An official website of the United States government
Molecular ionic composites (MICs) are a new class of solid electrolytes that combine ionic liquids (ILs) and a rigid-rod double helical polyelectrolyte, poly(2,2′-disulfonyl-4,4′benzidine terephthalamide) (PBDT). In this study, we focus on the mechanical, dielectric, and ion diffusive dynamics of MICs with a fixed PBDT weight percent (10 wt%) and varying IL chemistry and molecular volume ( V m ). All six MICs produce tensile moduli in the range of 50–500 MPa at 30 °C, up to 60× higher than the shear moduli of the same MICs. The high range of moduli and tensile to shear modulus ratio emphasizes that the distribution of PBDT chains and the strong ionic interactions between IL ions and PBDT chains dictate the modulus and the mechanical strength in MICs. Additionally, these MICs exhibit high ionic conductivities ranging from 1–6 mS cm −1 at 30 °C, consistent with the measured diffusion coefficients of the IL ions. The tunability of the extraordinary mechanical properties and high ionic conductivities of MIC electrolytes greatly inspire their use in advanced electrochemical devices.
more »
« less
The Impact of Water on Choline‐2‐Octenoic Ionic Liquid‐Facilitated Transdermal Transport
Abstract Ionic liquids (ILs) have been shown to be effective transdermal penetrants of pharmaceutically active ingredients, including small molecules and proteins. The presence of water within ionic liquids has been demonstrated to play a critical role in their structural organization on the molecular level. However, the impact of water on IL transdermal transport efficacy has yet to be investigated. Herein, a water concentration gradient (0%–100% v/v) is tested to evaluate choline trans‐2‐octenoic (CA2OE)‐mediated transport of a hydrophilic model drug dextran (10000 Da) in an ex vivo porcine skin model.Compared to 2:1, 1:1, 1:4, and 1:5 ionic ratio formulations, 50% v/v CA2OE 1:2‐water evidences the greatest success at transporting dextran to the acceptor fluid. Physicochemical characterization (dynamic light scattering (DLS), scanning electron microscopy (SEM), optical density (O.D.), Fourier transform infrared spectroscopy (FTIR), fluorescent microscopy, and rheology) is conducted to test both bulk and nanoscale‐level CA2OE 1:2–water interactions. It is hypothesized that the presence of microemulsions in the CA2OE 1:2 75% v/v formulation accounted for the severely decreased transport compared to the 50%. It is thus critical to comprehensively consider interactions between IL components, co‐solvents, anddrug molecules when formulating ILs for transdermal transport applications.
more »
« less
- PAR ID:
- 10443005
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Therapeutics
- Volume:
- 6
- Issue:
- 1
- ISSN:
- 2366-3987
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
null (Ed.)In the past decade, innovative protein therapies and bio-similar industries have grown rapidly. Additionally, ionic liquids (ILs) have been an area of great interest and rapid development in industrial processes over a similar timeline. Therefore, there is a pressing need to understand the structure and function of proteins in novel environments with ILs. Understanding the short-term and long-term stability of protein molecules in IL formulations will be key to using ILs for protein technologies. Similarly, ILs have been investigated as part of therapeutic delivery systems and implicated in numerous studies in which ILs impact the activity and/or stability of protein molecules. Notably, many of the proteins used in industrial applications are involved in redox chemistry, and thus often contain metal ions or metal-associated cofactors. In this review article, we focus on the current understanding of protein structure-function relationship in the presence of ILs, specifically focusing on the effect of ILs on metal containing proteins.more » « less
-
Since the interface between ionic liquids (ILs) and solids always plays a critical role in important applications such as coating, lubrication, energy storage and catalysis, it is essential to unravel the molecular structure and dynamics of ILs confined to solid surfaces. Here we report direct observation of a unique double-layering quantized growth of three IL ( i.e. [Emim][FAP], [Bmim][FAP] and [Hmim][FAP]) nanofilms on mica. AFM results show that the IL nanofilms initially grow only by covering more surface areas at the constant film thickness of 2 monolayers (ML) until a quantized increase in the film thickness by another 2 ML occurs. Based on the AFM results, we propose a double-layering model describing the molecular structure of IL cations and anions on the mica surface. The interesting double-layering structure can be explained as the result of several competing interactions at the IL–mica interface. Meanwhile, the time-dependent AFM results indicate that the topography of IL nanofilms could change with time and mobility of the nanofilm is lower for ILs with longer alkyl chains, which can be attributed to the stronger solvophobic interaction. The findings here have important implications on the molecular structure and dynamics of ILs confined to solid surfaces.more » « less
-
Ionic liquids (ILs) are gaining attention as protein stabilizers and refolding additives. However, varying degrees of success with this approach motivates the need to better understand fundamental IL-protein interactions. A combination of experiment and simulation is used to investigate the thermal unfolding of lysozyme in the presence of two imidazolium-based ILs (1-ethyl-3-methylimidazolium ethylsulfate, [EMIM][EtSO 4 ] and 1-ethyl-3-methylimidazolium diethylphosphate, [EMIM][Et 2 PO 4 ]). Both ILs reduce lysozyme melting temperature Tm , but more gradually than strong denaturants. [EMIM][Et 2 PO 4 ] lowers lysozyme Tm more readily than [EMIM][EtSO 4 ], as well as requiring less energy to unfold the protein, as determined by the calorimetric enthalpy ΔH. Intrinsic fluorescence measurements indicate that both ILs bind to tryptophan residues in a dynamic mode, and furthermore, molecular dynamics simulations show a high density of [EMIM] + near lysozyme’s Trp62 residue. For both ILs approximately half of the [EMIM] + cations near Trp62 show perfect alignment of their respective rings. The [EMIM] + cations, having a "local" effect in binding to tryptophan,likely perturb a critically important Arg-Trp-Arg bridge through favorable π − π and cation-π interactions. Simulations show that the anions, [EtSO 4 ] - and [Et 2 PO 4 ] - , interact in a "global" manner with lysozyme, due to this protein’s strong net positive charge. The anions also determine the local distribution of ions surrounding the protein. [Et 2 PO 4 ] - is found to have a closer first coordination shell around the protein and stronger Coulomb interactions with lysozyme than [EtSO 4 ] - , which could explain why the former anion is more destabilizing. Patching of ILs to the protein surface is also observed, suggesting there is no universal IL solvent for proteins, and highlighting the complexity of the IL-protein environment.more » « less
-
Abstract Electrostatic gating of two-dimensional (2D) materials with ionic liquids (ILs), leading to the accumulation of high surface charge carrier densities, has been often exploited in 2D devices. However, the intrinsic liquid nature of ILs, their sensitivity to humidity, and the stress induced in frozen liquids inhibit ILs from constituting an ideal platform for electrostatic gating. Here we report a lithium-ion solid electrolyte substrate, demonstrating its application in high-performance back-gated n-type MoS2and p-type WSe2transistors with sub-threshold values approaching the ideal limit of 60 mV/dec and complementary inverter amplifier gain of 34, the highest among comparable amplifiers. Remarkably, these outstanding values were obtained under 1 V power supply. Microscopic studies of the transistor channel using microwave impedance microscopy reveal a homogeneous channel formation, indicative of a smooth interface between the TMD and underlying electrolytic substrate. These results establish lithium-ion substrates as a promising alternative to ILs for advanced thin-film devices.more » « less
