Assessing the Roles of the Constituents of Ionic Liquids in Dynamic Solvation:  Comparison of an Ionic Liquid in Micellar and Bulk Form

Mukherjee, Prasun; Crank, Jeffrey A.; Halder, Mintu; Armstrong, Daniel W.; Petrich, Jacob W.

doi:10.1021/jp063433i

Cited by 51 publications

(52 citation statements)

References 43 publications

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“…This situation is comparable to that of [CVIM + ][Br -], where C153 is quenched more efficiently in the micelle than in the bulk reference solvent. 36 In both cases, C153 is interpreted to be located in Corresponding steady-state and time-zero spectra are also included. Note that the 4.1 and 20.1 ns spectra cross the steady-state spectrum, indicating that this spectrum does not adequately report on the completed solvation of C153, as would usually be expected.…”

Section: Resultsmentioning

confidence: 99%

“…Transient spectra were reconstructed from these fits in the standard manner. 23, 36 We have employed the traditional approach of fitting the timeresolved spectra to a log-normal function, from which we extract the peak frequency, ν(t), as a function of time.…”

Section: Methodsmentioning

confidence: 99%

“…[23][24][25] Previously, we attempted to address some of these questions by studying the solvation of the dye coumarin 153 in a bulk imidazolium ionic liquid, 1-cetyl-3-vinylimidazolium bromide ([CVIM + ][Br -]), and its corresponding micelle in water. 36 (There is a growing body of work on the subject of ionic liquids in micelles, microemulsions, and related systems. [37][38][39][40][41][42][43] ) Because coumarin 153 is only sparingly soluble and weakly fluorescent in water, a clear distinction can be made between its fluorescent properties in the bulk ionic liquid and those in the micelles formed from the ionic liquid.…”

Section: Introductionmentioning

confidence: 99%

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Dynamic Solvation in Phosphonium Ionic Liquids: Comparison of Bulk and Micellar Systems and Considerations for the Construction of the Solvation Correlation Function, C(t)

et al. 2008

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Dynamic solvation of the dye coumarin 153 is studied in a phosphonium ionic liquid: hexadecyltributylphosphonium bromide, [(C4)3C16P+][Br-]. It forms micelles in water, and the bulk also exists as a liquid under our experimental conditions. This system permits a comparison with an imidazolium ionic liquid studied earlier, which also formed micelles in water (J. Phys. Chem. A 2006, 110, 10725−10730). We conclude that our analysis of the comparable situation in a phosphonium liquid is not as definitive as we had proposed earlier, i.e., that the majority of the early-time solvation arises from the organic cation. Part of the difficulty in performing this analysis is most likely due to the amount of water that is associated with the micelle. In the course of this work, we have focused on the calculation of the solvation correlation function, C(t), and investigated how it depends upon the methods with which the "zero-time" spectrum is constructed. Arlington, Box 19065, Arlington, Texas 76019 ReceiVed: NoVember 8, 2007; In Final Form: December 7, 2007 Dynamic solvation of the dye coumarin 153 is studied in a phosphonium ionic liquid: hexadecyltributylphosphonium bromide, [(C 4 ) 3 C 16 P + ][Br -]. It forms micelles in water, and the bulk also exists as a liquid under our experimental conditions. This system permits a comparison with an imidazolium ionic liquid studied earlier, which also formed micelles in water (J. Phys. Chem. A 2006, 110, 10725-10730). We conclude that our analysis of the comparable situation in a phosphonium liquid is not as definitive as we had proposed earlier, i.e., that the majority of the early-time solvation arises from the organic cation. Part of the difficulty in performing this analysis is most likely due to the amount of water that is associated with the micelle. In the course of this work, we have focused on the calculation of the solvation correlation function, C(t), and investigated how it depends upon the methods with which the "zero-time" spectrum is constructed. Keywords

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Dynamic Solvation in Phosphonium Ionic Liquids: Comparison of Bulk and Micellar Systems and Considerations for the Construction of the Solvation Correlation Function, C(t)

et al. 2008

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“…In the recent years, IL has received more attention thanks to negligible vapor pressure, good thermal stability and high electrical conductivity [17]. Because of intriguing physicochemical properties, IL has shown tremendous applications in various analytical fields, such as sample preparation [18], electrochemistry [19], chromatography [20], spectroscopy [21] and an unorthodox matrix for analysis [22]. Among them, increasing number of investigations by employing IL in CE have provided significant advantages in the sample treatment [23], chiral analysis [24,25], the use of PSP [26,27], the addition of chemical modifier [28] and the support coating [29].…”

Section: Introductionmentioning

confidence: 99%

The use of novel ionic liquid‐in‐water microemulsion without the addition of organic solvents in a capillary electrophoretic system

Cao

Cheng

2010

Electrophoresis

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In this work, a new ionic liquid-in-water (IL/W) microemulsion without requiring toxic organic solvents was investigated as a pseudostationary phase (PSP) in CE. As observed during the IL/W microemulsion system, a fast and an efficient separation of eight phenolic acids was achieved using 1-butyl-3-methylimidazolivmhexa fluorophosphate (bmimPF(6)) as oil drops, Tween 20 as the surfactant, and borate as the BGE. The effects of oil phase, surfactant, buffer and pH on the separation were explored in detail to evaluate the novel PSP. In contrast, the detection efficiency of these same analytes was markedly decreased using oil-in-water (O/W) MEEKC. We have also validated the practicality of the IL/W microemulsion method by quantitative determination of acidic compounds in pharmaceutical injection. The results obtained indicated that an additional association between the IL cations and analytes tested seemed to play a prominent role in the separation mechanism exhibited by this novel PSP compared with the conventional O/W MEEKC.

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“…23,58 The specific synthesis of 1-hydroxyethyl-4-amino-1,2,4-triazolium bromide (HEATB) and 1-hydroxyethyl-4-amino-1,2,4-triazolium nitrate (HEATN) from metathesis of HEATB with silver nitrate follows the procedure described by Drake, Hawkins, and Tollison. 59 The synthesis of the other ionic liquids shown in Figure 1 is described elsewhere, 11,60,61 and they were decolorized according to the procedure described previously. 62 Briefly, the impure ionic liquid was diluted and was allowed to elute through a column packed with celite, silica gel, and activated charcoal.…”

Section: à48mentioning

confidence: 99%

Structure and Dynamics of the 1-Hydroxyethyl-4-amino-1,2,4-triazolium Nitrate High-Energy Ionic Liquid System

et al. 2011

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An investigation of the structure and dynamics of the high-energy ionic liquid, 1-hydroxyethyl-4-amino-1,2,4-triazolium nitrate (HEATN), was undertaken. Both experimental and computational methods were employed to understand the fundamental properties, characteristics, and behavior of HEATN. The charge separation, according to the electrostatic potential derived charges, was assessed. The MP2 (second-order perturbation theory) geometry optimizations find six dimer and five tetramer structures and allow one to see the significant highly hydrogen bonded network predicted within the HEATN system. Due to the prohibitive scaling of ab initio methods, the fragment molecular orbital (FMO) method was employed and assessed for feasibility with highly energetic ionic liquids using HEATN as a model system. The FMO method was found to adequately treat the HEATN ionic liquid system as evidenced by the small relative error obtained. The experimental studies involved the investigation of the solvation dynamics of the HEATN system via the coumarin 153 (C153) probe at five different temperatures. The rotational dynamics through the HEATN liquid were also measured using C153. Comparisons with previously studied imidazolium and phosphonium ionic liquids show surprising similarity. To the authors' knowledge, this is the first experimental study of solvation dynamics in a triazolium-based ionic liquid. Disciplines Chemistry CommentsThis article is from Journal of Physical Chemistry B 116 (2012): 503, doi:10.1021/jp207840q. RightsWorks produced by employees of the U.S. Government as part of their official duties are not copyrighted within the U.S. The content of this document is not copyrighted. There has been a steeper than exponential growth in the number of publications related to ionic liquids since the year 2000. Authors1 The interest in ionic liquids reflects their versatility and their environmentally friendly properties in comparison to commonly used compounds.2À4 Ionic liquids are molten salts, commonly composed of an organic cation and an inorganic anion that can often be liquid at room temperature. These low-melting salts are considered to be green solvents, in contrast to volatile organic compounds, due to their high chemical and thermal stabilities, negligible vapor pressure, 5 and high recoverability and reusability.6,7 Ionic liquids can be customized by varying the identity of the substituents on the cation or by adapting the moiety of the anion.8 This versatility and these unique properties have piqued the interest of the scientific community, and a variety of fundamental studies 9À16 have been performed on ionic liquids to obtain a better understanding of their characteristics.One interesting application of ionic liquids is in the highenergy density matter (HEDM) community, where many different molten salts have been explored and reported. 17 It is important to understand what characteristics make ionic liquids suited to HEDM applications. This very problem was explored computationally in a series of studies,...

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Assessing the Roles of the Constituents of Ionic Liquids in Dynamic Solvation: Comparison of an Ionic Liquid in Micellar and Bulk Form

Cited by 51 publications

References 43 publications

Dynamic Solvation in Phosphonium Ionic Liquids: Comparison of Bulk and Micellar Systems and Considerations for the Construction of the Solvation Correlation Function, C(t)

Dynamic Solvation in Phosphonium Ionic Liquids: Comparison of Bulk and Micellar Systems and Considerations for the Construction of the Solvation Correlation Function, C(t)

The use of novel ionic liquid‐in‐water microemulsion without the addition of organic solvents in a capillary electrophoretic system

Structure and Dynamics of the 1-Hydroxyethyl-4-amino-1,2,4-triazolium Nitrate High-Energy Ionic Liquid System

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