Abstract
The nuclear magnetic resonance (NMR)-relaxation characteristics of protons in pure aqueous and buffer solutions of highly hydroxylated endofullerenols with paramagnetic gadolinium ions at ambient temperature have been studied. These systems were thoroughly characterized by SANS and examined by NMR at various resonance frequencies: f = 2 kHz–500 MHz. In all the cases, we have discovered much higher longitudinal and transversal relaxation rates as compared to the reference salt solutions with Gd+3 ions in the same range of concentrations (0.1–10.0 mM/l). We suppose that this effect is due to the fact that the objects studied reveal well-manifested abilities to the self-assembly in acidic conditions. As a result, the transversal relaxation rate (1/T2) increases greatly, and also the longitudinal relaxation rate (1/T1) demonstrates a broad maximum at resonant frequencies f ~ 20–100 MHz that are determined by the time of fullerenol diffusive rotations. The relaxation rates, which increase linearly with fullerenol content (0.1–10.0 mM/l), testify the stable assembly. The studied features of fullerenol assembly and its strong influence on the proton relaxation make it possible to suppose good prospects of these metal–carbon structures for biomedical applications, in particular, as contrast agents in MRI.
Similar content being viewed by others
References
Y. Nomura, S. Sakai, M. Capone, R. Arita, Sci. Adv. 1, 1500568 (2015)
M.A. Shevtsov, B.P. Nikolaev, Y.Y. Marchenko, L.Y. Yakovleva, A.V. Dobrodumov, G. Török, V.T. Lebedev, Appl. Magn. Reson. 45, 303 (2014)
H. Kato, Y. Kanazawa, M. Okumura, A. Taninaka, T. Yokawa, H. Shinohara, J. Am. Chem. Soc. 125, 4391 (2003)
T. Zou, M. Zhen, J. Li, D. Chen, Y. Feng, R. Li, C. Wang, RSC Adv. 5, 96253 (2015)
G. Xing, J. Zhang, Y. Zhao, J. Tang, B. Zhang, X. Gao, K. Ibrahim, J. Phys. Chem. B 108, 11473 (2004)
S. Laus, B. Sitharaman, É. Tóth, R.D. Bolskar, L. Helm, L.J. Wilson, A.E. Merbach, J. Phys. Chem. C 111, 5633 (2007)
Patent RU2558121C1, V.P. Sedov, A.A. Szhogina, Method of producing highly water-soluble fullerenols
S.G. Semenov, M.E. Bedrina, A.V. Titov, J. Struct. Chem. 59, 506 (2018)
V.T. Lebedev, V.V. Runov, A.A. Szhogina, M.V. Suyasova, Nanosyst. Phys. Chem. Math. 7(1), 1–7 (2016)
M. Mikawa, H. Kato, M. Okumura, M. Narazaki, Y. Kanazawa, N. Miwa, H. Shinohara, J. Bioconj. Chem. 12, 510 (2001)
A.M. Panich, M. Salti, S.D. Goren, E.B. Yudina, A.E. Aleksenskii, A.Y. Vul’, A.I. Shames, J. Phys. Chem. 123, 2627 (2019). https://doi.org/10.1021/acs.jpcc.8b11655
Y.A. Mondjinou, B.P. Loren, C.J. Collins, S.H. Hyun, A. Demoret, J. Skulsky, D.H. Thompson, J. Bioconj. Chem. 29, 3550 (2018). https://doi.org/10.1021/acs.bioconjchem.8b00525
E.A. Suturina, K. Mason, C.F. Geraldes, N.F. Chilton, D. Parker, I. Kuprov, J. Phys. Chem. Chem. Phys. 9, 99 (2018). https://doi.org/10.1039/c8cp01332b
Patent RU2659972C1, V.P. Sedov, A.A. Szhogina, M.V. Suyasova, V.A. Shilin, V.T. Lebedev. Method for producing water-soluble hydroxylated derivatives of endometallofullerenes of lanthanides
A. Arrais, R. Gobetto, R. Rossetti, E. Diana, New Diamond Front. Carbon Technol. 16, 79 (2006)
T.H. Goswami, R. Singh, S. Alam, G.N. Mathur, Thermochim. Acta 419, 97 (2004)
M. Newville, J. Synchrotron Radiat. 8, 322 (2001)
K. Hedberg, L. Hedberg, D.S. Bethune, C.A. Brown, H.C. Dorn, R.D. Johnson, M. De Vries, Science 254, 410 (1991)
L. Soderholm, P. Wurz, K.R. Lykke, D.H. Parker, F.W. Lytle, J. Phys. Chem. 96, 7153 (1992)
K. Kikuchi, Y. Nakao, Y. Achiba, M. Nomura, Electrochem. Soc. 1, 1300 (1994)
H. Giefers, F. Nessel, S.I. Györy, M. Strecker, G. Wortmann, Y.S. Grushko, V.S. Kozlov, Carbon 37, 721 (1999)
M. Nomura, Y. Nakao, K. Kikuchi, Y. Achiba, Phys. B 208&209, 539 (1995)
D.I. Svergun, J. Appl. Crystallogr. 25, 495 (1992)
D. Franke, M.V. Petoukhov, P.V. Konarev, A. Panjkovich, A. Tuukkanen, H.D.T. Mertens, D.I. Svergun, J. Appl. Crystallogr. 50(4), 1212 (2017)
M.V. Suyasova, Y.V. Kul’velis, V.T. Lebedev, V.P. Sedov, Russ. J. Appl. Chem. 88, 1839 (2015)
D. Kruk, J. Kowalewski, D.S. Tipikin, J.H. Freed, M. Mościcki, A. Mielczarek, M. Port, J. Chem. Phys. 134(2), 024508 (2011)
V.T. Lebedev, A.A. Szhogina, M.V. Suyasova, J. Phys, Conf. Ser. 1, 012005 (2018)
B. Sitharaman, R.D. Bolskar, I. Rusakova, L.J. Wilson, Nano Lett. 4, 2373 (2004)
É. Tóth, R.D. Bolskar, A. Borel, G. González, L. Helm, A.E. Merbach, L.J. Wilson, J. Am. Chem. Soc. 2005(127), 799 (2005)
A.S. Merbach, The chemistry of contrast agents in medical magnetic resonance imaging. Wiley (2013)
J. Zhang, P.P. Fatouros, C. Shu, J. Reid, L.S. Owens, T. Cai, H.C. Dorn, Bioconj. Chem. 21, 610 (2010)
P. Fatouros, M.D. Shultz, Nanomedicine 8, 1853 (2013)
K.B. Ghiassi, M.M. Olmstead, A.L. Balch, Dalton Trans. 43, 7346 (2014)
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Suyasova, M.V., Lebedev, V.T., Sedov, V.P. et al. Proton Spin Relaxation in Aqueous Solutions of Self-assembling Gadolinium Endofullerenols. Appl Magn Reson 50, 1163–1175 (2019). https://doi.org/10.1007/s00723-019-01139-3
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00723-019-01139-3