Effect of in situ mixed micellization of ester-functionalized gemini surfactant at different pHs on solubilization and cosolubilization of various polycyclic aromatic hydrocarbons of varying hydrophobicities.

A pH controlled cleavability unfolds the 3-in-1 surfactant feature of an ester-bonded gemini surfactant, 2, 2'-[(oxybis (ethane-1,2-diyl))bis (oxy)]bis (N-hexadecyl-N,Ndimethyl-2-oxoethanaminium) dichloride (C16-C4O2-C16), by reinforcing in-situ mixed micellization between cleaved components at non-neutral pH (pH 3,12). The triplicity is assigned to two mixed-micelle variants at pH 3 and pH 12 besides the unhydrolyzed C16-C4O2-C16 at pH 7. The pH-controlled aggregation of such trichotomic surfactant dramatically enhances the micellar solubilization/cosolubilization of PAHs viz. naphthalene (Np), phenanthrene (Ph), pyrene (Py), perylene (Pe). The cosolubilization of binary/ternary PAH mixtures in such remarkable micellar assemblies at pH 3, 7 and 12 yields intriguing synergistic or antagonistic solubility outcomes correlated to PAH-PAH and PAH-micelle interactions. This study provides valuable insights into the potential applications of the ester-bonded gemini surfactant for the cosolubilization of undesirable hydrophobic compounds at natural sites having variable pH.

Chitosan Hydrogels with Embedded Thermo- and pH-Responsive Microgels as a Potential Carrier for Controlled Release of Drugs.

We report a promising strategy based on chitosan (CS) hydrogels and dual temperature- and pH-responsive poly(N-isopropylacrylamide-co-methacrylic acid) (PNIPAM-co-MAA) microgels to facilitate release of a model drug, moxifloxacin (MFX). In this protocol, first, the microgels were prepared using a free radical copolymerization method, and subsequently, these carboxyl-group-rich soft particles were incorporated inside the hydrogel matrix using an EDC-NHS amidation method. Interestingly, the resulting microgel-embedded hydrogel composites (MG-HG) acting as a double barrier system largely reduced the drug release rate and prolonged the delivery time for up to 68 h, which was significantly longer than that obtained using microgels or hydrogels alone (20 h). On account of the dual-responsive features of the embedded microgels and the variation of water-solubility of drug molecules as a function of pH, MFX could be released in a controllable manner by regulating the temperature and pH of the delivery medium. The release kinetics followed a Korsmeyer-Peppas model, and the drug delivery mechanism was described by Fickian diffusion. Both the gel precursors and the hydrogel composites exhibited low cytotoxicity against mammalian cell lines (HeLa and HEK-293) and no deleterious hemolytic activity up to a certain higher concentration, indicating excellent biocompatibility of the materials. Thus, the unprecedented combination of modularity of physical properties caused by soft particle entrapment, unique macromolecular architecture, biocompatibility, and the general utility of the stimuli-responsive polymers offers a great promise to use these composite materials in drug delivery applications.

Emission Color Tuning and White Light Generation from a Trimolecular Cocktail in Cationic Micellar System with Promising Applicability in the Anticounterfeiting Technology.

The development of photoluminescent (PL) systems, displaying multiple stimuli-responsive emission color tuning, has been the pressing priority in the recent times due to their huge role in contemporary lighting and anticounterfeiting technologies. Acknowledging this importance, we present a simple and eco-friendly PL system showing emission color tuning in response to different stimuli, that is, the composition of the system, pH, excitation wavelength, and the temperature with the plus point of getting significantly pure white light emission (WLE). The novel system is fabricated from the aqueous mixture of three organic fluorophores, umbelliferone (UMB), fluorescein (FLU), and Rhodamine-B (RB). By varying the fluorophore composition in the mixture at pH 12, nearly pure WLE with a Commission Internationale d'Eclairage (CIE) 1931 profile of (0.33, 0.33) was obtained at the excitation wavelength of 365 nm, the sustainability of which was ensured by employing the micellar self-assemblies of tetradecyltrimethylammonium bromide (TTAB) molecules. Similar WLE was obtained under mildly acidic conditions (pH 6) but at the excitation wavelength of 330 nm. By proper tuning of pH and the wavelengths of the system to use it as a fluorescent ink, we found a remarkable and highly applicable phenomenon observed for the first time, that is, triple-mode orthogonal emission color tuning with white light ON/OFF switching. We validate the vital applicability of this phenomenon in protecting the authenticity of the document with its hard-to-counterfeit property. The applicability of this phenomenon is also explored by synthesizing PVA-based fluorescent films from the tri-fluorophore mixture. Moreover, the emission color of the PL system was explored lucidly for its temperature dependence owing to the thermal responsiveness of RB emission, where the PL system proves to be a full-color RGB system.

pH Changes in the Micelle-Water Interface of Surface-Active Ionic Liquids Dictate the Stability of Encapsulated Curcumin: An Insight Through a Unique Interfacial Reaction between Arenediazonium Ions and t-Butyl Hydroquinone.

The chemical kinetic (CK) method, which involves the reduction of 4-hexadecylbenzenediazonium ions (16-ArN2 +) by antioxidants (in the present case, TBHQ) occurring exclusively at the interface of the association colloids, was employed to establish the changes in the chemical reactivity of anionic surface-active ionic liquids (SAILs) as a function of the concentration and the composition in their mixed states. We used sodium dodecyl sulfate and different SAILs based on the dodecylsulfate surfactant containing 1-alkyl-3-methylimidazolium cations as counterions having a varying alkyl chain length of 4 (bmim), 8 (omim), and 12 (ddmim) carbon atoms. The structural transitions of aggregates of the SAILs from the micellar to vesicular form were observed as a function of concentration in single surfactant systems and as a function of composition in mixed surfactant systems. Results of the reduction kinetics of 16-ArN2 + at the interface of such aggregates, which depends on the acid/base equilibria at the interface, gave an insight into the changes in the interfacial H+ ions with the change in the hydrophobicity of the counterions of SAILs and the morphological changes from micelles to vesicles as a function of concentration or composition. These changes in the interfacial pH correlate very well with the stability of curcumin within these self-assemblies, which exclusively depends on the pH of the medium and highlights the importance of the results obtained from the CK method in selecting the appropriate medium/conditions for the stabilization of the bioactive molecules.

Temperature- and Composition-Induced Multiarchitectural Transitions in the Catanionic System of a Conventional Surfactant and a Surface-Active Ionic Liquid.

The mixture of the cationic surfactant, cetyltrimethylammonium bromide (CTAB), and anionic surface-active ionic liquid, 1-butyl-3-methylimidazoliumdodecyl sulfate (bmimDS), has been studied as a function of the mole fraction of CTAB, X CTAB, with the total surfactant concentration fixed at 50 mM using turbidity measurements, rheology, dynamic light scattering, differential scanning calorimetry, small-angle neutron scattering, and small-angle X-ray scattering techniques. The catanionic mixture has been found to exhibit phase transitions from vesicles to micelles as a function of temperature, with some mole fractions of CTAB showing dual transitions. Solutions of X CTAB = 0.2 to 0.5 exhibited a single transition from vesicles to cylindrical micelles at 45 °C. With an increase in the mole fraction of CTAB from 0.55 to 0.65, dual structural transitions at 30 and 45 °C were observed. The microstructural transition at 30 °C is ascribed to the vesicle aggregation process with smaller vesicles fusing into bigger ones, whereas the transition at 45 °C was evaluated to be the vesicle-to-cylindrical micelle transition. However, at higher mole fractions of CTAB, X CTAB from 0.65 to 0.90, a single transition from vesicles to small cylindrical/spherical micelles was observed in the solutions, at a lower temperature of 30 °C. To the best of our knowledge, such a microstructural transitions as a function of temperature in a single mixture of cationic and anionic surfactants without any additive has not been reported so far.

Energy transduction through FRET in self-assembled soft nanostructures based on surfactants/polymers: current scenario and prospects.

The self-assembled systems of surfactants/polymers, which are capable of supporting energy funneling between fluorophores, have recently gained significant attraction. Surfactant and polymeric micelles form nanoscale structures spanning a radius of 2-10 nm are generally suitable for the transduction of energy among fluorophores. These systems have shown great potential in Förster resonance energy transfer (FRET) due to their unique characteristics of being aqueous based, tendency to remain self-assembled, spontaneous formation, tunable nature, and responsiveness to different external stimuli. This review presents current developments in the field of energy transfer, particularly the multi-step FRET processes in the self-assembled nanostructures of surfactants/polymers. The part one of this review presents a background and brief overview of soft systems and discusses certain aspects of the self-assemblies of surfactants/polymers and their co-solubilization property to bring fluorophores to close proximity to transduce energy. The second part of this review deals with single-step and multi-step FRET in the self-assemblies of surfactants/polymers and links FRET systems with advanced smart technologies including multicolor formation, data encryption, and artificial antenna systems. This review also discusses the diverse examples in the literature to present the emerging applications of FRET. Finally, the prospects regarding further improvement of FRET in self-assembled soft systems are outlined.

Co-solubilization of polycyclic aromatic hydrocarbon mixtures in aqueous micellar systems and its correlation with FRET for enhanced remediation processes.

Surfactant enhanced remediation (SER) is an effective approach for decontaminating the PAH polluted soils. Solubilization and Cosolubilization of Phenanthrene (Ph), Pyrene (Py) and Perylene (Pe) as single, binary and ternary mixtures have been studied employing cationic (CTAB), anionic (SDS), non-ionic surfactant (Brij 30) and block copolymer (P123) micelles. In the single solute solubilization studies, solubility of Pe follows the order Brij 30 > CTAB > SDS whereas Ph or Py followed the order of CTAB > Brij 30 > SDS. In the cosolubilization studies, an increase, decrease or no change in the mutual solubility of PAHs was observed. Synergism in solubilization was observed most in P123 in both binary and ternary PAH mixture where more PAHs could get solubilized in the dense micellar shell region, thereby enhancing the micellar core volume leading to enhanced solubilization of PAHs. The solubilizates as pairs (Ph-Pe and Py-Pe) were further tested for any possible energy transfer in presence of surfactant based restricted host environments using spectrofluorometry and spectrophotometry. Based on the solubilization and cosolubilization an efficient non-radiative energy transfer (FRET) was observed between Ph/Py (donor) and Pe (acceptor) in the non-ionic surfactant system as well as in CTAB-Brij 58 mixed system. The results of this work may improve the effective utilization of surfactants in their correct evaluation for the removal of PAHs from contaminated soils or aquifers treated with SER technology.

Broad Spectrum Tunable Photoluminescent Material Based on Cascade Fluorescence Resonance Energy Transfer between Three Fluorophores Encapsulated within the Self-Assembled Surfactant Systems.

A broad spectrum tunable photoluminescent material with dual encryption based on a two-step fluorescence resonance energy transfer (FRET) between pyrene (Py), coumarin 480 (Cou480), and rhodamine 6G (R6G) in micelles of SDS and bmimDS is presented. The phenomenon is achievable due to the encapsulation of the fluorophores within these micelles. The transfer of energy as FRET between the pair Py and Cou480 showed ON at 336 nm and OFF at 402 nm in contrast to the FRET observed between the pair Cou480 and R6G that showed ON at 402 nm and OFF at 336 nm. However, the transfer of energy as FRET occurs from Py to R6G in the presence of Cou480 when excited at 336 nm, thereby making it a chain of three fluorophores with Cou480 acting as a relay fluorophore receiving energy from Py and transferring it to R6G. The different FRET scenarios between the three fluorophores in micelles provide a window for the generation of a matrix of colors, which occupies a significant 2D area in the chromaticity diagram, having potential applications in security printing. The different fluorophoric ratios generate different colors based on their individual photonic emissions and the FRET processes taking place between them. Writing tests were carried out using varied ratios of the fluorophores in the micellar systems producing different colored outputs under the UV light with insignificant visibility under the white light. We envision that this as-discovered three fluorophoric FRET system could form the basis for the future development of multi-FRET light-harvesting devices and anti-counterfeiting security inks based on much simpler non-covalent interaction aided encapsulation of the fluorophores within the self-assembled soft systems.