Dissociation kinetics study of copper(II) complexes of DO3A,
DOTA and its monosubstituted derivatives

J 2013

Dissociation kinetics study of copper(II) complexes of DO3A, DOTA and its monosubstituted derivatives

VORÁČOVÁ, Ivona, Jakub VANĚK, Josef PASULKA, Zora STŘELCOVÁ, Přemysl LUBAL et. al.

Základní údaje

Originální název

Dissociation kinetics study of copper(II) complexes of DO3A, DOTA and its monosubstituted derivatives

Autoři

VORÁČOVÁ, Ivona (203 Česká republika), Jakub VANĚK (203 Česká republika, domácí), Josef PASULKA (203 Česká republika, domácí), Zora STŘELCOVÁ (203 Česká republika, domácí), Přemysl LUBAL (203 Česká republika, garant, domácí) a Petr HERMANN (203 Česká republika)

Vydání

Polyhedron, OXFORD, Elsevier Science Ltd. 2013, 0277-5387

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10402 Inorganic and nuclear chemistry

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 2.047

Kód RIV

RIV/00216224:14740/13:00066398

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1016/j.poly.2013.05.042

UT WoS

000322938100014

Klíčová slova anglicky

Macrocyclic ligands; Cyclen derivatives; Phosphonate complexes; Phosphinate complexes; Pyridine-N-oxide complexes; Copper complexes; Dissociation kinetics; Rate constants; Radiopharmaceuticals

Štítky

ok, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 11. 4. 2014 00:45, Olga Křížová

Anotace

V originále

The kinetic inertness of copper(II) complexes with cyclen-based ligands having three (H(3)do3a) or four (H(4)dota) acetic acid arms and those with three acetic acid and one phosphonic (H(5)do3ap), phosphinic (H(5)do(3)ap(PrA) , H(4)do3ap(ABn)) acid or methylpyridine-N-oxide (H(3)do3a-pyNox) pendant arms has been studied. The proton-assisted decomplexation reaction was studied under a wide range of conditions to fully assess the parameters influencing the reaction (temperature range 25-60 degrees C, proton concentration range 0.05-5 M and presence of perchlorate or nitrate anions). The empirical rate law k(d,obs) = k(0) + k(H) x [H+], involving solvolytic and proton-assisted dissociation pathways, shows that the complexes can be divided into two groups according to their kinetic behavior. Complexes of ligands having only carboxylate pendant arms (H(3)do(3)a, H(4)dota) show higher kinetic inertness than those of ligands with mixed pendant arms (H(5)do(3)ap, H(5)do(3)ap(PrA), H(4)do3ap(ABn), H(3)do3a-pyNox). Linear Free Energy Relationship (LFER) analysis of the activation parameters (Delta H#, Delta S#) proves that the reaction mechanism is generally the same for all copper(II) complexes and is independent of the inert electrolyte. Rate constants representing both solvolytic and acid-assisted pathways roughly correlate with the basicity of the ring nitrogen atoms. The nitrate anion from the supporting electrolyte was shown to accelerate (by about 3-5 times) the decomplexation reaction when compared to the reaction in perchlorate-containing media; the nitrate anion seems to interact with the reaction intermediates, changing the activation parameters of both reaction pathways. This effect is somewhat suppressed in the complex of the ligand with a hydrophobic p-aminobenzyl substituent on the phosphorus atom, H(5)do3ap(ABn). In perchlorate media, complexes of the monophosphorus acid H(4)dota analogs are less kinetically inert.

Návaznosti

ED1.1.00/02.0068, projekt VaV

Název: CEITEC - central european institute of technology

GA13-08336S, projekt VaV

Název: Hybridní materiály založené na makrocyklických ligandech pro využití v medicíně

Investor: Grantová agentura ČR, Hybridní materiály založené na makrocyklických ligandech pro využití v medicíně

ME09065, projekt VaV

Název: Výzkum nových detekčních systémů na bázi senzorových polí pro použití ve speciační analýze

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Výzkum nových detekčních systémů na bázi senzorových polí pro použití ve speciační analýze, Program výzkumu a vývoje KONTAKT (ME)

Citovat

VORÁČOVÁ, Ivona, Jakub VANĚK, Josef PASULKA, Zora STŘELCOVÁ, Přemysl LUBAL a Petr HERMANN. Dissociation kinetics study of copper(II) complexes of DO3A, DOTA and its monosubstituted derivatives. Polyhedron. OXFORD: Elsevier Science Ltd., 2013, roč. 61, Sep, s. 99-104. ISSN 0277-5387. Dostupné z: https://dx.doi.org/10.1016/j.poly.2013.05.042.

@article{1124390,
   author = {Voráčová, Ivona and Vaněk, Jakub and Pasulka, Josef and Střelcová, Zora and Lubal, Přemysl and Hermann, Petr},
   article_location = {OXFORD},
   article_number = {Sep},
   doi = {http://dx.doi.org/10.1016/j.poly.2013.05.042},
   keywords = {Macrocyclic ligands; Cyclen derivatives; Phosphonate complexes; Phosphinate complexes; Pyridine-N-oxide complexes; Copper complexes; Dissociation kinetics; Rate constants; Radiopharmaceuticals},
   language = {eng},
   issn = {0277-5387},
   journal = {Polyhedron},
   title = {Dissociation kinetics study of copper(II) complexes of DO3A, DOTA and its monosubstituted derivatives},
   url = {http://www.sciencedirect.com/science/article/pii/S0277538713004270#},
   volume = {61},
   year = {2013}
}

TY  - JOUR
ID  - 1124390
AU  - Voráčová, Ivona - Vaněk, Jakub - Pasulka, Josef - Střelcová, Zora - Lubal, Přemysl - Hermann, Petr
PY  - 2013
TI  - Dissociation kinetics study of copper(II) complexes of DO3A, DOTA and its monosubstituted derivatives
JF  - Polyhedron
VL  - 61
IS  - Sep
SP  - 99-104
EP  - 99-104
PB  - Elsevier Science Ltd.
SN  - 02775387
KW  - Macrocyclic ligands
KW  - Cyclen derivatives
KW  - Phosphonate complexes
KW  - Phosphinate complexes
KW  - Pyridine-N-oxide complexes
KW  - Copper complexes
KW  - Dissociation kinetics
KW  - Rate constants
KW  - Radiopharmaceuticals
UR  - http://www.sciencedirect.com/science/article/pii/S0277538713004270#
L2  - http://www.sciencedirect.com/science/article/pii/S0277538713004270#
N2  - The kinetic inertness of copper(II) complexes with cyclen-based ligands having three (H(3)do3a) or four (H(4)dota) acetic acid arms and those with three acetic acid and one phosphonic (H(5)do3ap), phosphinic (H(5)do(3)ap(PrA) , H(4)do3ap(ABn)) acid or methylpyridine-N-oxide (H(3)do3a-pyNox) pendant arms has been studied. The proton-assisted decomplexation reaction was studied under a wide range of conditions to fully assess the parameters influencing the reaction (temperature range 25-60 degrees C, proton concentration range 0.05-5 M and presence of perchlorate or nitrate anions). The empirical rate law k(d,obs) = k(0) + k(H) x [H+], involving solvolytic and proton-assisted dissociation pathways, shows that the complexes can be divided into two groups according to their kinetic behavior. Complexes of ligands having only carboxylate pendant arms (H(3)do(3)a, H(4)dota) show higher kinetic inertness than those of ligands with mixed pendant arms (H(5)do(3)ap, H(5)do(3)ap(PrA), H(4)do3ap(ABn), H(3)do3a-pyNox). Linear Free Energy Relationship (LFER) analysis of the activation parameters (Delta H#, Delta S#) proves that the reaction mechanism is generally the same for all copper(II) complexes and is independent of the inert electrolyte. Rate constants representing both solvolytic and acid-assisted pathways roughly correlate with the basicity of the ring nitrogen atoms. The nitrate anion from the supporting electrolyte was shown to accelerate (by about 3-5 times) the decomplexation reaction when compared to the reaction in perchlorate-containing media; the nitrate anion seems to interact with the reaction intermediates, changing the activation parameters of both reaction pathways. This effect is somewhat suppressed in the complex of the ligand with a hydrophobic p-aminobenzyl substituent on the phosphorus atom, H(5)do3ap(ABn). In perchlorate media, complexes of the monophosphorus acid H(4)dota analogs are less kinetically inert.
ER  -

VORÁČOVÁ, Ivona, Jakub VANĚK, Josef PASULKA, Zora STŘELCOVÁ, Přemysl LUBAL a Petr HERMANN. Dissociation kinetics study of copper(II) complexes of DO3A, DOTA and its monosubstituted derivatives. \textit{Polyhedron}. OXFORD: Elsevier Science Ltd., 2013, roč.~61, Sep, s.~99-104. ISSN~0277-5387. Dostupné z: https://dx.doi.org/10.1016/j.poly.2013.05.042.

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