The hydrophobicity of room-temperature ionic liquids (RTILs) has been shown to have a very significant effect on the optical and structural properties of and in RTILs. The average excited state lifetime of neat RTILs has been shown to be increasing with increasing hydrophobicity of the RTILs. By employing pico-nanosecond-based fluorescence anisotropy decay, the volume of the nanoaggregates in neat RTILs have been calculated. The volume of these nanoaggregates have been shown to be decreasing with increase in hydrophobicity of the RTILs. Thus, hydrophobicity has been shown to have an important role, i.e., hydrophobicity can be used as a handle to tune the properties of RTILs as designer solvents. Moreover, the excited-state lifetime of red-emitting fluorophores, i.e., whose fluorescence emission is not perturbed by the inherent emission of RTILs, has been shown to increase with the increasing hydrophobicity of the RTILs. Highly hydrophobic RTILs have been shown to exhibit positive deviation and highly hydrophilic RTIL has been shown to exhibit negative deviation from the linear correlation between average solvation time (τ) versus viscosity/temperature (η/).
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http://dx.doi.org/10.1021/acs.jpcb.1c08598 | DOI Listing |
J Chem Phys
January 2025
Department of Materials Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552, Japan.
The liquid/liquid interfaces of room-temperature ionic liquids (RTILs) play a pivotal role in chemical reactions owing to their characteristic microscopic structure, yet the structure of hydrophobic liquid/RTIL interfaces remains unclear. We studied the structure at the liquid/liquid interfaces of carbon tetrachloride (CCl4) and 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([Cnmim][TFSA]; n = 4 and 8) RTILs using infrared-visible sum frequency generation (SFG) vibrational spectroscopy. A comparison of the SFG spectra of the CCl4/RTIL and air/RTIL interfaces revealed that the solvation of the alkyl chains of the [Cnmim]+ cations by CCl4 reduces the number of gauche defects in the alkyl chain and the interface number density of the cation at the CCl4 interface.
View Article and Find Full Text PDFJ Phys Chem B
December 2023
Department of Biochemistry and Biophysics, Oregon State University, Corvallis, Oregon 97331, United States.
A major hurdle in utilizing carbon dioxide (CO) lies in separating it from industrial flue gas mixtures and finding suitable storage methods that enable its application in various industries. To address this issue, we utilized a combination of molecular dynamics simulations and experiments to investigate the behavior of CO in common room-temperature ionic liquids (RTIL) when in contact with aqueous interfaces. Our investigation of RTILs, [EMIM][TFSI] and [OMIM][TFSI], and their interaction with a pure water layer mimics the environment of a previously developed ultrathin enzymatic liquid membrane for CO separation.
View Article and Find Full Text PDFACS Appl Mater Interfaces
September 2023
National Institute of Advanced Industrial Science and Technology (AIST),1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.
The hydrophobicity of room-temperature ionic liquids (RTILs) has been shown to have a very significant effect on the optical and structural properties of and in RTILs. The average excited state lifetime of neat RTILs has been shown to be increasing with increasing hydrophobicity of the RTILs. By employing pico-nanosecond-based fluorescence anisotropy decay, the volume of the nanoaggregates in neat RTILs have been calculated.
View Article and Find Full Text PDFChem Commun (Camb)
January 2022
Universität Würzburg, Institut für Anorganische Chemie, Institut für nachhaltige Chemie & Kataylse mit Bor (ICB), Am Hubland, Würzburg 97074, Germany.
Ethyl-, vinyl- and ethynyltricyano and dicyanofluoroborates were prepared on a gram scale from commercially available potassium trifluoroborates and trimethylsilylcyanide. Salt metathesis resulted in the corresponding EMIm-salts that are hydrophobic room-temperature ionic liquids (RTILs). The new RTILs exhibit unprecedented large electrochemical windows in combination with high thermal stabilities, low dynamic viscosities and high specific conductivities.
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