Al(iii)-NTA-fluoride: A simple model system for Al-F binding with interesting thermodynamics

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00533646" target="_blank" >RIV/61388963:_____/20:00533646 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/20:10416616

Výsledek na webu

<a href="https://doi.org/10.1039/D0DT02644A" target="_blank" >https://doi.org/10.1039/D0DT02644A</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d0dt02644a" target="_blank" >10.1039/d0dt02644a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Al(iii)-NTA-fluoride: A simple model system for Al-F binding with interesting thermodynamics

Popis výsledku v původním jazyce

Al(III) complexes are extensively studied as [18F]fluoride carriers in positron emission tomography. However, our limited knowledge on their thermodynamic and kinetic properties has hindered efforts to easily prepare radiochemically pure compounds while simultaneously reducing the overall labeling time. Thus, to improve our understanding of fluoride binding to coordinatively unsaturated Al(III) complexes, we investigated the ternary system Al(III)–H3NTA–F− (H3NTA = nitrilo-triacetic acid) by NMR, potentiometry and X-ray diffraction. Our results show that the [Al(NTA)] complex binds two water molecules, which are replaced by fluorides. Individual species and isomers show separate 19F NMR signals and different stability constants. The two available positions on the [Al(NTA)] complex feature significantly different properties in terms of basicity of the coordinated water molecules and preferential binding of fluoride anions. Fluorides are effectively bound in weakly acidic or neutral solutions, whereas hydroxido species are preferentially formed in alkaline solutions. Our experimental observations were rationalized by theoretical calculations: predictions of the energy ordering of complexes and isomers, interpretation of 19F NMR chemical shifts, and natural bonding orbital analysis. Radiolabeling of [Al(NTA)] with [18F]fluoride gave low yields that confirmed a high affinity of the complex for hydroxide anions.

Název v anglickém jazyce

Al(iii)-NTA-fluoride: A simple model system for Al-F binding with interesting thermodynamics

Popis výsledku anglicky

Al(III) complexes are extensively studied as [18F]fluoride carriers in positron emission tomography. However, our limited knowledge on their thermodynamic and kinetic properties has hindered efforts to easily prepare radiochemically pure compounds while simultaneously reducing the overall labeling time. Thus, to improve our understanding of fluoride binding to coordinatively unsaturated Al(III) complexes, we investigated the ternary system Al(III)–H3NTA–F− (H3NTA = nitrilo-triacetic acid) by NMR, potentiometry and X-ray diffraction. Our results show that the [Al(NTA)] complex binds two water molecules, which are replaced by fluorides. Individual species and isomers show separate 19F NMR signals and different stability constants. The two available positions on the [Al(NTA)] complex feature significantly different properties in terms of basicity of the coordinated water molecules and preferential binding of fluoride anions. Fluorides are effectively bound in weakly acidic or neutral solutions, whereas hydroxido species are preferentially formed in alkaline solutions. Our experimental observations were rationalized by theoretical calculations: predictions of the energy ordering of complexes and isomers, interpretation of 19F NMR chemical shifts, and natural bonding orbital analysis. Radiolabeling of [Al(NTA)] with [18F]fluoride gave low yields that confirmed a high affinity of the complex for hydroxide anions.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

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

—

Svazek periodika

49

Číslo periodika v rámci svazku

39

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

11

Strana od-do

13726-13736

Kód UT WoS článku

000576736500023

EID výsledku v databázi Scopus

2-s2.0-85092944671