An ionic liquid-based surfactant
with ester functionality self-aggregates
in an aqueous medium and forms ionogels at 8.80% (w/v) concentration
at physiological pH. The ionogel exhibited a remarkable change in
its appearance with temperature from fibrillar opaque to transparent
because of the dynamic changes within its supramolecular structure.
This gel-to-gel phase transition occurs below the melting point of
the solid ionic liquid. The ionogels were investigated using turbidity,
differential scanning calorimetry, scanning electron microscopy (SEM),
field emission SEM (FE-SEM), inverted microscopy, transmission electron
microscopy imaging, Fourier transform infrared spectroscopy, and rheological
measurements. The fibrillar opaque ionogel and transparent ionogel
were studied for their ability to absorb dyes (methyl orange and crystal
violet) and to encapsulate drugs (diclofenac sodium and imatinib mesylate).
The motivation for designing low-molecular-weight gelators with selfhealing characteristics originates from elegant examples in biology such as vines of the genus Aristolochia whose internal secondary growth exhibits rapid self-healing in their stems. In the present work, we had explored the stimuli-responsive dual gelation characteristics for the ester-functionalized surfactant (4-(2-(hexadecyloxy)-2-oxoethyl)-4methylmorpholin-4-ium bromide, C 16 EMorphBr) in aqueous medium at 7.20% (w/v) critical gel concentration and pH 7.4. The hydrogel provides an excellent platform to study dynamic phase behavior within a supramolecular network as it exhibits transformation from a fibrillar opaque hydrogel to a transparent hydrogel upon heating. Molecular interactions, arrangement within the supramolecular framework, and mechanical properties of the hydrogels were characterized using Fourier transform infrared, small-angle neutron scattering, rheological analysis, and tensile strength and cyclic loading−unloading tests. The fibrillar opaque gel has been characterized for its morphology using scanning electron microscopy, field emission scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The self-sustained, self-healable porous fibrillar opaque xerogel was further explored for selectively absorbing anionic dyes and for its load-bearing characteristics. We conclude a perspective on designing a new-age gelator that can open entirely new avenues in environmental protection and wearable "smart" devices.
Conceptualising gelators with stimuli responsiveness is advantageous to design smart materials for emerging technologies. These gelators, if are surface active and made up of active pharmaceutical ingredients, can (i) exhibit an interesting pharmaceutical profile, (ii) be useful in drug formulations and (iii) exert direct effects on cell membranes. Herein, cetylpyridinium salicylate (CetPySal) that offers higher surface activity than its precursor surfactant, cetpylpyridinium chloride (CPCl), was synthesised. CetPySal forms a temperature‐responsive ionogel at a critical gelation concentration that changes its physical appearance with temperature, i. e. opaque to transparent, owing to its structural arrangement within its supramolecular framework, that are characterized through spectrometric, calorimetric, scattering and microscopic techniques. The viscoelastic nature of the ionogels was studied through dynamic rheological measurements and the interactions that governs the phase transition were studied through FTIR spectroscopy. The hybrid pharmaceutical ionogels was successfully constructed through encapsulation of the chemotherapeutic drug imatinib mesylate within the ionogel matrix. The sustained release of the drug was investigated from this hybrid ionogel matrix. These results suggest that this new thermo‐responsive ionogel may be used to improve sustained release of drugs and open up new avenues as low‐cost gelators for biomedical applications.
Stable vesicular aggregate is the primary requisite to transport and deliver the biological and pharmaceutical standards. The serendipitous discovery of nonlipid vesicles made with the nonlipid building blocks, such as ionic liquid based surfactants (ILBSs) proved to be advantageous over others. In a quest to achieve stable, more rigid and hydrophobic vesicles from ILBSs, here we have investigated the lipid (cholesterol) induced unilamellar vesicle formation in the aqueous functionalized and nonfunctionalized ILBSs. The vesicles show outstanding stability with time, temperature and dilution with water. Spectroscopic (turbidity, steady state absorbance and fluorescence), scattering (dynamic light scattering) and microscopic (transmission electron microscopy) techniques were used to characterize the vesicles. The hydration behavior and rigidity associated with the vesicular bilayer on transforming from micellar assembly was characterized through steady state absorbance and fluorescence techniques. The unilamellar vesicles derived are compared with the conventional surfactant, i. e. cetyltrimethyl ammonium bromide.[a] Dr.
An impetus for the sustained interest in the formation of vesicles is their potential application as efficient drug-delivery systems. A simple approach for ionic surfactants is to add a vesicle-inducing drug of opposite charge. In ionic gemini surfactants (GSs) two molecules are covalently linked by a spacer. Regarding drug delivery, GSs are more attractive candidates than their single-chain counterparts because of their high surface activity and the effect on the physicochemical properties of their solutions caused by changing the length of the spacer and inclusion of heteroatoms therein. Herein, the effect of the (anionic) anti-inflammatory drug diclofenac sodium (DS) on the morphology of aqueous micellar aggregates of gemini surfactant hexamethylene-1,6-bis (dodecyldimethylammonium) dibromide (12-6-12) at 25 °C is reported. Several independent techniques are used to demonstrate drug-induced micelle-to-vesicle transition. These include UV/Vis spectrophotometry, dynamic light scattering, TEM, and small-angle neutron scattering. The micelles are transformed into vesicles with increasing [DS]/[12-6-12] molar ratio; precipitation of the catanionic (DS-GS) complex then occurred, followed by partial resuspension of the weakly anionic precipitate. The stability of some of the prepared vesicles at human body temperature shows their potential use in drug delivery.
Surfactant-mediated
coacervates are termed as the new age microreactors
for their ability to spontaneously sequester the molecules with varied
polarities and functionalities. Efforts to emulate this applicability
of coacervates through synthetic control of surfactant structures
are finding success; however, there is little understanding of how
to translate these changes into tailor-made properties. Herein, we
designed 3-methyl-1-(octyloxycarbonylmethyl)imidazolium bromide (C
8
EMeImBr), an ester-functionalized ionic liquid-based surfactant,
which shows better surface active properties than the nonfunctionalized
and conventional cationic surfactant and forms complex coacervates
over the broad range of concentration with sodium salicylate (NaSal).
Mono- and divalent cations as well as ionic strength, viscosity, and
time-dependent stability of the coacervates had also been addressed
in order to study whether these coacervates could work as microreactors
to encapsulate various molecules. The anionic charged complex coacervates
with sponge morphology and honey comb-like interior show good efficiency
to sequester cationic dyes from water because of electrostatic and
hydrophobic interactions and good encapsulation efficiency for curcumin
owing to their high surface area. Results suggest that ionic liquid-based
coacervates studied here could be exploited as a novel low-cost, effective,
and environmentally benign alternative to sequester dyes from the
contaminated water and their recovery.
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