Aqueous shift reagents for high-resolution cation NMR spectroscopy. 4. DybPPPpob5-

Janio Szklaruk, James F. Marecek, Charles Jr Springer, Charles S. Springer

Research output: Contribution to journalArticle

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Abstract

The chelate Dy(PPP)27- (where PPP5- is tripolyphosphate) is a very effective shift reagent for the 23Na NMR signal. However, it is also quite toxic to living animals. In addition to the effects of the equilibrium competitions of the biological metal cations Mg2+ and Ca2+ with Na+ for Dy(PPP)27-, this toxicity is most likely due to the potentially irreversible effects of ligand dissociation in vivo. In order to avoid this latter problem, two PPP moieties have been covalently linked so as to take advantage of the chelate effect. Thus, this paper reports the synthesis of the new shift reagent DybPPPpob5- (where bPPPpob8- is o-bis((3-(tripolyphosphato)propyl)oxy)benzene). In vitro 23Na and 31P NMR experiments show that (1) DybPPPpob5- is an upfield shift reagent (like Dy(PPP)27-), which shifts the 23Na signal more than a third as well as Dy(PPP)27-, (2) the 23Na shift has a pH profile similar to that of Dy(PPP)27-, (3) competition by Ca2+ and Mg2+ with Na+ for DybPPPpob5- is not as severe as it is for Dy(PPP)27- and (4) DybPPPpob5- hydrolysis is catalyzed by alkaline phosphatase but neither as rapidly nor as extensively as that of Dy(PPP)27-. This latter result presumably implies that an uncoordinated PPP moiety of an incompletely dissociated DybPPPpob5- chelate can still act as a substrate for the enzyme. The hydrolysis is slow enough that, with proper care, DybPPPpob5- may be useful as an in vivo shift reagent.

Original languageEnglish (US)
Pages (from-to)660-667
Number of pages8
JournalInorganic Chemistry
Volume29
Issue number4
StatePublished - 1990
Externally publishedYes

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Nuclear magnetic resonance spectroscopy
reagents
Cations
cations
nuclear magnetic resonance
shift
high resolution
chelates
spectroscopy
Hydrolysis
Nuclear magnetic resonance
hydrolysis
Poisons
Benzene
Alkaline Phosphatase
Toxicity
Animals
phosphatases
Metals
Ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Aqueous shift reagents for high-resolution cation NMR spectroscopy. 4. DybPPPpob5-. / Szklaruk, Janio; Marecek, James F.; Springer, Charles Jr; Springer, Charles S.

In: Inorganic Chemistry, Vol. 29, No. 4, 1990, p. 660-667.

Research output: Contribution to journalArticle

Szklaruk, J, Marecek, JF, Springer, CJ & Springer, CS 1990, 'Aqueous shift reagents for high-resolution cation NMR spectroscopy. 4. DybPPPpob5-', Inorganic Chemistry, vol. 29, no. 4, pp. 660-667.
Szklaruk, Janio ; Marecek, James F. ; Springer, Charles Jr ; Springer, Charles S. / Aqueous shift reagents for high-resolution cation NMR spectroscopy. 4. DybPPPpob5-. In: Inorganic Chemistry. 1990 ; Vol. 29, No. 4. pp. 660-667.
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N2 - The chelate Dy(PPP)27- (where PPP5- is tripolyphosphate) is a very effective shift reagent for the 23Na NMR signal. However, it is also quite toxic to living animals. In addition to the effects of the equilibrium competitions of the biological metal cations Mg2+ and Ca2+ with Na+ for Dy(PPP)27-, this toxicity is most likely due to the potentially irreversible effects of ligand dissociation in vivo. In order to avoid this latter problem, two PPP moieties have been covalently linked so as to take advantage of the chelate effect. Thus, this paper reports the synthesis of the new shift reagent DybPPPpob5- (where bPPPpob8- is o-bis((3-(tripolyphosphato)propyl)oxy)benzene). In vitro 23Na and 31P NMR experiments show that (1) DybPPPpob5- is an upfield shift reagent (like Dy(PPP)27-), which shifts the 23Na signal more than a third as well as Dy(PPP)27-, (2) the 23Na shift has a pH profile similar to that of Dy(PPP)27-, (3) competition by Ca2+ and Mg2+ with Na+ for DybPPPpob5- is not as severe as it is for Dy(PPP)27- and (4) DybPPPpob5- hydrolysis is catalyzed by alkaline phosphatase but neither as rapidly nor as extensively as that of Dy(PPP)27-. This latter result presumably implies that an uncoordinated PPP moiety of an incompletely dissociated DybPPPpob5- chelate can still act as a substrate for the enzyme. The hydrolysis is slow enough that, with proper care, DybPPPpob5- may be useful as an in vivo shift reagent.

AB - The chelate Dy(PPP)27- (where PPP5- is tripolyphosphate) is a very effective shift reagent for the 23Na NMR signal. However, it is also quite toxic to living animals. In addition to the effects of the equilibrium competitions of the biological metal cations Mg2+ and Ca2+ with Na+ for Dy(PPP)27-, this toxicity is most likely due to the potentially irreversible effects of ligand dissociation in vivo. In order to avoid this latter problem, two PPP moieties have been covalently linked so as to take advantage of the chelate effect. Thus, this paper reports the synthesis of the new shift reagent DybPPPpob5- (where bPPPpob8- is o-bis((3-(tripolyphosphato)propyl)oxy)benzene). In vitro 23Na and 31P NMR experiments show that (1) DybPPPpob5- is an upfield shift reagent (like Dy(PPP)27-), which shifts the 23Na signal more than a third as well as Dy(PPP)27-, (2) the 23Na shift has a pH profile similar to that of Dy(PPP)27-, (3) competition by Ca2+ and Mg2+ with Na+ for DybPPPpob5- is not as severe as it is for Dy(PPP)27- and (4) DybPPPpob5- hydrolysis is catalyzed by alkaline phosphatase but neither as rapidly nor as extensively as that of Dy(PPP)27-. This latter result presumably implies that an uncoordinated PPP moiety of an incompletely dissociated DybPPPpob5- chelate can still act as a substrate for the enzyme. The hydrolysis is slow enough that, with proper care, DybPPPpob5- may be useful as an in vivo shift reagent.

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