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Statements

Subject Item
n2:RIV%2F60461373%3A22340%2F11%3A43877198%21RIV12-MSM-22340___
rdf:type
n8:Vysledek skos:Concept
dcterms:description
The interaction of natural alpha-, beta-, and gamma-cyclodextrins (CDs) with 14 hydrophobic ionic moieties of ionic liquids (ILs) was systematically examined in dilute aqueous solutions using isothermal titration microcalorimetry (ITC) and NMR spectroscopy. The studied cationic and anionic moieties involved some recently developed heavily fluorinated structures, as well as some others of common use. To isolate the effect of a given ion, the measurements were performed on salts containing the hydrophobic IL ion in question and a complexation-inactive counterion. Additional ITC experiments on ILs whose both cation and anion can interact appreciably with the CD cavity demonstrated that to resolve the effect of individual ions from such data is generally a tricky task and confirmed the superiority of the isolation strategy adopted for the purpose throughout this work. The binding constant, enthalpy and entropy determined at 298.15 K for the 1:1 (ion:CD) inclusion complex formation range in broad limits, being 0 { K { 2.10^5, 0 { -?rH_/(kJ/mol) { 44, and _28 { T?rS_/(kJ/mol) { 14, respectively. The stabilities of complexes of perfluorohexyl bearing ions with beta-CD belong to the highest ever observed with natural CDs in water. The established binding affinity scales were discussed in both thermodynamic and molecular terms. The concepts of hydrophobic interaction and guest_host size matching supported by simple molecular modeling proved useful to rationalize the observed widely different binding affinities and suggest possible binding modes. Enthalpy and entropy contributions to the stability of the ion-CD complexes were found to compensate each other considerably obeying more or less the linear compensation relationship marked by existing literature data on binding other guests to natural CDs. The interaction of natural alpha-, beta-, and gamma-cyclodextrins (CDs) with 14 hydrophobic ionic moieties of ionic liquids (ILs) was systematically examined in dilute aqueous solutions using isothermal titration microcalorimetry (ITC) and NMR spectroscopy. The studied cationic and anionic moieties involved some recently developed heavily fluorinated structures, as well as some others of common use. To isolate the effect of a given ion, the measurements were performed on salts containing the hydrophobic IL ion in question and a complexation-inactive counterion. Additional ITC experiments on ILs whose both cation and anion can interact appreciably with the CD cavity demonstrated that to resolve the effect of individual ions from such data is generally a tricky task and confirmed the superiority of the isolation strategy adopted for the purpose throughout this work. The binding constant, enthalpy and entropy determined at 298.15 K for the 1:1 (ion:CD) inclusion complex formation range in broad limits, being 0 { K { 2.10^5, 0 { -?rH_/(kJ/mol) { 44, and _28 { T?rS_/(kJ/mol) { 14, respectively. The stabilities of complexes of perfluorohexyl bearing ions with beta-CD belong to the highest ever observed with natural CDs in water. The established binding affinity scales were discussed in both thermodynamic and molecular terms. The concepts of hydrophobic interaction and guest_host size matching supported by simple molecular modeling proved useful to rationalize the observed widely different binding affinities and suggest possible binding modes. Enthalpy and entropy contributions to the stability of the ion-CD complexes were found to compensate each other considerably obeying more or less the linear compensation relationship marked by existing literature data on binding other guests to natural CDs.
dcterms:title
Interaction of Ionic Liquids Ions with Natural Cyclodextrins Interaction of Ionic Liquids Ions with Natural Cyclodextrins
skos:prefLabel
Interaction of Ionic Liquids Ions with Natural Cyclodextrins Interaction of Ionic Liquids Ions with Natural Cyclodextrins
skos:notation
RIV/60461373:22340/11:43877198!RIV12-MSM-22340___
n8:predkladatel
n13:orjk%3A22340
n3:aktivita
n18:Z n18:S
n3:aktivity
S, Z(MSM6046137307)
n3:cisloPeriodika
34
n3:dodaniDat
n9:2012
n3:domaciTvurceVysledku
n4:8961131 n4:8169985 n4:9659099 n4:9628924
n3:druhVysledku
n20:J
n3:duvernostUdaju
n17:S
n3:entitaPredkladatele
n14:predkladatel
n3:idSjednocenehoVysledku
205237
n3:idVysledku
RIV/60461373:22340/11:43877198
n3:jazykVysledku
n19:eng
n3:klicovaSlova
NMR spectroscopy; titration microcalorimetry; ionic liquid; Cyclodextrin
n3:klicoveSlovo
n10:titration%20microcalorimetry n10:ionic%20liquid n10:Cyclodextrin n10:NMR%20spectroscopy
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[3CCFC7E63F3C]
n3:nazevZdroje
JOURNAL OF PHYSICAL CHEMISTRY B
n3:obor
n6:CF
n3:pocetDomacichTvurcuVysledku
4
n3:pocetTvurcuVysledku
8
n3:rokUplatneniVysledku
n9:2011
n3:svazekPeriodika
115
n3:tvurceVysledku
Rak, Jakub Tkadlecová, Marcela Lehmann, Jochen K. Dohnal, Vladimír Ignatiev, Nikolai Ondo, Daniel Heintz, Andreas Kvíčala, Jaroslav
n3:wos
000294146200011
n3:zamer
n16:MSM6046137307
s:issn
1520-6106
s:numberOfPages
13
n11:doi
10.1021/jp205039g
n15:organizacniJednotka
22340