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001-es BibID:	BIBFORM106980
Első szerző:	Garda Zoltán (vegyész)
Cím:	Complexation of Mn(II) by Rigid Pyclen Diacetates: Equilibrium, Kinetic, Relaxometric, Density Functional Theory, and Superoxide Dismutase Activity Studies / Zoltán Garda, Enikő Molnár, Nadège Hamon, José Luis Barriada, David Esteban-Gómez, Balázs Váradi, Viktória Nagy, Kristof Pota, Ferenc Krisztián Kálmán, Imre Tóth, Norbert Lihi, Carlos Platas-Iglesias, Éva Tóth, Raphaël Tripier, Gyula Tircsó
Dátum:	2020
ISSN:	0020-1669 1520-510X
Megjegyzések:	We report the Mn(II) complexes with two pyclenbased ligands (pyclen = 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca- 1(15),11,13-triene) functionalized with acetate pendant arms at either positions 3,6 (3,6-PC2A) or 3,9 (3,9-PC2A) of the macrocyclic fragment. The 3,6-PC2A ligand was synthesized in five steps from pyclen oxalate by protecting one of the secondary amine groups of pyclen using Alloc protecting chemistry. The complex with 3,9-PC2A is characterized by a higher thermodynamic stability [log KMnL = 17.09(2)] than the 3,6-PC2A analogue [log KMnL = 15.53(1); 0.15 M NaCl]. Both complexes contain a water molecule coordinated to the metal ion, which results in relatively high 1H relaxivities (r1p = 2.72 and 2.91 mM?1 s?1 for the complexes with 3,6-PC2A and 3,9-PC2A, respectively, at 25 ?C and 0.49 T). The coordinated water molecule displays fast exchange kinetics with the bulk in both cases; the rates (kex 298) are 140 ? 106 and 126 ? 106 s?1 for [Mn(3,6-PC2A)(H2O)] and [Mn(3,9- PC2A)(H2O)], respectively. The two complexes were found to be remarkably inert with respect to their dissociation, with half-lives of 63 and 21 h, respectively, at pH = 7.4 in the presence of excess Cu(II). The r1p values recorded in blood serum remain constant at least over a period of 120 h. Cyclic voltammetry experiments show irreversible oxidation features shifted to higher potentials with respect to [Mn(EDTA)(H2O)]2? (H4EDTA = ethylenediaminetetraacetic acid) and [Mn(PhDTA)(H2O)]2? (H4PhDTA = phenylenediamine-N,N,N·,N·-tetraacetic acid), indicating that the PC2A complexes reported here have a lower tendency to stabilize Mn(III). The superoxide dismutase activity of the Mn(II) complexes was tested using the xanthine/xanthine oxidase/p-nitro blue tetrazolium chloride assay at pH = 7.8. The Mn(II) complexes of 3,6-PC2A and 3,9-PC2A are capable of assisting decomposition of the superoxide anion radical. The kinetic rate constant of the complex of 3,9-PC2A is smaller by 1 order of magnitude than that of 3,6-PC2A.
Tárgyszavak:	Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban folyóiratcikk
Megjelenés:	Inorganic Chemistry. - 60 : 2 (2020), p. 1133-1148. -
További szerzők:	Molnár Enikő (1991-) (vegyész) Hamon, Nadège Barriada, José Luis Esteban-Gómez, David Váradi Balázs (1990-) (vegyész) Nagy Viktória Póta Kristóf Kálmán Ferenc K. (1978-) (vegyész) Tóth Imre (1950-) (vegyész) Lihi Norbert (1990-) (vegyész) Platas-Iglesias, Carlos Tóth Éva (1967-) (koordinációs kémia) Tripier, Raphaël Tircsó Gyula (1977-) (vegyész, kémia tanár)
Pályázati támogatás:	K-120224 OTKA 128201 OTKA 134694 OTKA PD-128326 OTKA 2019-2.1.11- 1179 TET-2019-00084 Egyéb
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001-es BibID:	BIBFORM076231
Első szerző:	Molnár Enikő (vegyész)
Cím:	Remarkable differences and similarities between the isomeric Mn(II)-cis- and trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetate complexes / Enikő Molnár, Balázs Váradi, Zoltán Garda, Richárd Botár, Ferenc K. Kálmán, Éva Tóth, Imre Tóth, Ernő Brücher, Gyula Tircsó
Dátum:	2018
ISSN:	0020-1693
Megjegyzések:	Equilibrium, kinetic (solvent exchange and dissociation of the complex) and relaxometric studies (1H and 17O NMR) have been performed with the [M(II)(c-cdta)]2 complexes (c-cdta = cis-1,2-diaminocyclohexane- N,N,N0 ,N0-tetraacetic acid, M(II) = Mn(II), Zn(II), Cu(II),Ca(II), Mg(II)) and the physico-chemical data are compared to the isomeric complexes with trans-1,2-cdta (t-cdta) with the aim of searching appropriate ligands for Mn(II) complexation for safe MRI contrast agents. The total basicity (R log Ki H) of the c-cdta ligand appears to be very similar to that of the trans-derivative under the conditions applied (I = 0.15 M NaCl and 25 C), but the first two protonation constants notably differ. log K1 H is 1.5 log units higher, while the log K2 H is 0.8 log units lower than those determined for the trans-derivative. Similar basicity of the ligands results in similar complex stability (log K[Mn(L)] values are 14.19(2) and 14.32), whereas the conditional stabilities near to physiological pH are different (pMn values are 7.82 and 8.68) for the [Mn (c-cdta)]2 and the [Mn(t-cdta)]2 derivatives, respectively. Dissociation kinetic studies revealed that the [Mn(c-cdta)]2 dissociates 250 times faster than the [Mn(t-cdta)]2 complex. The water exchange rate (kex 298) of [Mn(c-cdta)]2 is ca. 60% higher than that of [Mn(t-cdta)]2 . The differences can likely be attributed to the different distances between the individual donor atoms, and the arrangement of the donor atoms around the metal ions in the cis- and trans- isomers. Interestingly, the relaxivity values of the Mn (II) complexes are very close (r1p = 3.79 mM 1 s 1 and 3.62 mM 1 s 1; 20 MHz, 25 C for the cis- and trans-isomers, respectively). DFT calculations were used to gain insight into the different properties of the [Mn(c-cdta)]2 and the [Mn(t-cdta)]2 complexes. The results gained in our studies confirm that the trans-1,2-cyclohexanediamine ♭♭building block" displays better features for further ligand development.
Tárgyszavak:	Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
Megjelenés:	Inorganica Chimica Acta. - 472 : 1 (2018), p. 254-263. -
További szerzők:	Váradi Balázs (1990-) (vegyész) Garda Zoltán (1989-) (vegyész) Botár Richárd (1992-) (vegyész) Kálmán Ferenc K. (1978-) (vegyész) Tóth Éva Tóth Imre (1950-) (vegyész) Brücher Ernő (1935-) (vegyész) Tircsó Gyula (1977-) (vegyész, kémia tanár)
Pályázati támogatás:	OTKA K-120224 OTKA GINOP-2.3.2-15-2016-00008 GINOP
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