Transition metal complexes of the (2,2,2-trifluoroethyl)phosphinate NOTA analogue as potential contrast agents for 19F magnetic resonance imaging

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F24%3A10481279" target="_blank" >RIV/00216208:11310/24:10481279 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=idJrzIXZuI" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=idJrzIXZuI</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4dt00507d" target="_blank" >10.1039/d4dt00507d</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Transition metal complexes of the (2,2,2-trifluoroethyl)phosphinate NOTA analogue as potential contrast agents for 19F magnetic resonance imaging

Popis výsledku v původním jazyce

A new hexadentate 1,4,7-triazacyclononane-based ligand bearing three coordinating methylene-(2,2,2-trifluoroethyl)phosphinate pendant arms was synthesized and its coordination behaviour towards selected divalent (Mg(2+), Ca(2+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+)) and trivalent (Cr(3+), Fe(3+), Co(3+)) transition metal ions was studied. The ligand forms stable complexes with late divalent transition metal ions (from Co(2+) to Zn(2+)) and the complexes of these metal ions are formed above pH ~3. A number of complexes with divalent metal ions were structurally characterized by means of single-crystal X-ray diffraction. The complex of the larger Mn(2+) ion adopts a twisted trigonally antiprismatic geometry with a larger coordination cavity and smaller torsion of the pendant arms, whereas the smaller ions Ni(2+), Cu(2+) and Zn(2+) form octahedral species with a smaller cavity and larger pendant arm torsion. In the case of the Co(2+) complexes, both coordination arrangements were observed. The complexes with paramagnetic metal ions were studied from the point of view of potential utilization in F-19 magnetic resonance imaging. A significant shortening of the (19)F NMR longitudinal relaxation times was observed: a sub-millisecond range for complexes of Cr(3+), Mn(2+) and Fe(3+) with symmetric electronic states (t(2g)(3) and HS-d(5)), the millisecond range for the Ni(2+) and Cu(2+) complexes and tens of milliseconds for the Co(2+) complex. Such short relaxation times are consistent with a short distance between the paramagnetic metal ion and the fluorine atoms (approx.5.5-6.5 Å). Among the redox-active complexes (Mn(3+)/Mn(2+), Fe(3+)/Fe(2+), Co(3+)/Co(2+), Cu(2+)/Cu(+)), the cobalt complexes show sufficient stability and a paramagnetic-diamagnetic changeover with the redox potential lying in a physiologically relevant range. Thus, the Co(3+)/Co(2+) complex pair can be potentially used as a smart redox-responsive contrast agent for (19)F MRI.

Název v anglickém jazyce

Transition metal complexes of the (2,2,2-trifluoroethyl)phosphinate NOTA analogue as potential contrast agents for 19F magnetic resonance imaging

Popis výsledku anglicky

A new hexadentate 1,4,7-triazacyclononane-based ligand bearing three coordinating methylene-(2,2,2-trifluoroethyl)phosphinate pendant arms was synthesized and its coordination behaviour towards selected divalent (Mg(2+), Ca(2+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+)) and trivalent (Cr(3+), Fe(3+), Co(3+)) transition metal ions was studied. The ligand forms stable complexes with late divalent transition metal ions (from Co(2+) to Zn(2+)) and the complexes of these metal ions are formed above pH ~3. A number of complexes with divalent metal ions were structurally characterized by means of single-crystal X-ray diffraction. The complex of the larger Mn(2+) ion adopts a twisted trigonally antiprismatic geometry with a larger coordination cavity and smaller torsion of the pendant arms, whereas the smaller ions Ni(2+), Cu(2+) and Zn(2+) form octahedral species with a smaller cavity and larger pendant arm torsion. In the case of the Co(2+) complexes, both coordination arrangements were observed. The complexes with paramagnetic metal ions were studied from the point of view of potential utilization in F-19 magnetic resonance imaging. A significant shortening of the (19)F NMR longitudinal relaxation times was observed: a sub-millisecond range for complexes of Cr(3+), Mn(2+) and Fe(3+) with symmetric electronic states (t(2g)(3) and HS-d(5)), the millisecond range for the Ni(2+) and Cu(2+) complexes and tens of milliseconds for the Co(2+) complex. Such short relaxation times are consistent with a short distance between the paramagnetic metal ion and the fluorine atoms (approx.5.5-6.5 Å). Among the redox-active complexes (Mn(3+)/Mn(2+), Fe(3+)/Fe(2+), Co(3+)/Co(2+), Cu(2+)/Cu(+)), the cobalt complexes show sufficient stability and a paramagnetic-diamagnetic changeover with the redox potential lying in a physiologically relevant range. Thus, the Co(3+)/Co(2+) complex pair can be potentially used as a smart redox-responsive contrast agent for (19)F MRI.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA22-34083S" target="_blank" >GA22-34083S: Komplexy fluorovaných ligandů s paramagnetickými ionty kovů pro 19F MRI a bimodální 1H/19F kontrastní látky</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

53

Číslo periodika v rámci svazku

22

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

19

Strana od-do

9267-9285

Kód UT WoS článku

001199517400001

EID výsledku v databázi Scopus

2-s2.0-85190165907