Design of High-Relaxivity Polyelectrolyte Nanocapsules Based on Citrate Complexes of Gadolinium(III) of Unusual Composition
Abstract
:1. Introduction
2. Results and Discussion
2.1. Formation of Gadolinium(III) Citrate Complexes in Water
2.2. Effect of PEI on the Complexation of Gadolinium(III) Ions with Citric Acid
2.3. Effect of Molecular Mass and Nature of Cationic Polymer on the Complexation of Gadolinium(III) Ions with Citric Acid
2.4. Morphology of Gadolinium(III) Complexes with Citric Acid in Polyethyleneimine Solution
3. Conclusions
4. Materials and Methods
4.1. Materials
4.2. NMR Relaxation
4.3. Modeling of Equilibria
4.4. Size and Morphology
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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No. | Equilibrium | lgK | pKa | lgβ | R2, mM−1s−1 |
---|---|---|---|---|---|
1 | H4L ⇆ H3L− + H+ | −3.09 ± 0.01 | 3.09 | - | |
2 | H4L ⇆ H2L2− + H+ | −7.78 ± 0.01 | 4.69 | - | |
3 | H4L ⇆ HL3− + H+ | −13.95 ± 0.02 | 6.17 | - | |
4 | Gd3+ + H4L ⇆ GdH2L+ + 2H+ | −1.90 ± 0.03 | 5.88 | (15.5) | |
5 | Gd3+ + H4L ⇆ GdHL0 + 3H+ | −5.51 ± 0.02 | 8.44 | (15) | |
6 | Gd3+ + H4L ⇆ GdL− + 4H+ | −12.31 ± 0.04 | 15.64 | 7.2 ± 0.2 | |
7 | 3Gd3+ + 3H4L ⇆ Gd3L3H-25− + 14H+ | −50.14 ± 0.16 | 19.71 | 3.8 ± 0.4 | |
8 | Gd3+ + 2H4L ⇆ Gd(HL)23− + 6H+ | −15.15 ± 0.08 | 12.75 | 12.2 ± 0.2 | |
9 | Gd3+ + 2H4L ⇆ GdL25− + 8H+ | −32.25 ± 0.14 | 23.65 | 4 ± 0.1 |
Reaction of Formation | lgKapp (R2, mM−1s−1) | ||
---|---|---|---|
5 mM PEI | 10 mM PEI | 25 mM PEI | |
Gd3+ + 3H4L ⇆ Gd(H2L)33− + 6H+ | −5.71 ± 0.07 (38 ± 0.2) | −5.48 ± 0.15 (44.6 ± 0.7) | −5.68 ± 0.14 (44.8 ± 0.9) |
Gd3+ + 3H4L ⇆ Gd(H2L)2HL4− + 7H+ | −10.02 ± 0.22 (40.3 ± 0.3) | −10.01 ± 0.12 (48.5 ± 0.6) | −9.47 ± 0.10 (49.6 ± 0.6) |
Reaction of Formation | lgKapp (R2, mM−1s−1) | ||
---|---|---|---|
PEI3 | PEI2 | PEI1 | |
Gd3+ + 3H4L ⇆ Gd(H2L)33− + 6H+ | −5.94 ± 0.21 (22.5 ± 0.2) | −5.97 ± 0.26 (23.0 ± 0.3) | −5.71 ± 0.09 (44.8 ± 0.4) |
Gd3+ + 3H4L ⇆ Gd(H2L)2HL4− + 7H+ | −10.98 ± 0.15 (22.6 ± 0.3) | −11.17 ± 0.12 (22.5 ± 0.3) | −11.01 ± 0.10 (49.8 ± 0.5) |
Composition | ZP (mV) | |
---|---|---|
pH 4 | pH 6 | |
5 mM PEI0 | +17 ± 1 | +14 ± 1 |
1.5 mM Gd(III) + 5 mM PEI0 | +19 ± 1 | +13 ± 1 |
1.5 mM Cit + 5 mM PEI0 | +17 ± 1 | +4 ± 0.4 |
0.5 mM Gd(III) + 1.5 mM Cit + 5 mM PEI0 | +29 ± 0.3 | +18 ± 1 |
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Burilova, E.; Solodov, A.; Shayimova, J.; Zhuravleva, J.; Shurtakova, D.; Evtjugin, V.; Zhiltsova, E.; Zakharova, L.; Kashapov, R.; Amirov, R. Design of High-Relaxivity Polyelectrolyte Nanocapsules Based on Citrate Complexes of Gadolinium(III) of Unusual Composition. Int. J. Mol. Sci. 2021, 22, 11590. https://doi.org/10.3390/ijms222111590
Burilova E, Solodov A, Shayimova J, Zhuravleva J, Shurtakova D, Evtjugin V, Zhiltsova E, Zakharova L, Kashapov R, Amirov R. Design of High-Relaxivity Polyelectrolyte Nanocapsules Based on Citrate Complexes of Gadolinium(III) of Unusual Composition. International Journal of Molecular Sciences. 2021; 22(21):11590. https://doi.org/10.3390/ijms222111590
Chicago/Turabian StyleBurilova, Evgenia, Alexander Solodov, Julia Shayimova, Julia Zhuravleva, Darya Shurtakova, Vladimir Evtjugin, Elena Zhiltsova, Lucia Zakharova, Ruslan Kashapov, and Rustem Amirov. 2021. "Design of High-Relaxivity Polyelectrolyte Nanocapsules Based on Citrate Complexes of Gadolinium(III) of Unusual Composition" International Journal of Molecular Sciences 22, no. 21: 11590. https://doi.org/10.3390/ijms222111590