824984-75-0Relevant articles and documents
Dimer formation of GdDO3A-arylsulfonamide complexes causes loss of pH-dependency of relaxivity
Wacker, Anja,Carniato, Fabio,Platas-Iglesias, Carlos,Esteban-Gomez, David,Wester, Hans-Jürgen,Tei, Lorenzo,Notni, Johannes
, p. 16828 - 16836 (2017)
Gadolinium(iii) complexes with pH-dependent relaxivities have been proposed as responsive magnetic resonance imaging (MRI) contrast agents (CA) for mapping of pH value in living subjects. The latter is clinically relevant because hypoxia-induced reduction of interstitial pH (acidosis) is a hallmark of tumor progression and resistance against chemotherapy. In order to obtain versatile building blocks for integration of a pH-responsive MRI-CA functionality into larger molecular assemblies, such as bioconjugates, micelles or nanoparticles, we equipped the structural motif GdDO3A-ethylene(arylsulfonic acid) with additional carboxylic acid moieties in the aromatic para-position. Two novel compounds were characterized concerning their pH-dependent relaxivity as well as by 17O NMR and 1H NMRD, augmented by determination of luminescence lifetimes of the respective Eu(iii) complexes and structural modelling by density functional theory (TPSSh/LCRECP/6-31G(d)). Unexpected involvement of the peripheral carboxylates into metal ion complexation effected self-assembly of the lanthanide(iii) complexes, resulting in dimeric species comprising two lanthanide ions, two symmetrically bridging ligands, and one coordinated water molecule per Gd(iii) (q = 1). These structures are stable even at low concentrations and in presence of competing anions like phosphate. The pH-sensitive sulfonamide moieties are not involved into Gd(iii) coordination, resulting in virtually constant relaxivities of r1 = 6.7 mM-1 s-1 (298 K, 20 MHz) over the biologically relevant pH range (4 to 9). Since further functionalisation on the peripheral carboxylates would effectively inhibit dimer formation, the compounds are nonetheless suited for the initially envisaged field of application.
Preparation method of compound
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Page/Page column 9-15, (2019/12/25)
A preparation method of a compound represented by the formula (IV) includes the steps: carrying out addition reaction of a compound represented by the formula (III) with fluorescein isothiocyanate, and further carrying out hydrolysis reaction with trifluoroacetic acid to remove tert-butyl ester to obtain a compound represented by the formula (IV). The reactant obtained by the method only need to be purified by column chromatography to obtain the compound represented by the formula (IV) and having the purity of 95% or more. The preparation method of the compound represented by the formula (IV)has low cost and is suitable for large-scale production. In addition, the invention also discloses a preparation method of the compound represented by the formula (V), wherein the preparation method of the compound represented by the formula (V) includes the preparation method for a compound represented by the formula (IV).
Synthesis of a new family of protected 1,4,7,10-tetraazacyclododecane-1,4, 7-triacetic acid derivatives with thioctic acid pending arms
De La Reberdiere, Arnaud,Lachaud, Fabien,Chuburu, Francoise,Cadiou, Cyril,Lemercier, Gilles
, p. 6115 - 6118,4 (2020/08/20)
The synthesis and characterization of a new family of ester protected N-substituted [1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (H3DO3A) derivatives containing a pendant thioctic acid (α lipoic acid, LA) are reported. These compounds (DO3AtBu-NLA, DO3AtBu-NMeNLA, and DO3AtBu-NEtNLA) are suitable for the functionalization of gold surfaces with rare-earth complexes.