Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/8104
Title: Spectroscopic Study of the Hydration Equilibria and Water Exchange Dynamics of Lanthanide(III) Complexes of 1,7-Bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (DO2A)
Authors: Yerly, Fabrice 
Dunand, Frank A. 
Tóth, Éva 
Figueirinha, Artur 
Kovács, Zoltán 
Sherry, A. Dean 
Geraldes, Carlos F. G. C. 
Merbach, André E. 
Issue Date: 2000
Citation: European Journal of Inorganic Chemistry. 2000:5 (2000) 1001-1006
Abstract: The hydration state of a series of [Ln(DO2A)(H2O)n]+ complexes in aqueous solution at pH = 6.4-7.0 was studied by measuring the lanthanide-induced 17O shifts (LIS) of water [Ln includes elements from Ce to Yb; DO2A = 1,7-bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane]. Their contact contribution, obtained from Reilley plots, indicated a decrease in the inner-sphere water coordination number of the [Ln(DO2A)(H2O)n]+ complexes from n = 3 (Ce-Eu), to n = 2 (Tb-Yb). A temperature-dependent UV/Vis absorption study of the 578-582 nm 7F0 rarr 5D0 transition band of [Eu(DO2A)(H2O)n]+ in aqueous solution showed that this complex is present in an equilibrium between eight- and nine-coordinate species with n = 2 and n = 3, respectively. The hydration equilibrium parameters (2 harr 3), K2-3298 = 4.0 ± 0.2, ΔH2-30 = -12.1 ± 1 kJ mol-1 and ΔS2-30 = -28.9 ± 3 J mol-1 K-1,correspond to an average hydration number of 2.65-2.85 in the temperature range 273-363 K. A variable temperature, multiple field 17O NMR study combined with direct EPR measurements of the transverse electronic relaxation rates has been used to obtain the parameters characterizing water exchange, rotation and electronic relaxation, all influencing the proton relaxivity of [Gd(DO2A)(H2O)2-3]+. The small increase in the water exchange rate of [Gd(DO2A)(H2O)2-3]+ (kex298 = (10 ± 5) × 106s-1) relative to that of[Gd(DOTA)(H2O)]- (4.8 × 106 s-1) is a consequence of an unfavorable interplay of charge and hydration equilibria. The value of τR298 = 40 ± 1 ps is short, and the electronic relaxation rate (1/T2e asymp 1.2 × 1010 s-1) is fast relative to [Gd(DOTA)(H2O)]- (1.3-2.4 × 109 s-1 for B = 0.34 T). These parameters negate to some extent the expected increase in proton relaxivity of the [Gd(DO2A)(H2O)2-3]+ complex.
URI: http://hdl.handle.net/10316/8104
DOI: 10.1002/(SICI)1099-0682(200005)2000:5<1001::AID-EJIC1001>3.0.CO;2-J
Rights: openAccess
Appears in Collections:FCTUC Ciências da Vida - Artigos em Revistas Internacionais

Files in This Item:
File Description SizeFormat
obra.pdf294.64 kBAdobe PDFView/Open
Show full item record

Page view(s)

161
checked on Jul 9, 2020

Download(s)

133
checked on Jul 9, 2020

Google ScholarTM

Check

Altmetric

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.