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Title: Relaxometry, luminescence measurements, electrophoresis, and animal biodistribution of lanthanide(III) complexes of some polyaza macrocyclic acetates containing pyridine

Abstract

Four Gd{sup 3+} complexes [Gd(BP2A){sup +}, Gd(PC2A){sup +}, Gd(PCTA){sup 0}, and Gd(BPO4A){sup {minus}}] with polyazamacrocyclic ligands that contain a pyridine moiety were prepared and examined for possible use as MRI contrast enhancement agents. The authors estimated the number of inner sphere water molecules (q{sub Gd}) for the Gd{sup 3+} complexes from the values of q found for the Tb{sup 3+} and/or Eu{sup 3+} complexes by luminescence lifetime measurements. It was estimated that q{sub Gd} = 3.5, 3.3, 2.4, and 0.2 for Gd(BP2A){sup +}, Gd(PC2A){sup +}, Gd(PCTA){sup 0}, and Gd(BPO4A){sup {minus}}, respectively. The inner sphere relaxivities (r{sub 1,inner}) of these tetraaza macrocyclic complexes were higher than that of Gd(DOTA){sup {minus}} [i.e. 6.79 for Gd(BP2A){sup +}, 6.21 for Gd(PC2A){sup +}, and 4.60 for Gd(PCTA){sup 0} mM{sup {minus}1}s{sup {minus}1} at 40 MHz and 25{degrees}C], but the normalized relaxivities per q{sub Gd} (1.94, 1.88, and 1.92 mM{sup {minus}1}s{sup {minus}1}, respectively) were comparable to that of Gd(DOTA){sup {minus}}. A quantitative treatment of the NMRD profiles based on Solomon-Bloembergen-Morgan theory, using the NMRD profile of Gd(BPO4A){sup {minus}} to correct for an outer sphere contribution, showed that the complexes exhibit characteristics similar to that of Gd(DOTA){sup {minus}} but with shorter electronic relaxation times. Tissue biodistribution results usingmore » radioactive {sup 153}Sm and {sup 159}Gd complexes in rats indicate that the cationic [{sup 153}Sm-(BP2A){sup +} and {sup 153}Sm(PC2A){sup +}] complexes accumulate preferably in the bone tissue while the neutral [{sup 153}Sm-(PCTA){sup 0}] and anionic [{sup 153}Sm(BPO4A){sup {minus}}] complexes appear to have renal clearances similar to those of other low molecular weight contrast agents [i.e. Gd(DTPA){sup 2{minus}} and Gd(DOTA){sup {minus}}].« less

Authors:
;  [1]; ;  [2]; ;  [3]
  1. Univ. of Texas, Dallas, Richardson, TX (United States)
  2. Dow Chemical Co., Freeport, TX (United States)
  3. Univ. of Mons-Hainault (Belgium)
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
75715
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 34; Journal Issue: 8; Other Information: PBD: 12 Apr 1995
Country of Publication:
United States
Language:
English
Subject:
55 BIOLOGY AND MEDICINE, BASIC STUDIES; 40 CHEMISTRY; RARE EARTH COMPLEXES; UPTAKE; STRUCTURAL CHEMICAL ANALYSIS; LUMINESCENCE; ELECTROPHORESIS; ACETATES; PYRIDINES; SAMARIUM 135; GADOLINIUM 159; LABELLED COMPOUNDS; RATS; SKELETON

Citation Formats

Kim, W.D., Sherry, A.D., Kiefer, G.E., McMillan, K., Maton, F., and Muller, R.N. Relaxometry, luminescence measurements, electrophoresis, and animal biodistribution of lanthanide(III) complexes of some polyaza macrocyclic acetates containing pyridine. United States: N. p., 1995. Web. doi:10.1021/ic00112a041.
Kim, W.D., Sherry, A.D., Kiefer, G.E., McMillan, K., Maton, F., & Muller, R.N. Relaxometry, luminescence measurements, electrophoresis, and animal biodistribution of lanthanide(III) complexes of some polyaza macrocyclic acetates containing pyridine. United States. doi:10.1021/ic00112a041.
Kim, W.D., Sherry, A.D., Kiefer, G.E., McMillan, K., Maton, F., and Muller, R.N. 1995. "Relaxometry, luminescence measurements, electrophoresis, and animal biodistribution of lanthanide(III) complexes of some polyaza macrocyclic acetates containing pyridine". United States. doi:10.1021/ic00112a041.
@article{osti_75715,
title = {Relaxometry, luminescence measurements, electrophoresis, and animal biodistribution of lanthanide(III) complexes of some polyaza macrocyclic acetates containing pyridine},
author = {Kim, W.D. and Sherry, A.D. and Kiefer, G.E. and McMillan, K. and Maton, F. and Muller, R.N.},
abstractNote = {Four Gd{sup 3+} complexes [Gd(BP2A){sup +}, Gd(PC2A){sup +}, Gd(PCTA){sup 0}, and Gd(BPO4A){sup {minus}}] with polyazamacrocyclic ligands that contain a pyridine moiety were prepared and examined for possible use as MRI contrast enhancement agents. The authors estimated the number of inner sphere water molecules (q{sub Gd}) for the Gd{sup 3+} complexes from the values of q found for the Tb{sup 3+} and/or Eu{sup 3+} complexes by luminescence lifetime measurements. It was estimated that q{sub Gd} = 3.5, 3.3, 2.4, and 0.2 for Gd(BP2A){sup +}, Gd(PC2A){sup +}, Gd(PCTA){sup 0}, and Gd(BPO4A){sup {minus}}, respectively. The inner sphere relaxivities (r{sub 1,inner}) of these tetraaza macrocyclic complexes were higher than that of Gd(DOTA){sup {minus}} [i.e. 6.79 for Gd(BP2A){sup +}, 6.21 for Gd(PC2A){sup +}, and 4.60 for Gd(PCTA){sup 0} mM{sup {minus}1}s{sup {minus}1} at 40 MHz and 25{degrees}C], but the normalized relaxivities per q{sub Gd} (1.94, 1.88, and 1.92 mM{sup {minus}1}s{sup {minus}1}, respectively) were comparable to that of Gd(DOTA){sup {minus}}. A quantitative treatment of the NMRD profiles based on Solomon-Bloembergen-Morgan theory, using the NMRD profile of Gd(BPO4A){sup {minus}} to correct for an outer sphere contribution, showed that the complexes exhibit characteristics similar to that of Gd(DOTA){sup {minus}} but with shorter electronic relaxation times. Tissue biodistribution results using radioactive {sup 153}Sm and {sup 159}Gd complexes in rats indicate that the cationic [{sup 153}Sm-(BP2A){sup +} and {sup 153}Sm(PC2A){sup +}] complexes accumulate preferably in the bone tissue while the neutral [{sup 153}Sm-(PCTA){sup 0}] and anionic [{sup 153}Sm(BPO4A){sup {minus}}] complexes appear to have renal clearances similar to those of other low molecular weight contrast agents [i.e. Gd(DTPA){sup 2{minus}} and Gd(DOTA){sup {minus}}].},
doi = {10.1021/ic00112a041},
journal = {Inorganic Chemistry},
number = 8,
volume = 34,
place = {United States},
year = 1995,
month = 4
}
  • The synthesis of the branched-macrocyclic ligand 1 incorporating two 2,2[prime]-bipyridine units in the macrocycle and two 9-methyl-1,10-phenanthroline units in the branches is described as well as the synthesis and the photophysical properties of its Eu[sup 3+], Tb[sup 3+], and Gd[sup 3+] complexes. These complexes do not decompose in water in contrast to those of the related ligand containing 2,2[prime]-bipyridine instead of 1,10-phenanthroline. They show intense absorption bands in the UV region due to absorption in the ligand. The emission spectra of the [Eu[contained in]1][sup 3+] and [Tb[contained in]1][sup 3+] complexes obtained upon ligand excitation show the usual Eu[sup 3+] andmore » Tb[sup 3+] transitions. The pattern of the emission spectrum of the [Eu[contained in]1][sup 3+] complex allows one to assess a low (presumably C[sub 2]) symmetry as the probable site symmetry of the metal ion in the complex. For [Eu[contained in]1][sup 3+] and [Tb[contained in]1][sup 3+], the metal luminescence excitation spectra in water match the ligand absorption spectra while in methanol the absorption due to the phenanthroline is missing. This suggests that in water the efficiency of the ligand-to-metal energy transfer is similar for the two chromophores while in methanol phenanthroline transfers energy to the metal ion less efficiently than bipyridine. The luminescence quantum yield values in water and methanol confirm this interpretation. The lifetimes of the Eu[sup 3+] and Tb[sup 3+] emitting state indicate that the shielding of the metal ion from solvent molecules is rather inefficient. For the [Tb[contained in]1][sup 3+] complex the lifetimes are temperature dependent which is attributed to the presence of an equilibrium between the metal emitting state and triplet excited states of the ligand; this process is most likely responsible for the low luminescence quantum yields and the oxygen effect on the Tb[sup 3+] luminescence.« less
  • The reaction of Eu{sup 3+} with 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate was followed by luminescence of the Eu{sup 3+} center. Reaction kinetics for the formation of intermediates and the final product, [Eu(dota)H{sub 2}O]{sup {minus}}, are reported. The rate limiting step is found to be the rearrangement of EuHdotato from the final product.
  • 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
  • A new family of five lanthanide-organic coordination polymers incorporating multi-functional N-hetrocyclic dicarboxylate ligand, namely, [Ln{sub 2}(Hdpp){sub 2}(dpp){sub 2}]{sub n}Ln=Pr(1), Eu(2), Gd(3), Dy(4), Er(5) (H{sub 2}dpp=1-(3, 4-dicarboxyphenyl) pyridin-4-ol) have been fabricated successfully through solvothermal reaction of 1-(3,4-dicarboxyphenyl)-4-hydroxypyridin-1-ium chloride with trivalent lanthanide salts, and have been characterized systematically. The complexes 1–5 are isomorphous and isostructural. They all feature three dimensional (3D) frameworks based on the interconnection of 1D double chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 4+} basic carboxylate as secondary building unit (SBU). The results of magnetic analysis shows the same bridging fashion of carboxylic group in this casemore » results in the different magnetic properties occurring within lanthanide polymers. Moreover, the Eu(III) and Dy(III) complexes display characteristic luminescence emission in the visible regions. - Graphical abstract: A new family of lanthanide-organic frameworks incorporating multi-donor twisted ligand has been fabricated successfully, and has been characterized systematically. The complexes 1–5 are isostructural, and all feather three dimensional (3D) frameworks based on the interconnection of 1D double stride chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 2+} basic carboxylate as secondary building unit (SBU). Display Omitted - Highlights: • New family of lanthanide–organic coordination polymers incorporating multifunctional N-hetrocyclic dicarboxylate ligand has been fabricated. • They have been characterized systematically. • They all feather three dimensional frameworks based on the binuclear moiety of [Ln{sub 2}(Hdpp){sub 2}]{sup 2+}. • The Eu(III) and Dy(III) analogues exhibit intense photoluminescence.« less