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Title: Quantitative two-dimensional EXSY spectroscopy and dynamic behavior of a paramagnetic lanthanide macrocyclic chelate: YbDOTA (DOTA = 1,4,7,10-tetraazacyclododecane-N,N{prime},N{double_prime},N{double_prime}{prime}-tetraacetic acid)

Abstract

The chelate, YbDOTA (DOTA = 1,4,7,10-tetraazacyclododecane-N,N{prime},N{double_prime},N{double_prime}{prime}-tetraacetic acid) has two possible conformations. Interconversion between isomers was studied by EXSY NMR spectroscopy. The activation energy for conversion was found to be 65.6 kJ/mol for conversion from the major to the minor species.

Authors:
;  [1]
  1. Univ. of Liege, Sart Tilman (Belgium)
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
457880
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 33; Journal Issue: 18; Other Information: PBD: 31 Aug 1994
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; YTTERBIUM COMPLEXES; NUCLEAR MAGNETIC RESONANCE; CHELATES; ACTIVATION ENERGY

Citation Formats

Jacques, V., and Desreux, J.F. Quantitative two-dimensional EXSY spectroscopy and dynamic behavior of a paramagnetic lanthanide macrocyclic chelate: YbDOTA (DOTA = 1,4,7,10-tetraazacyclododecane-N,N{prime},N{double_prime},N{double_prime}{prime}-tetraacetic acid). United States: N. p., 1994. Web. doi:10.1021/ic00096a033.
Jacques, V., & Desreux, J.F. Quantitative two-dimensional EXSY spectroscopy and dynamic behavior of a paramagnetic lanthanide macrocyclic chelate: YbDOTA (DOTA = 1,4,7,10-tetraazacyclododecane-N,N{prime},N{double_prime},N{double_prime}{prime}-tetraacetic acid). United States. doi:10.1021/ic00096a033.
Jacques, V., and Desreux, J.F. 1994. "Quantitative two-dimensional EXSY spectroscopy and dynamic behavior of a paramagnetic lanthanide macrocyclic chelate: YbDOTA (DOTA = 1,4,7,10-tetraazacyclododecane-N,N{prime},N{double_prime},N{double_prime}{prime}-tetraacetic acid)". United States. doi:10.1021/ic00096a033.
@article{osti_457880,
title = {Quantitative two-dimensional EXSY spectroscopy and dynamic behavior of a paramagnetic lanthanide macrocyclic chelate: YbDOTA (DOTA = 1,4,7,10-tetraazacyclododecane-N,N{prime},N{double_prime},N{double_prime}{prime}-tetraacetic acid)},
author = {Jacques, V. and Desreux, J.F.},
abstractNote = {The chelate, YbDOTA (DOTA = 1,4,7,10-tetraazacyclododecane-N,N{prime},N{double_prime},N{double_prime}{prime}-tetraacetic acid) has two possible conformations. Interconversion between isomers was studied by EXSY NMR spectroscopy. The activation energy for conversion was found to be 65.6 kJ/mol for conversion from the major to the minor species.},
doi = {10.1021/ic00096a033},
journal = {Inorganic Chemistry},
number = 18,
volume = 33,
place = {United States},
year = 1994,
month = 8
}
  • The authors investigated novel synthetic routes to pendant-type {rho}-NO{sub 2}-BZ-DOTA, 1 and 2, containing a (carboxymethyl) amino group appended to the DOTA structure via a methylene (1) and an ethylene (2) spacer, respectively. The complexation of Yttrium (III) with these chelates is reported. 1 fig., 1 tab.
  • A promising cancer therapy involves the use of the macrocyclic polyaminoacetate DOTA (1,4,6,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) attached to a tumor-targeting antibody complexed with the {beta} emitter {sup 90}Y{sup 3+}. However, incorporation of the {sup 90}Y into the DOTA conjugate is too slow. To identify the origins of this problem, ab initio quantum chemistry methods (B3LYP/:ACVP* and HF/LACVP*) were used to predict structures and energetics. The authors find that the initial complex YH{sub 2}(DOTA){sup +} is 4-coodinate (the four equivalent carboxylate oxygens), which transforms to YH(DOTA) (5-coordinate with one ring N and four carboxylate oxygens), and finally to Y(DOTA){sup {minus}}, which is 8-coordinatemore » (four oxygens and four nitrogens). The rate-determining step is the conversion of YH(DOTA) to Y(DOTA){sup {minus}}, which was calculated to have an activation free energy (aqueous phase) of 8.4 kcal/mol, in agreement with experimental results (8.1--9.3 kcal/mol) for various metals to DOTA [Kumar, K.; Tweedle, M.F. Inorg. Chem. 1993, 32, 4193--4199; Wu, S.L.; Horrocks, W.D., Jr., Inorg. Chem. 1995, 34, 3724--2732]. On the basis of this mechanism the authors propose a modified chelate, DO3AlPr, which has calculated at a much faster rate of incorporation.« less
  • The tetraazatricarboxylic macrocycle, (1R,4R,7R)-[alpha],[alpha][prime],[alpha][double prime]-trimethyl-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3MA) (4) was synthesized by the simultaneous hydrogenolysis and deformylation of 10-formyl-1,4,7-tris(benzyloxycarbonylmethyl)-1,4,7,10-tetraazacyclododecane (N-CHO-DO3MA-TBE) (11). Chelation of DO3MA with gadolinium acetate resulted in a diastereomerically pure Gd(III) chelate, Gd(DO3MA) (4a). X-ray structure analysis of Gd(DO3MA) crystals revealed that the three asymmetric carbons bearing [alpha]-methyl groups all have the (R)-configuration and that the chelate crystallizes as a dimer, [(DO3MA)Gd][(DO3MA)Gd(H[sub 2]O)[sub 2]], in which both the Gd atoms are enneacoordinate. Crystal data are as follows: [2(GdC[sub 17]H[sub 29]N[sub 4]O[sub 6])[center dot]2H[sub 2]O][center dot]4H[sub 2]O, a = 17.471(6) [angstrom], b = 25.495(6) [angstrom], c = 10.146(3) [angstrom], Vmore » = 4520(4) [angstrom][sup 3], P2[sub 1]2[sub 1]2[sub 1], Z = 4, R = 0.035, R[sub w] = 0.044. The relaxivity of Gd(DO3MA) was found to be 4.4 [+-] 0.1 mM[sup [minus]1] s[sup [minus]1] at 20 MHz and 40[degrees]C. The measured stability constant of Gd(DO3MA) was log K[sub eq] = 25.3, which makes Gd(DO3MA) the most stable heptadentate chelate known for Gd(III). 28 refs., 3 figs., 4 tabs.« less
  • Solution and solid-state properties of the Eu(III) complex of the tetramide macrocyclic ligand TCMC (TCMC = 1,4,7,10-tetrakis(carbamoylmethyl)-1,4-7,10-tetraazacyclododecane) are investigated as part of an effort to develop lanthanide(III) macrocyclic catalysts. (Eu(TCMC)(H{sub 2}O))(CF{sub 3}SO{sub 3}){sub 3}{center_dot}2CH{sub 3}OH crystallizes in the centrosymmetric monoclinic space group. The structure was solved and refined to R=4.02% and R{sub w}=4.33% for 3510 reflections with F>6{omega}(F). (R=7.04%, R{sub w}=6.48% for all 5322 independent reflections). Four stereoisomers (two enantiomeric pairs) of the (Eu(TCMC)(H{sub 2}O)){sup 3+} cation appear in the crystal. The structure is disordered, containing two overlapping diastereomers that are interrelated by different conformations of the 1,4,7,10-tetraazacyclododecane ring definingmore » the asymmetric unit. Two enantiomers are related to these by operations of the second king (i,n-glide). The nine-coordinate Eu(III) center has a 4:4:1 coordination geometry formed by the octadentate TCMC ligand and a single bound water molecule. The laser-induced luminescence excitation band of a single crystal of (Eu(TCMC)H{sub 2}O)(CF{sub 3}SO{sub 3}){sub 3}{center_dot}2CH{sub 3}OH resolves into two peaks, suggesting that each diastereomer gives rise to a separate excitation peak. Similarly, the luminescence excitation spectrum of a solution of (Eu(TCMC)){sup 3+} in water indicates that two species are present in solution. The {sup 31}P NMR resonance of diethyl phosphate is monitored at 18{+-}2{degrees}C, pH 7.4, upon addition of (Eu(TCMC)){sup 3+} as well as upon addition of several lanthanide(III) complexes that are catalysts for RNA cleavage. No binding of diethyl phosphate to (Eu(TCMC)){sup 3+} is observed. The hexadentate Schiff-base complex (La(L{sup 1})){sup 3+} binds to diethyl phosphate with a binding constant of 47.7{+-}0.5 M{sup -1}.« less
  • The synthesis and dynamic properties of La(THED)(CF[sub 3]SO[sub 3])[sub 3] and Eu(THED)(CF[sub 3]SO[sub 3])[sub 3] are described. (THED is 1,47,10-tetrakis(2-hydroxyethyl)-1,4,7,10-tetraazacyclododecane.) Variable-temperature [sup 1]H and [sup 13]C NMR studies indicate that the ethylenic groups of the 12-membered tetraaza macrocycle are rigid on the NMR time scale at low temperatures (-40[degrees]C), and all adopt the same conformation. Macrocycle rigidity is lost at elevated temperatures. A dynamic process involving conformational changes of the ethylenic groups in the tetraazamacrocycle is consistent with NMR data. An energy barrier of 52 ([plus minus]0.7) kJ mol[sup [minus]1] is calculated for this process from line-shape analysis of [supmore » 13]C NMR spectra of La(THED)(CF[sub 3]SO[sub 3])[sub 3] at four temperatures. Both complexes are stable in water at near-neutral pH. The dissociation of La[sup 3+] or Eu[sup 3+] from their respective complexes is investigated in the presence of excess Cu[sup 2+] by monitoring an absorbance at 312 nm attributed to the Cu(THED)[sup 2+] complex. For La(THED)(CF[sub 3]SO[sub 3])[sub 3], dissociation is first-order in lanthanum complex and independent of Cu[sup 2+] with a first-order rate constant of 9.2 ([plus minus]0.5) x 10[sup [minus]6] s[sup [minus]1] at 37 [degrees]C, pH 6.0. Eu(THED)(CF[sub 3]SO[sub 3])[sub 3] is substantially more inert to metal ion release than is the lanthanum complex. The first-order rate constant for dissociation of the europium complex at pH 6.0 and 37 [degrees]C is 7.1 ([plus minus]0.4) x 10[sup [minus]7] s[sup [minus]1]; there is a slight dependence of the rate constant on pH in the pH range 3.0-6.8.« less