title: Novel 15-crown-5 ether or beta-diketone incorporated gadolinium complexes for the detection of potassium ions or magnesium and calcium ions.
abstract: Novel gadolinium complexes (KMR-series: KMR-K and KMR-Mg), which have a bis-15-crown-5 ether or a charged beta-diketone structure as a recognition site, have been designed, synthesized and applied for the detection of K(+) or of Mg(2+) and Ca(2+) using MRI or NMR techniques. The measurements are based on the modulation of the longitudinal relaxation time (T(1)) of water protons in proximity of the gadolinium complexes. Relaxivity measurements of KMR-K1 in aqueous solution showed that the initial longitudinal relaxivity value (r(1)) of 5.05 mM(-1) s(-1) is monotonously decreasing with increasing K(+) concentrations, reaching a final value of 4.78 mM(-1) s(-1). This decrease is attributed to a change in the second sphere of hydration of the gadolinium (Gd(3+)) complex (KMR-K), resulting in a K(+) concentration-dependent contrast in MR images. From stoichiometric analysis using mass spectrometry and UV/VIS spectrometry, a 1 : 1 complex formation between KMR-K1 and K(+) in a sandwich-type manner with a log K of 3.20 was confirmed. In the case of KMR-Mg, the initial r(1) value of 4.98 mM(-1) s(-1) is monotonously decreasing with increasing Mg(2+) or Ca(2+) concentrations, reaching a final value of 3.95 or 4.16 mM(-1) s(-1), respectively, resulting in Mg(2+) and Ca(2+) concentration-dependent contrast in MR images. The formation of a 1:1 complex with a log K of 2.33 for Mg(2+) and 1.91 for Ca(2+) was confirmed. KMR-K1 and KMR-Mg are the first ion-selective or ion-sensitive gadolinium complexes for K(+) or Mg(2+) and Ca(2+), respectively.
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan.
authors.forename: Hiroki
authors.initials: H
authors.lastname: Hifumi
authors.forename: Akihiro
authors.initials: A
authors.lastname: Tanimoto
authors.forename: Daniel
authors.initials: D
authors.lastname: Citterio
authors.forename: Hirokazu
authors.initials: H
authors.lastname: Komatsu
authors.forename: Koji
authors.initials: K
authors.lastname: Suzuki
mesh_terms: D002118:Calcium / Q000032:analysis; D003287:Contrast Media / Q000138:chemical synthesis* / Q000737:chemistry; D043844:Crown Ethers; D005682:Gadolinium; D007476:Ionophores / Q000138:chemical synthesis / Q000737:chemistry; D007477:Ions / Q000032:analysis*; D007659:Ketones / Q000032:analysis; D008274:Magnesium / Q000032:analysis; D008279:Magnetic Resonance Imaging / Q000379:methods*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D011188:Potassium / Q000032:analysis; D011522:Protons
chemical_list: D003287:Contrast Media; D043844:Crown Ethers; D007476:Ionophores; D007477:Ions; D007659:Ketones; D009942:Organometallic Compounds; D011522:Protons; C042148:15-crown-5; D005682:Gadolinium; D008274:Magnesium; D011188:Potassium; D002118:Calcium