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001-es BibID:BIBFORM120539
035-os BibID:(WoS)000362460800037 (Scopus)84942934285
Első szerző:Forgács Attila (vegyész)
Cím:Mono-, Bi-, and TrinUclear Bis-Hydrated Mn2+ Complexes as Potential MRI Contrast Agents / Attila Forgacs, Martín Regueiro-Figueroa, JoséLuis Barriada, David Esteban-Gomez, Andres de Blas, Teresa Rodríguez-Blas, Mauro Botta, Carlos Platas-Iglesias
Dátum:2015
ISSN:0020-1669 1520-510X
Megjegyzések:We report a series of ligands containing pentadentate 6,6'-((methylazanediyObis(methylene))dipicolinic acid binding units that form mono- (H(2)dpama), di- (mX(H(2)dpama)(2)), and trinudear (mX(H(2)dpama)(3)) complexes with Mn2+ containing two coordinated water molecules per metal ion, which results in pentagonal bipyramidal coordination around the metal ions. In contrast, the hexadentate ligand 6,6'-((ethane-1,2-diylbis(azanediyl))bis(methylene))dipicolinic acid (H2bcpe) forms a complex with distorted octahedral coordination around Mn2+ that lacks coordinated water molecules. The protonation constants of the ligands and the stability constants of the Mn2+, Cu2+, and Zn2+ complexes were determined using potentiometric and spectrophotometric titrations in 0.15 M NaCl. The "pentadentate dpama(2-) ligand and the di- and trinudeating mX(dpama)(2)(4-) and mX(dpama)(3)(6-) ligands provide metal complexes with stabilities that are very similar to that of the complex with the hexadentate ligand bcpe2-, with log beta(101) values in the range 10.1-11.6. Cyclic voltammetry experiments on aqueous solutions of the [Mn(bcpe)] complex reveal a quasireversible system with a half-wave potential of +595 mV versus Ag/AgCl. However, [Mn(dpama)] did not suffer oxidation in the range 0.0-1.0 V, revealing a higher resistance toward oxidation. A detailed H-1 NMRD and O-17 NMR study provided insight into the parameters that govern the relaxivity for these systems. The exchange rate of the coordinated water molecules in [Mn(dpama)] is relatively fast, k(ex)(298) = (3.06 +/- 0.16) X 10(8) s(-1). The trinudear [mX(Mn(dpama)(H2O)(2))(3)] complex was found to bind human serum albumin with an association constant of 1286 +/- 55 M-1 and a relaxivity of the adduct of 45.2 +/- 0.6 mM(-1) at 310 K and 20 MHz.
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Megjelenés:Inorganic Chemistry. - 54 : 19 (2015), p. 9576-9587. -
További szerzők:Regueiro-Figueroa, Martín Barriada, José Luis Esteban-Gómez, David de Blas, Andrés Rodríguez-Blas, Teresa Botta, Mauro Platas-Iglesias, Carlos
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2.

001-es BibID:BIBFORM120538
035-os BibID:(Scopus)85021996032 (WoS)000404860300021
Első szerző:Forgács Attila (vegyész)
Cím:Optimising the relaxivities of Mn2+ complexes by targeting human serum albumin (HSA) / Attila Forgács, Lorenzo Tei, Zsolt Baranyai, David Esteban-Gómez, Carlos Platas-Iglesias, Mauro Botta
Dátum:2017
ISSN:1477-9226
Megjegyzések:We report two novel macrocyclic ligands based on the 1,4-DO2AM platform (1,4-DO2AM = 2,2'-(1,4,7,10-tetraazacyclododecane- 1,4-diyl) diacetamide) and containing two benzyl groups attached either to the nitrogen atoms of the macrocyclic unit (1,4-BzDO2AM) or to the amide pendant arms (1,4-DO2AMBz). The protonation constants of the ligands and the stability constants of their Mn2+ complexes were determined using pH potentiometry. The introduction of benzyl groups results in a slight decrease of the stability constants of the Mn2+ complexes and a slight increase of their acid-catalysed dissociation reactions. A detailed relaxometric characterisation of the complexes using nuclear magnetic dispersion relaxation (NMRD) and O-17 NMR studies indicated that the increase in molecular weight associated with the presence of benzyl groups results in a remarkable increase of proton relaxivities r(1p), which take values of 3.8, 3.5 and 2.5 mM(-1) s(-1) for [Mn(1,4-BzDO2AM)](2+), [Mn(1,4-DO2AMBz)](2+) and [Mn(1,4-DO2AM)] (2+) (at 25 degrees C and 20 MHz). The [Mn(1,4-BzDO2AM)](2+) and [Mn(1,4-DO2AMBz)](2+) complexes form relatively strong adducts with Human Serum Albumin (HSA) with association constants of (3.9 +/- 0.6) x 103 and (2.0 +/- 0.3) x 103 M-1, respectively. The interaction with the protein slows down the rotational tumbling of the complex in solution, which results in adducts endowed with remarkably high proton relaxivities (r(1p) (b) = 18.5 +/- 0.7 and 27.4 +/- 1.4 mM(-1) s(-1) for [Mn(1,4-BzDO2AM)](2+) and [Mn(1,4-DO2AMBz)](2+), respectively).
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Megjelenés:Dalton Transactions. - 46 : 26 (2017), p. 8494-8504. -
További szerzők:Tei, Lorenzo Baranyai Zsolt Esteban-Gómez, David Platas-Iglesias, Carlos Botta, Mauro
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3.

001-es BibID:BIBFORM120536
035-os BibID:(WoS)000395442700024 (Scopus)85011024075
Első szerző:Forgács Attila (vegyész)
Cím:Developing the family of picolinate ligands for Mn2+ complexation / Attila Forgács, Rosa Pujales-Paradela, Martín Regueiro-Figueroa, Laura Valencia, David Esteban-Gómez, Mauro Botta, Carlos Platas-Iglesias
Dátum:2017
ISSN:1477-9226
Megjegyzések:We have reported here a series of ligands containing pentadentate 6,6'-(azanediylbis(methylene)) dipicolinic acid units that differ in the substituent present at the amine nitrogen atom (acetate: H(3)DPAAA; phenyl: H(2)DPAPhA; dodecyl: H(2)DPAC12A; 4-hexylphenyl: H(2)DPAC6PhA). The protonation constants of the hexadentate DPAAA(3-) and pentadentate DPAPhA(2-) ligands and the stability constants of their Mn2+ complexes were determined using pH-potentiometry (25 degrees C, 0.15 M NaCl). The mono-hydrated [Mn(DPAAA)](-) complex (log K-MnL = 13.19(5)) was found to be considerably more stable than the bis-hydrated [Mn(DPAPhA)] analogue (log K-MnL = 9.55(1)). A detailed H-1 and O-17 NMR relaxometric study was carried out to determine the parameters that govern the proton relaxivities of these complexes. The [Mn(DPAC12A)] complex, which contains a dodecyl lipophilic chain, forms micelles in solution characterized by a critical micellar concentration (cmc) of 96(9) mu M. The lipophilic [Mn(DPAC6PhA)] and [Mn(DPAC12A)] derivatives form rather strong adducts with Human Serum Albumin (HSA) with association constants of 7.1 +/- 0.1 x 10(3) and 1.3 +/- 0.4 x 10(5) M (1), respectively. The X-ray structure of the complex {K(H2O)(4)}{[Mn(DPAAA)(H2O)]}(2) shows that the Mn2+ ion in [Mn(DPAAA)](-) is coordinated to the six donor atoms of the ligand, a coordinated water molecule completing the pentagonal bipyramidal coordination environment.
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
magnetic resonance imaging
manganese complexes
picolinate ligands
relaxivity
DFTcalculations
Megjelenés:Dalton Transactions. - 46 : 5 (2017), p. 1546-1558. -
További szerzők:Pujales-Paradela, Rosa Regueiro-Figueroa, Martín Valencia, Laura Esteban-Gómez, David Botta, Mauro Platas-Iglesias, Carlos
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4.

001-es BibID:BIBFORM120545
035-os BibID:(WoS)000302861900019 (Scopus)84859904566
Első szerző:Forgács Attila (vegyész)
Cím:Influence of gem-Dimethyl Substitution on the Stability, Kinetics and Relaxometric Properties of PDTA Complexes / Attila Forgács, Giovanni B. Giovenzana, Mauro Botta, Erno Brücher, Imre Tóth, Zsolt Baranyai
Dátum:2012
ISSN:1434-1948
Megjegyzések:The protonation constants of DMPDTA (H4DMPDTA = 2,2-dimethylpropylenediamine-N,N,N',N'-tetraacetic acid) and the stability and protonation constants of its Ln3+ and some divalent metal complexes have been determined by pH potentiometry and spectrophotometry (Cu2+) and compared with the corresponding properties of the complexes formed with PDTA (H4PDTA = propylenediamine-N,N,N',N'-tetraacetic acid). The log?K2H value of DMPDTA is lower by 1.5 logK units than that of PDTA. The stability constants (log?KML) of the Ln3+ complexes formed with DMPDTA are lower by 1.01.5 logK units than those of PDTA. The kinetics of the transmetallation reactions of Gd(DMPDTA) and Gd(PDTA) with Cu2+ and Eu3+ have been studied by spectrophotometry. The reactions with Cu2+ and Eu3+ occur predominantly by spontaneous and proton-assisted dissociation of the Gd(DMPDTA) and Gd(PDTA) complexes. The rates of the metal-exchange reactions of Gd(DMPDTA) are significantly lower than those of Gd(PDTA). The presence of the two methyl groups on the ligand backbone increases the kinetic inertness of Gd(DMPDTA) due to the higher conformational rigidity of DMPDTA. Temperature-dependent 17O NMR spectra and 1/T1 1H nuclear magnetic relaxation dispersion profiles of the Gd3+ complexes were measured and analyzed to obtain the parameters that influence the water exchange rate and rotational dynamics.
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Lanthanides
Thermodynamics
Kinetics
Relaxation
Megjelenés:European Journal Of Inorganic Chemistry. - 2012 : 12 (2012), p. 2074-2086. -
További szerzők:Giovenzana, Giovanni Battista Botta, Mauro Brücher Ernő (1935-) (vegyész) Tóth Imre (1950-) (vegyész) Baranyai Zsolt (1977-) (vegyész)
Pályázati támogatás:K 84291
OTKA
TÁMOP4.2.1./B-09/1/KONV-2010-0007
TÁMOP
TÁMOP4.2.2./B-10/1-2010-0024
TÁMOP
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5.

001-es BibID:BIBFORM081346
Első szerző:Forgács Attila (vegyész)
Cím:A Bisamide Derivative of [Mn(1,4-DO2A)] - Solution Thermodynamic, Kinetic, and NMR Relaxometric Studies / Attila Forgács, Lorenzo Tei, Zsolt Baranyai, Imre Tóth, László Zékány, Mauro Botta Mauro
Dátum:2016
ISSN:1434-1948
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Macrocyclic ligands
Manganese
Magnetic resonance imaging
Imaging agents
Kinetics
Megjelenés:European Journal Of Inorganic Chemistry. - 2016 : 8 (2016), p. 1165-1174. -
További szerzők:Tei, Lorenzo Baranyai Zsolt (1977-) (vegyész) Tóth Imre (1950-) (vegyész) Zékány László (1948-) (vegyész) Botta, Mauro
Pályázati támogatás:OTKA K-84291
OTKA
OTKA K-109029
OTKA
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6.

001-es BibID:BIBFORM069371
Első szerző:Tei, Lorenzo
Cím:Thermodynamic stability, kinetic inertness and relaxometric properties of monoamide derivatives of lanthanide(III) DOTA complexes / Lorenzo Tei, Zsolt Baranyai, Luca Gaino, Attila Forgács, Adrienn Vágner, Mauro Botta
Dátum:2015
ISSN:1477-9226
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
termodinamika
relaxivitás
kinetika
Megjelenés:Dalton Transactions 44 : 12 (2015), p. 5467-5478. -
További szerzők:Baranyai Zsolt (1977-) (vegyész) Gaino, Luca Forgács Attila (1988-) (vegyész) Vágner Adrienn (1990-) (vegyész, kémikus) Botta, Mauro
Pályázati támogatás:TÁMOP-4.2.4. A/2-11-1-2012-0001
TÁMOP
OTKA-109029
OTKA
HU11MO2-TET_10-1-2011-0202
Egyéb
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7.

001-es BibID:BIBFORM120543
035-os BibID:(WoS)000328531000043 (Scopus)84890969291
Első szerző:Verma, Kirti Dhingra
Cím:New Calcium-Selective Smart Contrast Agents for Magnetic Resonance Imaging / Kirti Dhingra Verma, Attila Forgács, Hyounsoo Uh, Michael Beyerlein, Martin E. Maier, Stéphane Petoud, Mauro Botta, Nikos K. Logothetis
Dátum:2013
ISSN:0947-6539 1521-3765
Megjegyzések:Calcium plays a vital role in the human body and especially in the central nervous system. Precise maintenance of Ca2+ levels is very crucial for normal cell physiology and health. The deregulation of calcium homeostasis can lead to neuronal cell death and brain damage. To study this functional role played by Ca2+ in the brain noninvasively by using magnetic resonance imaging, we have synthesized a new set of Ca2+-sensitive smart contrast agents (CAs). The agents were found to be highly selective to Ca2+ in the presence of other competitive anions and cations in buffer and in physiological fluids. The structure of CAs comprises Gd3+-DO3A (DO3A=1,4,7-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecane) coupled to a Ca2+ chelator o-amino phenol-N,N,O-triacetate (APTRA). The agents are designed to sense Ca2+ present in extracellular fluid of the brain where its concentration is relatively high, that is, 1.2-0.8mM. The determined dissociation constant of the CAs to Ca2+ falls in the range required to sense and report changes in extracellular Ca2+ levels followed by an increase in neural activity. In buffer, with the addition of Ca2+ the increase in relaxivity ranged from 100-157%, the highest ever known for any T-1-based Ca2+-sensitive smart CA. The CAs were analyzed extensively by the measurement of luminescence lifetime measurement on Tb3+ analogues, nuclear magnetic relaxation dispersion (NMRD), and O-17 NMR transverse relaxation and shift experiments. The results obtained confirmed that the large relaxivity enhancement observed upon Ca2+ addition is due to the increase of the hydration state of the complexes together with the slowing down of the molecular rotation and the retention of a significant contribution of the water molecules of the second sphere of hydration.
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
calcium
gadolinium
magnetic resonance imaging
relaxivity
sensors
Megjelenés:Chemistry-A European Journal. - 19 : 52 (2013), p. 18011-18026. -
További szerzők:Forgács Attila (1988-) (vegyész) Uh, Hyounsoo Beyerlein, Michael Maier, Martin E. Petoud, Stéphane Botta, Mauro Logothetis, Nikos K.
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