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001-es BibID:	BIBFORM006199
Első szerző:	Kálmán Ferenc K. (vegyész)
Cím:	Stability constants and dissociation rates of the EDTMP complexes of Samarium(III) and Yttrium(III) / Kalman, F. K., Kiraly, R., Brucher, E.
Dátum:	2008
Megjegyzések:	The stability constants of Sm(EDTMP) (log K-ML = 20.71) and Y(EDTMP) (log K-ML = 19.19) were determined by a competition reaction between the Ln(3+) ion (Ln(3+) = Sm3+ or Y3+) and Cu2+ for the EDTMP ligand by spectrophotometry at pH approximate to 10, in the presence of an excess amount of citrate (0.15 M NaCl, 25 degrees C). For determining the stability constants of Cu(EDTMP) (log K-ML = 19.36) and Ca(EDTMP) (log K-ML = 8.71) pH-potentiometry was used. In the pH range 4-9 the EDTMP complexes are present in the form of nonprotonated and mono-, di- and triprotonated species. The Ca2+ ion forms a dinuclear complex with Ln(EDTMP). In a simplified blood plasma model consisting of Sm3+, Ca2+ and Zn2+ metal ions, EDTMP, citrate, cysteine and histidine ligands, Sm3+ is practically present in the form of [Sm(HEDTMP)Ca](2-), whereas Zn2+ predominantly forms [Zn(HEDTMP)](5-) and [Zn(H2EDTMP)](4-) complexes. For studying the dissociation rates of the complexes, the kinetics of the metal exchange (transmetallation) reactions between the Ln(EDTMP) complexes and Cu2+-citrate were investigated in the pH range 7-9 by the stopped-flow method. The rates of the exchange reactions are independent of the Cu2+ concentration and increase with the H+ concentration. The rate constants, characterizing the proton-assisted dissociation of the Ln(EDTMP) complexes, are several orders of magnitude higher than those of the similar Ln(EDTA) complexes, because the protonation constants of Ln(EDTMP) are high and the protonated Ln(HEDTMP) and Ln(H2EDTMP) species are present in higher concentration. The half-times of dissociation of Sm(EDTMP) and Y(EDTMP) at pH = 7.4 and 25 degrees C are 4.9 and 7.5 s, respectively. These relatively short dissociation half-time values do not predict the deposition of Ln(3+) ions in bones in the form of intact Ln(EDTMP) complexes. It is more probable that sorption of the EDTMP ligand and Sm3+ or Y3+ ions occurs independently after the dissociation of complexes.
Tárgyszavak:	Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
Megjelenés:	European Journal Of Inorganic Chemistry. - 30 (2008), p. 4719-4727. -
További szerzők:	Király Róbert (1947-) (vegyész) Brücher Ernő (1935-) (vegyész)
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001-es BibID:	BIBFORM067450
Első szerző:	Kotek, Jan
Cím:	Study of thermodynamic and kinetic stability of transition metal and lanthanide complexes of DTPA analogues with a phosphorus acid pendant arm / Jan Kotek, Ferenc K. Kálmán, Petr Hermann, Ernő Brücher, Koen Binnemans, Ivan Lukes
Dátum:	2006
ISSN:	1434-1948
Megjegyzések:	The thermodynamic and kinetic stabilities of the complexes of phosphonate and phenylphosphinate analogues of H5dtpa with selected transition- and lanthanide-metal ions are presented. Both phosphorus-containing ligands form thermodynamically very stable complexes, with stability constants comparable with or even higher than those reported for the parent H5dtpa. However, the kinetic inertness of their gadolinium(III) complexes against acid- and metal-assisted decomplexations is surprisingly much lower. The half-life times of gadolinium(III) complexes of the new ligands in the presence of excess of concurrent metal ions [copper(II) or europium(III)] are about 2?3 orders of magnitude shorter compared to H5dtpa and its amide derivatives. The behaviour can probably be attributed to steric strain in the new complexes, to the high affinity of phosphonate ligand for proton, and/or to easy formation of binuclear complexes, which act as intermediates in the complex dissociation.
Tárgyszavak:	Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban Phosphonate complexes Phosphinate complexes MRI contrast agents Kinetics Thermodynamics
Megjelenés:	European Journal of Inorganic Chemistry 2006 : 10 (2006), p. 1976-1986. -
További szerzők:	Kálmán Ferenc K. (1978-) (vegyész) Hermann, Petr Brücher Ernő (1935-) (vegyész) Binnemans, Koen Lukeš, Ivan
Pályázati támogatás:	FP6-projects EMIL (LSHC-2004-503569) Egyéb DiMI (LSHB-CT-2005-512146) Egyéb COST D18 Egyéb
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001-es BibID:	BIBFORM038091
Első szerző:	Tircsó Gyula (vegyész, kémia tanár)
Cím:	Lanthanide Complexes Formed with the Tri- and Tetraacetate Derivatives of Bis(aminomethyl)phosphinic Acid : Equilibrium, Kinetic and NMR Spectroscopic Studies / Gyula Tircsó, Ferenc K. Kálmán, Róbert Pál, István Bányai, Tamás R. Varga, Róbert Király, István Lázár, Laurent Québatte, André E. Merbach, Éva Tóth, Ernő Brücher
Dátum:	2012
ISSN:	1434-1948
Megjegyzések:	The lanthanide(III) complexes formed with the tri- and tetraacetate derivatives of bis(aminomethyl)phosphinic acid, L1 and L2, respectively, have been studied by pH potentiometry, spectrophotometry and 1H and 17O NMR spectroscopy. L1 forms [Ln(L1)]?, [Ln(L1)2]4?, protonated [Ln(HL1)] and Ln(H2L1)]+, and [Ln(L1)(OH)]2? hydroxido complexes. Heptadentate L2 forms [Ln(L2)]2? and protonated [Ln(HL2)]? and [Ln(H2L2)] complexes in solution and it shows a strong propensity to form [Ln2(L2)]+ dinuclear complexes, which has not been observed previously. The stability constants (log?KLnL) of the complexes increase in the order [Ln(L1)]? < [Ln(L2)]2? following the order of increasing number of acetate pendants attached to the bis(aminomethyl)phosphinic acid (BAP) backbone. Within the LnIII series, the log?KLnL values increase from La3+ to Gd3+ and remain practically constant for the heavier lanthanides. Despite the lower basicity, the ligands that contain a phosphinate group generally form similar (L1) or more stable (L2) Ln3+ complexes than the structurally similar N-benzylethylenediamine-N,N·,N·-triacetic acid (L3) and propylenediamine-N,N,N·,N·-tetraacetic acid (L4), respectively. This indicates that the hard phosphinate group may be coordinated to the Ln3+ ions in the complexes, whereas the larger negative charge of the BAP derivatives may also have an extra stabilizing effect. The kinetic inertness of [Ln(L1)] and [Ln(L2)] is lower than that of similar [Ln(EDTA)]? (EDTA = ethylenediamine-N,N,N·,N·-tetraacetic acid), but the rate constants that characterize the dissociation of [Ln(L2)]2? are at least two orders of magnitude lower than those obtained for [Ln(L4)]?. Variable-temperature 17O transverse and longitudinal relaxation rates and NMR spectroscopic chemical shifts have been measured to assess the water exchange and rotational dynamics of [Gd(L2)]. The chemical shifts evidenced monohydration of the complex. The water exchange rate, kex298 = (2.7???0.4)???107 s?1 is about ten times higher than that of [Ln(DTPA)]2? (DTPA = diethylenetriamine-N,N,N·,Nı,Nı-pentaacetic acid). The rotational correlation time, ?RO298 = 270???30 ps, is long considering the small size of the chelate, which points to aggregation in aqueous solution, in accordance with the high value of the proton relaxivity measured.
Tárgyszavak:	Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban Lanthanides Imaging agents Kinetics Protonation constants Stability constants Water exchange rate Molekulatudomány
Megjelenés:	European Journal Of Inorganic Chemistry. - 12 (2012), p. 2062-2073. -
További szerzők:	Kálmán Ferenc K. (1978-) (vegyész) Pál Róbert Bányai István (1953-) (vegyész) Varga Tamás Róbert (1967-) (kémia tanár) Király Róbert (1947-) (vegyész) Lázár István (1959-) (vegyész) Québatte, Laurent Merbach, André E. Tóth Éva (1967-) (koordinációs kémia) Brücher Ernő (1935-) (vegyész)
Pályázati támogatás:	TÁMOP-4.2.1/B-09/1/KONV-2010-0007 TÁMOP Bimodális kontrasztanyagok tervezése, előállítása és komplexeik fizikai-kémiai tulajdonságaik jellemzése TÁMOP-4.2.2./B-10/1-2010-0024 TÁMOP K84291 OTKA PD83253 OTKA
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