Lanthanide complexes with polyaminopolycarboxylates as prospective NMR/MRI diagnostic probes: peculiarities of molecular structure, dynamics and paramagnetic properties

Zapolotsky, Eugeny N.; Qu, Yanyang; Babailov, Sergey P.

doi:10.1007/s10847-021-01112-3

Cited by 24 publications

(20 citation statements)

References 197 publications

(365 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This maximum value for I appeared to be ∂ δ /∂ T = 0.16 ppm/K. It should be noted that other complex compounds, which were investigated earlier by 1 H NMR in both organic and aqueous media, are characterized by the chemical shifts temperature sensitivity in the range from 0 to 1.5 ppm/K [ 22 , 29 , 30 ]. The obtained results indicate that the coordination compound I may be considered as amoderately sensitive 1 H NMR d - element paramagnetic probe.…”

Section: Resultsmentioning

confidence: 92%

“…Regardless of the coordination equilibrium, the conformational pinched cone ↔ pinched cone dynamics manifests itself in a typical way, and some difference between the corresponding magnetic chemical shifts on temperature in the working range is adequately described by the Curie–Weiss approximation [ 28 , 29 , 30 ]: δ = a + b / T where a and b are the parameters of linear regression. We analyzed the linear dependence of the observed chemical shifts on parameter 1 / T (see Figure 6 and Figure S3 ) and found it to be well-described by the Curie–Weiss law.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Paramagnetic Properties and Moderately RapidConformational Dynamics in the Cobalt(II) Calix[4]arene Complex by NMR

2022

View full text Add to dashboard Cite

1H NMR measurements are reported for the CD2Cl2/CDCl3 solutions of the Co(II) calix[4]arenetetraphosphineoxide complex (I). Temperature dependences of the 1H NMR spectra of I have been analyzed using the line shape analysis, taking into account the temperature variation of paramagnetic chemical shifts, within the frame of the dynamic NMR method. Conformational dynamics of the 2:1 Co(II) calix[4]arene complexes was conditioned by the pinched cone ↔pinched cone interconversion of I (with activation Gibbs energy ΔG≠(298K) = 40 ± 3 kJ/mol. Due to substantial temperature dependence of paramagnetic shifts, complex I can be used as model compound for designing an NMR thermosensor reagent for local temperature monitoring.

show abstract

Section: Resultsmentioning

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Paramagnetic Properties and Moderately RapidConformational Dynamics in the Cobalt(II) Calix[4]arene Complex by NMR

2022

View full text Add to dashboard Cite

show abstract

“…The exchange rate of this coordinated water is an important factor for the efficiency of an MRI contrast agent. ,− It has been reported that the water exchange rate of the TSAP conformer is about two orders of magnitude faster than that of SAP, making it the preferred conformation for MRI contrast agents. − In contrast, for the application as a luminescent probe, the absence of this water molecule is crucial as it can decrease the excitation lifetime of Ln(III) . For the application of the complex in paramagnetic NMR spectroscopy on proteins, which is the focus of this study, the water dynamics is not relevant because it is fast on the applicable NMR timescale, determined by the lanthanoid-induced pseudocontact shifts …”

Section: Introductionmentioning

confidence: 97%

Rigidified and Hydrophilic DOTA-like Lanthanoid Ligands: Design, Synthesis, and Dynamic Properties

et al. 2023

View full text Add to dashboard Cite

Limiting the dynamics of paramagnetic tags is crucial for the accuracy of the structural information derived from paramagnetic nuclear magnetic resonance (NMR) experiments. A hydrophilic rigid 2,2′,2″,2‴-(1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetraacetic acid (DOTA)-like lanthanoid complex was designed and synthesized following a strategy that allows the incorporation of two sets of two adjacent substituents. This resulted in a C 2 symmetric hydrophilic and rigid macrocyclic ring, featuring four chiral hydroxyl-methylene substituents. NMR spectroscopy was used to investigate the conformational dynamics of the novel macrocycle upon complexation with europium and compared to DOTA and its derivatives. The twisted square antiprismatic and square antiprismatic conformers coexist, but the former is favored, which is different from DOTA. Twodimensional 1 H exchange spectroscopy shows that ring flipping of the cyclen-ring is suppressed due to the presence of the four chiral equatorial hydroxyl-methylene substituents at proximate positions. The reorientation of the pendant arms causes conformational exchange between two conformers. The reorientation of the coordination arms is slower when the ring flipping is suppressed. This indicates that these complexes are suitable scaffolds to develop rigid probes for paramagnetic NMR of proteins. Due to their hydrophilic nature, it is anticipated that they are less likely to cause protein precipitation than their more hydrophobic counterparts.

show abstract

“…Compounds of rare-earth elements are effectively used in contrasting reagents for MRI imaging of organ and tissue pathologies [ 1 , 2 , 3 ]. To date, among the designated in-organic ions, the most significant for practical commercial use are lanthanide complexes, in particular, gadolinium (T1 contrast agents) and dysprosium (T2 contrast agents) [ 4 , 5 , 6 ]. For the effective use of lanthanide complex compounds for these purposes, it is necessary to ensure their bioavailability and target properties, as well as guarantee their safety and low toxicity to humans [ 7 ].…”

Section: Introductionmentioning

confidence: 99%

Hyperbranched Polyester Polyfumaratomaleate Doped with Gd(III) and Dy(III) Ions: Synthesis, Structure and Properties

et al. 2022

View full text Add to dashboard Cite

For the first time, metal–polymer complexes have been synthesized using hyperbranched polyester polyfumaratomaleate as a matrix, the structure of which has been established by 1H NMR, IR, electron spectroscopy, and elemental analysis methods. The formation of complexes with Gd(III) and Dy(III) ions involving fumarate and maleate groups of the polyester was proved by IR and electron spectroscopy methods. It was established that the structure of the coordination units has the form of a square antiprism. The compositions and conditional logarithms of the stability constants of the complexes were determined. It was established that complexation with lanthanide ions promotes emission enhancement in the ligand.

show abstract

Lanthanide complexes with polyaminopolycarboxylates as prospective NMR/MRI diagnostic probes: peculiarities of molecular structure, dynamics and paramagnetic properties

Cited by 24 publications

References 197 publications

Paramagnetic Properties and Moderately RapidConformational Dynamics in the Cobalt(II) Calix[4]arene Complex by NMR

Paramagnetic Properties and Moderately RapidConformational Dynamics in the Cobalt(II) Calix[4]arene Complex by NMR

Rigidified and Hydrophilic DOTA-like Lanthanoid Ligands: Design, Synthesis, and Dynamic Properties

Hyperbranched Polyester Polyfumaratomaleate Doped with Gd(III) and Dy(III) Ions: Synthesis, Structure and Properties

Contact Info

Product

Resources

About