and L-alanine binding to a series of lanthanide-edta chelates at high pH (edta = ethylenediaminetetra-acetate). Slow exchange of these substrates between their bound and free environments precludes the use of the heavier Ln(edta) chelates at 25 °C. The cydmp proton l.i.s. ratios at 90 °C are independent of the Ln(edta) used, indicative of effective axial symmetry for this substrate. The alanine l.i.s. values contain large contact shift components which once removed yield corrected pseudo-contact shifts which also are adequately described by an effective axial symmetry model. The results indicate that chemically reasonable structures may be determined from l.i.s. data for substrates acting as bidentate chelators of the lanthanide, providing rapid exchange conditions are met and contact shift contributions are extracted from experimental l.i.s. values for nuclei near the co-ordination site(s). Therefore the fact that the substrate acts as a bidentate chelator does not necessarily exclude the possibility that the axially symmetric model for the l.i.s. is a satisfactory model.

UR - http://www.scopus.com/inward/record.url?scp=37049097203&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=37049097203&partnerID=8YFLogxK

U2 - 10.1039/DT9810002078

DO - 10.1039/DT9810002078

M3 - Article

AN - SCOPUS:37049097203

SP - 2078

EP - 2082

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

SN - 1472-7773

IS - 10

ER -