Diffusional Dynamics of Tetraalkylphosphonium Ionic Liquid Films Measured by Fluorescence Correlation Spectroscopy

Mendivelso-Perez, Deyny; Farooq, Muhammad Qamar; Santra, Kalyan; Anderson, Jared L.; Petrich, Jacob W.; Smith, Emily A.

doi:10.1021/acs.jpcb.9b01476

Cited by 6 publications

(6 citation statements)

References 43 publications

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“…Also, a higher temperature is required to disrupt this nanoscale ordering for both ILs in 10 and 100 μm films. The α values were expected to be 1 for glycerol, which would be consistent with our previous measurements as well as a lack of expected nanoscale organization. , In the glycerol films, deviations from the expected α = 1 could be due to the strong three-dimensional hydrogen bonding network that induces aggregate structures . With increasing temperature, the strength of this hydrogen bonding network decreases, thereby allowing for Brownian motion of ATTO 647.…”

Section: Resultssupporting

confidence: 86%

“…The α values were expected to be 1 for glycerol, which would be consistent with our previous measurements as well as a lack of expected nanoscale organization. 105,106 In the glycerol films, deviations from the expected α = 1 could be due to the strong three-dimensional hydrogen bonding network that induces aggregate structures. 106 With increasing temperature, the strength of this hydrogen bonding network decreases, thereby allowing for Brownian motion of ATTO 647. is more similar to glycerol, a solvent that lacks the nanoscale structure when it is not in the proximity of a substrate.…”

Section: ■ Results and Discussionmentioning

confidence: 97%

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Temperature-Dependent Constrained Diffusion of Micro-Confined Alkylimidazolium Chloride Ionic Liquids

et al. 2022

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Alkylimidazolium chloride ionic liquids (ILs) have many uses in a variety of separation systems, including micro-confined separation systems. To understand the separation mechanism in these systems, the diffusion properties of analytes in ILs under relevant operating conditions, including micro-confinement dimension and temperature, should be known. For example, separation efficiencies for various IL-based microextraction techniques are dependent on the sample volume and temperature. Temperature-dependent (20–100 °C) fluorescence recovery after photobleaching (FRAP) was utilized to determine the diffusion properties of a zwitterionic, hydrophilic dye, ATTO 647, in alkylimidazolium chloride ILs in micro-confined geometries. These micro-confined geometries were generated by sandwiching the IL between glass substrates that were separated by ∼1 to 100 μm. From the measured temperature-dependent FRAP data, we note alkyl chain length-, thickness-, and temperature-dependent diffusion coefficients, with values ranging from 0.021 to 46 μm2/s. Deviations from Brownian diffusion are observed at lower temperatures and increasingly less so at elevated temperatures; the differences are attributed to alterations in intermolecular interactions that reduce temperature-dependent nanoscale structural heterogeneities. The temperature- and thickness-dependent data provide a useful foundation for efficient design of micro-confined IL separation systems.

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Section: Resultssupporting

confidence: 86%

Section: ■ Results and Discussionmentioning

confidence: 97%

Temperature-Dependent Constrained Diffusion of Micro-Confined Alkylimidazolium Chloride Ionic Liquids

et al. 2022

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“…FCS is a highly sensitive technique with a single molecular-level resolution to study molecular diffusion using solvent media . While FCS has been used to establish the existence of heterogeneity in ionic liquids, − there are only few reports on the FCS study of DESs. ,− The translational diffusion of various probe molecules in choline chloride/ethylene glycol DES was found to be anomalous instead of the simple single-component diffusion and this has been attributed to the presence of dynamic heterogeneity . A similar result was observed for choline chloride/alcohol DESs .…”

Section: Introductionmentioning

confidence: 68%

Partial Viscosity Decoupling of Solute Solvation, Rotation, and Translation Dynamics in Lauric Acid/Menthol Deep Eutectic Solvent: Modulation of Dynamic Heterogeneity with Length Scale

2020

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Deep eutectic solvents (DESs) are new-generation media that can be fine-tuned to have desired properties circumventing economic and environmental issues. Typically, these are ionic, and only recently, nonionic DESs, having interesting properties, are being explored. In this report, we examined the structure and dynamics of a nonionic lauric acid/menthol (LA/Men) DES through steady-state emission, solvation dynamics, time-resolved fluorescence anisotropy, and translational diffusion dynamics. The zero shift in the emission spectra of coumarin 153 (a solvatochromic dye) as a function of the excitation wavelength suggests that LA/Men DES is spatially homogenous. Decoupling (p = 0.63) of the average solvation time, ⟨τs⟩, from medium viscosity suggests the presence of mild dynamic heterogeneity in the system. Rotational time, ⟨τr⟩, which reflects the nature of the first solvation shell, shows little decoupling (p = 0.81), suggesting it to be fairly dynamically homogeneous at a shorter length scale. An Arrhenius-type analysis also proves that rotation is mainly controlled by medium viscosity. Translational diffusion time, ⟨τD⟩, which provides information at a larger length scale, is strongly decoupled from medium viscosity (p = 0.29). This indicates that at a larger length scale, the DES is quite dynamically heterogeneous. The slow component of solvation time, which is believed to originate at a larger length scale, correlates well with the translational diffusion timescale having similar activation energies. This suggests that their origin is same. Expectedly, for the long component of solvation time, the decoupling is quite strong (p = 0.30). Overall, our result demonstrates the structure and dynamics of the nonionic LA/Men DES, and the existence of length scale-dependent heterogeneity has been proposed.

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“…Fluorescence microscopy can provide insight into transport mechanisms within polymer brushes. Techniques such as fluorescence correlation spectroscopy (FCS) are widely used to study motion in complex structures . Studies applying FCS found that molecule motion in a polymer brush is controlled by grafting density, , as well as structural change and solution ionic strength in a charged system .…”

Section: Introductionmentioning

confidence: 99%

“…Techniques such as fluorescence correlation spectroscopy (FCS) are widely used to study motion in complex structures. 15 Studies applying FCS found that molecule motion in a polymer brush is controlled by grafting density, 16,17 as well as structural change and solution ionic strength in a charged system. 18 Other than fluorophore motion, orientation can also be monitored with polarization-resolved FCS, 19 whereas the effect of flow velocity is explored with the Forster resonance energy transfer (FRET) method.…”

Section: ■ Introductionmentioning

confidence: 99%

Imaging Heterogeneous 3D Dynamics of Individual Solutes in a Polyelectrolyte Brush

Fan,

Bajgiran,

Samghabadi

et al. 2023

Langmuir

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Understanding molecular transport in polyelectrolyte brushes (PEBs) is crucial for applications such as separations, drug delivery, anti-fouling, and biosensors, where structural features of the polymer control intermolecular interactions. The complex structure and local heterogeneity of PEBs, while theoretically predicted, are not easily accessed with conventional experimental methods. In this work, we use 3D single-molecule tracking to understand transport behavior within a cationic poly(2-(N,N-dimethylamino)ethyl acrylate) (PDMAEA) brush using an anionic dye, Alexa Fluor 546, as the probe. The analysis is done by a parallelized, unbiased 3D tracking algorithm. Our results explicitly demonstrate that spatial heterogeneity within the brush manifests as heterogeneity of single-molecule displacements. Two distinct populations of probe motion are identified, with anticorrelated axial and lateral transport confinement, which we believe to correspond to intra-vs inter-chain probe motion.

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Diffusional Dynamics of Tetraalkylphosphonium Ionic Liquid Films Measured by Fluorescence Correlation Spectroscopy

Cited by 6 publications

References 43 publications

Temperature-Dependent Constrained Diffusion of Micro-Confined Alkylimidazolium Chloride Ionic Liquids

Temperature-Dependent Constrained Diffusion of Micro-Confined Alkylimidazolium Chloride Ionic Liquids

Partial Viscosity Decoupling of Solute Solvation, Rotation, and Translation Dynamics in Lauric Acid/Menthol Deep Eutectic Solvent: Modulation of Dynamic Heterogeneity with Length Scale

Imaging Heterogeneous 3D Dynamics of Individual Solutes in a Polyelectrolyte Brush

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