Ionogels: Squeeze flow rheology and ionic conductivity of quasi-solidified nanostructured hybrid materials containing ionic liquids immobilized on halloysite

Агафонов, А. В.; Гришина, Е. П.; Kudryakova, N.O.; Ramenskaya, L. M.; Краев, А. С.; Shibaeva, Valeriya D.

doi:10.1016/j.arabjc.2021.103470

Cited by 9 publications

(6 citation statements)

References 90 publications

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“…We suggest that IL inclusion promotes the formation of diverse ionogels via electrostatic, inter- and intramolecular hydrogen bonding interactions. ,, We consider that for the [Cho][Cl]-ionogel formulations, of highest ionic strength, [Cho][Cl] incorporation could result in surface charge accumulation on the silk fibroin chains and weak intermolecular hydrogen bonding interactions. ,− This would explain our findings of higher T ionogel values, lower phenobarbital solubility, and impeded [Cho][Cl]-ionogel formation. In contrast, the extended structure of the dihydrogen phosphate anions could contribute to the formation of strong intermolecular hydrogen bonding networks and steric effects. − This aligns with our observations of a shorter formation period, greater strength, structural and energetic stability for the [Cho][DHP]-ionogels compared to the [Cho][Cl]-ionogels.…”

Section: Discussionmentioning

confidence: 81%

“…We suggest that IL inclusion promotes the formation of diverse ionogels via electrostatic, inter- and intramolecular hydrogen bonding interactions. 8 , 54 , 55 We consider that for the [Cho][Cl]-ionogel formulations, of highest ionic strength, [Cho][Cl] incorporation could result in surface charge accumulation on the silk fibroin chains and weak intermolecular hydrogen bonding interactions. 13 , 56 − 61 This would explain our findings of higher T ionogel values, lower phenobarbital solubility, and impeded [Cho][Cl]-ionogel formation.…”

Section: Discussionmentioning

confidence: 99%

“…9 However, in general, imidazolium ILbased ionogels are of high viscosity, poor biocompatibility, and low biodegradability; limiting the exploitation of existing ionogels in pharmaceutical applications. 10 Given the highly tunable mechanical and structural properties of ionogels, [6][7][8][9]11,12 we were inspired to leverage rational formulation design to develop diverse, proof-of-concept, thermoresponsive ionogel formulations. These will encompass ionogels which form at distinct periods under 25 °C storage and instantaneously upon heating from 25 to 60 °C, optimally below 37 °C.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Ionogels are intriguing hybrid materials exhibiting high transparency, electroconductivity, thermal and structural stability. − Conventionally, an ionogel is comprised of a given ionic liquid (IL), consisting of a cation and an anion, entrapped within a polymer network. The majority of studies examining ionogels for biomedical applications resort to imidazolium-based ILs, showing high conductivity and self-healing characteristics .…”

Section: Introductionmentioning

confidence: 99%

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Unveiling the Rational Development of Stimuli-Responsive Silk Fibroin-Based Ionogel Formulations

et al. 2023

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We present an approach for the rational development of stimuli-responsive ionogels which can be formulated for precise control of multiple unique ionogel features and fill niche pharmaceutical applications. Ionogels are captivating materials, exhibiting self-healing characteristics, tunable mechanical and structural properties, high thermal stability, and electroconductivity. However, the majority of ionogels developed require complex chemistry, exhibit high viscosity, poor biocompatibility, and low biodegradability. In our work, we overcome these limitations. We employ a facile production process and strategically integrate silk fibroin, the biocompatible ionic liquids (ILs) choline acetate ([Cho][OAc]), choline dihydrogen phosphate ([Cho][DHP]), and choline chloride ([Cho][Cl]), traditional pharmaceutical excipients, and the model antiepileptic drug phenobarbital. In the absence of ILs, we failed to observe gel formation; yet in the presence of ILs, thermoresponsive ionogels formed. Systems were assessed via visual tests, transmission electron microscopy, confocal reflection microscopy, dynamic light scattering, zeta potential and rheology measurements. We formed diverse ionogels of strengths ranging between 18 and 642 Pa. Under 25 °C storage, formulations containing polyvinylpyrrolidone (PVP) showed an ionogel formation period ranging over 14 days, increasing in the order of [Cho][DHP], [Cho][OAc], and [Cho][Cl]. Formulations lacking PVP showed an ionogel formation period ranging over 32 days, increasing in the order of [Cho][OAc], [Cho][DHP] and [Cho][Cl]. By heating from 25 to 60 °C, immediately following preparation, thermoresponsive ionogels formed below 41 °C in the absence of PVP. Based on our experimental results and density functional theory calculations, we attribute ionogel formation to macromolecular crowding and confinement effects, further enhanced upon PVP inclusion. Holistically, applying our rational development strategy enables the production of ionogels of tunable physicochemical and rheological properties, enhanced drug solubility, and structural and energetic stability. We believe our rational development approach will advance the design of biomaterials and smart platforms for diverse drug delivery applications.

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Section: Discussionmentioning

confidence: 81%

Section: Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Unveiling the Rational Development of Stimuli-Responsive Silk Fibroin-Based Ionogel Formulations

et al. 2023

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“…, since they can have high ionic conductivity with a large proportion of the reinforcing component. 44–46 We have previously shown 46 that ionogels based on coagulation structures of halloysite in bis (trifluoromethylsulfonyl) imide ILs with cations EMIm + , BMIm + , BM 2 Im + , BMPyrr + , BMPip + and MOc 3 Am + could be classified as pseudoplastic fluids of the Bingham type. The fluidity of these ionogels linearly correlates with the dynamic viscosity and molar volumes of pure ionic liquids, and the temperature dependence of the ionic conductivity of ionogels in the range from −20 to +80 °C obeys the Vogel–Fulcher–Tamman equation.…”

Section: Introductionmentioning

confidence: 99%