Aggregation of metallacarborane mixtures in aqueous solutions: Iron bis(1,2-dicarbollide) as paramagnetic probe in aggregates of diamagnetic cobalt bis(1,2-dicarbollide)

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F25%3A10500079" target="_blank" >RIV/00216208:11310/25:10500079 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=HqnVuB01Ra" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=HqnVuB01Ra</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.molliq.2025.127232" target="_blank" >10.1016/j.molliq.2025.127232</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Aggregation of metallacarborane mixtures in aqueous solutions: Iron bis(1,2-dicarbollide) as paramagnetic probe in aggregates of diamagnetic cobalt bis(1,2-dicarbollide)

Popis výsledku v původním jazyce

Metallacarboranes are surface active inorganic boron cluster compounds, and they exhibit solution behavior comparable to organic amphiphiles. We compared the aggregation abilities of two anionic metallacarborane clusters, cobalt(III) bis(1,2-dicarbollide), COSAN, and iron(III) bis(1,2-dicarbollide), FESAN, in aqueous solutions using of NMR spectroscopy, isothermal titration calorimetry, tensiometry, and all-atom molecular dynamics simulations. Leveraging strong paramagnetic effect of FESAN, we used it as a probe in COSAN/FESAN mixed aggregates in order to understand their structure and dynamics. Calculations confirmed that both COSAN and FESAN clusters have the same propensity to form small aggregates with bound sodium counterions. It was confirmed that both COSAN and FESAN are moderately surface active, and the surface activity is monotonically decreasing even above the critical aggregation concentration, CAC. All the techniques confirmed that the aggregation process as well as the structure of the aggregates of COSAN, FESAN and their mixtures are practically the same. Consequently, FESAN is an effective paramagnetic probe. The thorough paramagnetic NMR study revealed that the dynamics of the aggregates in respect to clusters exchange is very fast. The paramagnetic induced shifts, PISs, did not provide any conclusive picture of the aggregate structure because of the rapid averaging. However, the investigation of the paramagnetic relaxation enhancements, PREs, clearly showed that the CH1,2 and CH1&apos;,2&apos; groups of the metallacarborane clusters in the cisoid conformation are preferentially oriented inwards the aggregates, and the rotation and dynamics of the clusters are restricted.

Název v anglickém jazyce

Aggregation of metallacarborane mixtures in aqueous solutions: Iron bis(1,2-dicarbollide) as paramagnetic probe in aggregates of diamagnetic cobalt bis(1,2-dicarbollide)

Popis výsledku anglicky

Metallacarboranes are surface active inorganic boron cluster compounds, and they exhibit solution behavior comparable to organic amphiphiles. We compared the aggregation abilities of two anionic metallacarborane clusters, cobalt(III) bis(1,2-dicarbollide), COSAN, and iron(III) bis(1,2-dicarbollide), FESAN, in aqueous solutions using of NMR spectroscopy, isothermal titration calorimetry, tensiometry, and all-atom molecular dynamics simulations. Leveraging strong paramagnetic effect of FESAN, we used it as a probe in COSAN/FESAN mixed aggregates in order to understand their structure and dynamics. Calculations confirmed that both COSAN and FESAN clusters have the same propensity to form small aggregates with bound sodium counterions. It was confirmed that both COSAN and FESAN are moderately surface active, and the surface activity is monotonically decreasing even above the critical aggregation concentration, CAC. All the techniques confirmed that the aggregation process as well as the structure of the aggregates of COSAN, FESAN and their mixtures are practically the same. Consequently, FESAN is an effective paramagnetic probe. The thorough paramagnetic NMR study revealed that the dynamics of the aggregates in respect to clusters exchange is very fast. The paramagnetic induced shifts, PISs, did not provide any conclusive picture of the aggregate structure because of the rapid averaging. However, the investigation of the paramagnetic relaxation enhancements, PREs, clearly showed that the CH1,2 and CH1&apos;,2&apos; groups of the metallacarborane clusters in the cisoid conformation are preferentially oriented inwards the aggregates, and the rotation and dynamics of the clusters are restricted.

Druh

J_SC - Článek v periodiku v databázi SCOPUS

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GF21-20008K" target="_blank" >GF21-20008K: Metallakarboranové klastry pro přípravu funkčních nanostruktur a polymerních materiálů</a><br>

Návaznosti

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

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

Journal of Molecular Liquids

ISSN

0167-7322

e-ISSN

1873-3166

Svazek periodika

425

Číslo periodika v rámci svazku

May

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

12

Strana od-do

127232

Kód UT WoS článku

—

EID výsledku v databázi Scopus

2-s2.0-85218911787