Spectroscopic Characterization of the 3+and 2+Oxidation States of Europium in a Macrocyclic Tetraglycinate Complex

被引：50

作者：

Ekanger, Levi A. ^{[1
]}

Mills, Devin R. ^{[1
]}

Ali, Meser M. ^{[2
]}

Polin, Lisa A. ^{[3
,4
]}

Shen, Yimin ^{[5
]}

Haacke, E. Mark ^{[4
,5
]}

Allen, Matthew J. ^{[1
,4
]}

机构：

[1] Wayne State Univ, Dept Chem, 5101 Cass Ave, Detroit, MI 48202 USA

[2] Henry Ford Hosp, Dept Neurol, 1 Ford Pl, Detroit, MI 48202 USA

[3] Wayne State Univ, Sch Med, Dept Oncol, 110 East Warren Ave, Detroit, MI 48201 USA

[4] Barbara Ann Karmanos Canc Inst, 4100 John R St, Detroit, MI 48201 USA

[5] Wayne State Univ, Sch Med, Dept Radiol, 3990 John R St, Detroit, MI 48201 USA

来源：

INORGANIC CHEMISTRY | 2016年 / 55卷 / 20期

关键词：

MRI CONTRAST AGENT; EUROPIUM(III)-BASED PARACEST AGENT; DOTA-TETRAAMIDE COMPLEXES; IN-VIVO; ELECTRONIC RELAXATION; WATER EXCHANGE; LANTHANIDE(III) COMPLEXES; DIVALENT EUROPIUM; LUMINESCENCE; CRYPTATE;

D O I：

10.1021/acs.inorgchem.6b00629

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The 3+ and 2+ oxidation states of europium have drastically different magnetic and spectroscopic properties. Electrochemical measurements are often used to probe Eu-III/II oxidation state changes, but a full suite of spectroscopic characterization is necessary to demonstrate conversion between these two oxidation states in solution. Here, we report the facile conversion of an europium(III) tetraglycinate complex into its Eu-II analogue. We present electrochemical, luminescence, electron paramagnetic resonance, UV-visible, and NMR spectroscopic data demonstrating complete reversibility from the reduction and oxidation of the 3+ and 2+ oxidation states, respectively. The Eu-II-Containing analogue has kinetic stability within the range of clinically approved Gd-III-containing complexes using an acid-catalyzed dissociation experiment. Additionally, we demonstrate that the 3+ and 2+ oxidation states provide redox-responsive behavior through chemical-exchange saturation transfer or proton relaxation, respectively. These results will be applicable to a wide range of redox-responsive contrast agents and Eu-containing complexes.

引用

页码：9981 / 9988

页数：8

共 59 条

[1]

Aime S, 2000, ANGEW CHEM INT EDIT, V39, P747, DOI 10.1002/(SICI)1521-3773(20000218)39:4<747::AID-ANIE747>3.0.CO

[2]

2-2

[3]

Aime S, 1998, ANGEW CHEM INT EDIT, V37, P2673, DOI 10.1002/(SICI)1521-3773(19981016)37:19<2673::AID-ANIE2673>3.0.CO

[4]

2-#

[5] Paramagnetic lanthanide(III) complexes as pH-sensitive chemical exchange saturation transfer (CEST) contrast agents for MRI applications [J].

Aime, S ;

Barge, A ;

Delli Castelli, D ;

Fedeli, F ;

Mortillaro, A ;

Nielsen, FU ;

Terreno, E .

MAGNETIC RESONANCE IN MEDICINE, 2002, 47 (04) :639-648

[6] Aqueous Lanthanide Chemistry in Asymmetric Catalysis and Magnetic Resonance Imaging [J].

Allen, Matthew J. .

SYNLETT, 2016, 27 (09) :1310-1317

[7] Complexation properties of N,N′,N",N′"-[1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayltetrakis(1-oxoethane-2,1-diyl)]tetrakis[glycine] (H4dotagl).: Equilibrium, kinetic, and relaxation behavior of the lanthanide(III) complexes [J].

Baranyai, Z ;

Brücher, E ;

Iványi, T ;

Király, R ;

Lázár, I ;

Zékány, L .

HELVETICA CHIMICA ACTA, 2005, 88 (03) :604-617

[8]

Bard A.J., 2001, Electrochemical Methods: Fundamentals and Applications, V2nd, P3

[9] Homoleptic Cerium(III) and Cerium(IV) Nitroxide Complexes: Significant Stabilization of the 4+Oxidation State [J].

Bogart, Justin A. ;

Lewis, Andrew J. ;

Medling, Scott A. ;

Piro, Nicholas A. ;

Carroll, Patrick J. ;

Booth, Corwin H. ;

Schelter, Eric J. .

INORGANIC CHEMISTRY, 2013, 52 (19) :11600-11607

[10] EuII-cryptate with optimal water exchange and electronic relaxation:: a synthon for potential pO2 responsive macromolecular MRI contrast agents [J].

Burai, L ;

Scopelliti, R ;

Tóth, É .

CHEMICAL COMMUNICATIONS, 2002, (20) :2366-2367

← 1 2 3 4 5 6 →