22541-19-1

Upstream product

• 22541-18-0 europium(III) 
• 19229-79-9 zinc(II) cation 

Downstream Products

• 15213-88-4 {GdEDTA}^(1-) 
• 18923-26-7 cerium(III) ion 

Relevant academic research and scientific papers

Auto-assembling of ditopic macrocyclic lanthanide chelates with transition-metal ions. Rigid multimetallic high relaxivity contrast agents for magnetic resonance imaging

PhenHDO3A is a ditopic ligand featuring a tetraazacyclododecane unit substituted by three acetate arms and one 6-hydroxy-5,6-dihydro-1,10- phenanthroline group (PhenHDO3A = rel-10-[(5R,6R)-5,6-dihydro-6-hydroxy-1,10- phenantholin-5-yl)-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid). This ligand was specially designed so as to obtain highly stable heteropolymetallic assemblies. PhenHDO3A has been prepared starting from phenanthroline epoxide and either a triprotected tetraazacyclododecane or tert-butyl triester of N,N′,N″-tetraazacyclododecane-triacetic acid. The latter yields PhenHDO3A in a single step. PhenHDO3A forms kinetically stable lanthanide complexes (acid-catalyzed kinetic constant kH = (1.2 ± 0.2) × 10-3 s-1 M-1) whose solution structure has been deduced from a quantitative analysis of the paramagnetic shifts and the longitudinal relaxation times of the proton nuclei of YbPhenHDO3A. The alcohol group of the dihydro-phenanthroline unit remains coordinated to the encapsulated metal ion despite the steric crowding brought about by this group. Furthermore, the complexes are monohydrated, as shown by luminescence lifetime measurements on EuPhenHDO3A solutions. Relaxivity titrations at 20 MHz clearly indicate that the phenanthroline unit of GdPhenHDO3A is available for the spontaneous formation of highly stable tris complexes with the Fe2+ and Ni 2+ ions. The water-exchange times and the rotational correlation times of GdPhenHDO3A and Fe(GdPhenHDO3A)32+ have been deduced from variable temperature 17O NMR studies and from nuclear relaxation dispersion curves. Despite rather slow water-exchange rates (τm0 = 1.0-1.2 × 10-6 s), relaxivity gains of 90% have been observed upon the formation of the heterometallic tris complexes. The latter rotate about four times more slowly (τ r0 = 398 ps) than the monomeric unit (τ r0 = 105 ps) and their relaxivity is, accordingly, twice as high. The relaxivity of the tris complexes between 10 and 50 MHz is comparable to relaxivities reported for Gd3+-containing dendrimers of much higher molecular weights. The high relaxivity of the tris-PhenHDO3A lanthanide complexes is attributed to their internal rigidity.

Gadolinium complexes of macrocyclic diethylenetriamine-: N -oxide pentaacetic acid-bisamide as highly stable MRI contrast agents with high relaxivity

Gadolinium(iii) complexes are generally considered efficient magnetic resonance imaging (MRI) contrast agents (CAs) and widely used in clinical applications. High relaxivity and stability are two essential criteria for a Gd(iii)-complex to be used as a MRI-CA. One crucial strategy to achieve high relaxivity for small molecular Gd(iii)-based MRI contrast agents is to increase the hydration number q. Meanwhile, metal complexes with macrocyclic ligands have been proved to inherit high thermodynamic stability and kinetic inertness. Herein, a series of macrocyclic ligands based on diethylenetriamine-N-oxide pentaacetic acid-bisamide were synthesized. Among them, cyclo-DTPA-NO-C6O2 (3d) was the strongest ligand for Gd(iii) as confirmed by experimental results. The hydration number of the Gd-cyclo-DTPA-NO-C6O2 (4d) complex was characterized by luminescence measurements to be 3 and the coordination structure was confirmed with computational simulations. Consequently, the relaxivity of this complex (14.3 mM-1 s-1, 1.5 T, 25 °C) is about triple that of commercial MRI CAs. The conditional stability constant of the Gd(iii) complex, pGd, calculated from spectrophotometric titration studies, was comparable to that of one of the most stable commercial MRI-CAs, Gd-DTPA (Magnevist). Meanwhile, the kinetic inertness of the complex was even higher than that of Gd-DTPA thanks to its macrocyclic coordination structure.

Order—Disorder transformation and its effect on the properties of (Lanthanide)2Zr1.5Hf0.5O7 functional nanoceramics

Order disorder transformations and its effect on the structural, optical and ionic transport properties of the cubic pyrochlore – defect fluorite structures are the prime focus of this study. Nanoceramics of Ln2Zr1.5Hf0.5O7 (Ln = Pr, Nd, Sm, Gd, Dy and Er) are prepared through the modified combustion technique. X – ray diffraction analysis and electron microscopic studies show the cubic nano crystallite nature of the materials. Vibrational studies reveal the pyrochlore–fluorite phase transformation in the series. Highly dense bulk ceramics are prepared from the nano particles at relatively low temperatures. The gradual replacement of Ln3+ ions in Ln2Zr1.5Hf0.5O7 changes the pyrochlores (Ln = Pr-Sm) to defect fluorite (Ln = Er) through the weakly ordered defect fluorites (Ln = Gd and Dy). Impedance spectroscopic analysis carried on the bulk ceramics shows the influence of phase transformation on the oxide ion conduction of bulk materials. The peak oxide ion conduction is observed for the Ln = Dy ceramic, which is at the pyrochlore fluorite phase boundary.

Synthesis, potentiometric, kinetic, and NMR studies of 1,4,7,10- tetraazacyclododecane-1,7-bis(acetic acid)-4,10-bis(methylenephosphonic acid) (DO2A2P) and its complexes with Ca(II), Cu(II), Zn(II) and lanthanide(III) ions

A cyclen-based ligand containing trans-acetate and trans- methylenephosphonate pendant groups, H6DO2A2P, was synthesized and its protonation constants (12.6, 11.43, 5.95, 6.15, 2.88, and 2.77) were determined by pH-potentiometry and 1H NMR spectroscopy. The first two protonations were shown to occur at the two macrocyclic ring N-CH 2-PO32- nitrogens while the third and fourth protonations occur at the two phosphonate groups. In parallel with protonation of the two -PO32- groups, the protons from the NH +-CH2-PO32- are transferred to the N-CH2-COO- nitrogens. The stability constants of the Ca2+, Cu2+, and Zn2+ (ML, MHL, MH2L, and M2L) complexes were determined by direct pH-potentiometry. Lanthanide(III) ions (Ln3+) form similar species, but the formation of complexes is slow; so, out-of-cell pH-potentiometry (La 3+, Eu3+, Gd3+, Y3+) and competitive spectrophotometry with Cu(II) ion (Lu3+) were used to determine the stability constants. By comparing the log KML values with those of the corresponding DOTA (H4DOTA = 1,4,7,10-tetraazacyclododecane-1,4, 7,10-tetraacetic acid) and DOTP (H8DOTP = 1,4,7,10- tetraazacyclododecane-1,4,7,10-tetramethylenephosphonic acid) complexes, the order DOTA 2+ complexes, for which the order is reversed. The relaxivity of Gd(DO2A2P) decreases between pH 2 and 7 but remains constant in the pH range of 7 1 = 3.6 mM-1 s-1). The linewiths of the 17O NMR signals of water in the absence and presence of Gd(DO2A2P) (at pH = 3.45 and 8.5) between 274 and 350 K are practically the same, characteristic of a q = 0 complex. Detailed kinetic studies of the Ce3+ and Gd3+ complexes with DO2A2P showed that complex formation is slow and involves a high stability diprotonated intermediate Ln(H2DO2A2P)*. Rearrangement of the diprotonated intermediate into the final complex is an OH- assisted process but, unlike formation of Ln(DOTA) complexes, rearrangement of Ln(H2DO2A2P)* also takes place spontaneously likely as a result of transfer of one of the protons from a ring nitrogen to a phosphonate group. The order of the OH- assisted formation rates of complexes is DOTA > DO2A2P > DOTP while the order of the proton assisted dissociation rates of the Gd3+ complexes is reversed, DOTP > DO2A2P > DOTA. 1H and 13C NMR spectra of Eu(DO2A2P) and Lu(DO2A2P) were assigned using two-dimensional correlation spectroscopy (2D COSY), heteronuclear multiple quantum coherence (HMQC), heteronuclear chemical shift correlation (HETCOR), and exchange spectroscopy (EXSY) NMR methods. Two sets of 1H NMR signals were observed for Eu(DO2A2P) characteristic of the presence of two coordination isomers in solution, a twisted square antiprism (TSAP) and a square antiprism (SAP), in the ratio of 93% and 7%, respectively. Line shape analysis of the 1H NMR spectra of Lu(DO2A2P) gave lower activation parameters compared to La(DOTP) for interconversion between coordination isomers. This indicates that the Ln(DO2A2P) complexes are less rigid probably due to the different size and spatial requirements of the carboxylate and phosphonate groups.

Effect of the 18-crown-6 and benzo-18-crown-6 on the solvent extraction and separation of lanthanide(III) ions with 8-hydroxyquinoline

The synergistic solvent extraction of 13 lanthanides with mixtures of 8-hydroxyquinoline (HQ) and the crown ethers (S) 18-crown-6 (18C6) or benzo-18-crown-6 (B18C6) in 1,2-dichloroethane has been studied. The composition of the extracted species has been

Kinetics of formation and dissociation of lanthanide(III) complexes with the 13-membered macrocyclic ligand TRITA

The tetraazamacrocyclic ligand TRITA4- is intermediate in size between the widely studied and medically used 12-membered DOTA4- and the 14-membered TETA4-. The kinetic inertness of GdTRITA- was characterized by the rates of exchange reactions with Zn2+ and Eu3+. In the Zn2+ exchange, a second order [H+] dependence was found for the pseudo-first-order rate constant (k0 = (4.2 ± 0.5) × 10-7 s-1; k′ = (3.5 ± 0.3) × 10-1 M-1S-1, k″ = (1.4 ±0.4) × 103 M-2s-1)- In the Eu3+ exchange, at pH 2+ species. At physiological pH, the kinetic inertness of GdTRITA- is considerably lower than that of GdDOTA- (t1/2 = 444 h (25°C) vs. 3.8 × 105 h (37°C), respectively). However, GdTRITA - is still kinetically more inert than GdDTPA2-, the most commonly used MRI contrast agent (t1/2 = 127 h). The formation reactions of LnTRITA- complexes (Ln = Ce, Gd and Yb) proceed via the rapid formation of a diprotonated intermediate and its subsequent deprotonation and rearrangement in a slow, OH- catalyzed process. The stability of the LnH2TRITA* intermediates (log KLnH2L* = 3.1-3.9) is lower than that of the DOTA-analogues. The rate constants of the OH- catalyzed step increase with decreasing lanthanide ion size, and are about twice as high as for DOTA-complexes. The Royal Society of Chemistry 2005.

Acid Solvolysis Kinetics of Lanthanide Porphyrins

The kinetics of the acid solvolysis reactions of twelve water-soluble lanthanide tetrakis(N-methyl-4-pyridyl)porphyrins (Ln-P) follow rate = k1+>2/ (k-1/k2) + +>> at 25 deg C, I = 0.8M (LiNO3/HNO3) indicating that two protons are required for solvolysis, and since log (k1k2/k-1) = 45.0R0 - 39.4 (R0 is the ionic radius in Angstroem), a 0.1 Angstroem change in radius has a 32000 fold rate effect.