Exploring the Properties of Unilamellar Vesicle Bilayers Formed by Ionic Liquid Surfactants for Future Applications in Nanomedicine.

Two ionic liquids (ILs) with amphiphilic properties composed of 1-butyl-3-methylimidazolium dioctylsulfosuccinate (bmim-AOT) and 1-hexyl-3-methylimidazolium dioctylsulfosuccinate (hmim-AOT) form unilamellar vesicles spontaneously simply by dissolving the IL-like surfactant in water. These novel vesicles were characterized using two different and highly sensitive fluorescent probes: 6-propionyl-2-(dimethylaminonaphthalene) (PRODAN) and trans-4-[4-(dimethylamino)-styryl]-1-methylpyridinium iodide (HC). These fluorescent probes provide information about the physicochemical properties of the bilayer, such as micropolarity, microviscosity, and electron-donor capacity. In addition, the biocompatibility of these vesicles with the blood medium was evaluated, and their toxicity was determined using Dictyostelium discoideum amoebas. First, using PRODAN and HC, it was found that the bilayer composition and the chemical structure of the ions at the interface produced differences between both amphiphiles, making the vesicles different. Thus, the bilayer of hmim-AOT vesicles is less polar, more rigid, and has a lower electron-donor capacity than those made by bmim-AOT. Finally, the results obtained from the hemolysis studies and the growth behavior of unicellular amoebas, particularly utilizing the D. discoideum assay, showed that both vesicular systems do not produce toxic effects up to a concentration of 0.02 mg/mL. This elegant assay, devoid of animal usage, highlights the potential of these newly organized systems for the delivery of drugs and bioactive molecules of different polarities.

Epoxiconazole degradation in water samples: a comparative study of Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis processes.

Epoxiconazole (EPO) is classified as a persistent organic pollutant due to its ability to persist in the environment for prolonged periods. Its degradation is pivotal in mitigating its environmental impact. This investigation focuses on assessing the degradation of EPO using various methodologies, namely Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis, conducted in both Milli-Q water and groundwater. These experiments encompassed evaluations at both the standard pH typically used in photo-Fenton reactions and the natural pH levels inherent to the respective aqueous environments. Additionally, EPO degradation products were analyzed after a 60-min reaction. Notably, in systems utilizing groundwater, the inclusion of additional iron was unnecessary, as the naturally occurring iron content in the groundwater facilitated the intended processes. Specifically, in Milli-Q water, solar photo-Fenton demonstrated an EPO degradation efficiency of 97%. Furthermore, the substitution of Milli-Q water with groundwater in Fenton-like processes did not significantly affect the efficacy of EPO degradation. These findings underscore the potential of solar photo-Fenton as an economically viable and environmentally sustainable strategy for EPO degradation.

Speciation and Proton Conductivity of Phosphoric Acid Confined in Mesoporous Silica.

Phosphoric acid (PA) confined in a commercial mesoporous silica (CARIACT G) with porous size in the range of 3 to 10 nm was studied in relation to its coordination with the silanol groups on the silica surface as a function of temperature, up to 180 °C, using 31P and 29Si MAS NMR spectroscopy. As the temperature increases, the coordination of Si and P in the mesopores depends on the pore size, that is, on the area/volume ratio of the silica matrix. In the mesoporous silica with the higher pore size (10 nm), a considerable fraction of PA is nonbonded to the silanol groups on the surface, and it seems to be responsible for its higher conductivity at temperatures above 120 °C as compared to the samples with a smaller pore size. The electrical conductivity of the functionalized mesoporous silica was higher than that reported for other silico-phosphoric composites synthesized by sol-gel methods using soft templates, which require high-temperature calcination and high-cost reagents and are close to that of the best PA-doped polybenzimidazole membranes used in high-temperature proton exchange membrane fuel cells (HT-PEMFCs). The rate of PA release from the mesoporous silica matrix when the system is exposed to water has been measured, and it was found to be strongly dependent on the pore size. The low cost and simplicity of the PA-functionalized mesoporous silica preparation method makes this material a promising candidate to be used as an electrolyte in HT-PEMFCs.

Biocompatible Solvents and Ionic Liquid-Based Surfactants as Sustainable Components to Formulate Environmentally Friendly Organized Systems.

In this review, we deal with the formation and application of biocompatible water-in-oil microemulsions commonly known as reverse micelles (RMs). These RMs are extremely important to facilitate the dissolution of hydrophilic and hydrophobic compounds for biocompatibility in applications in drug delivery, food science, and nanomedicine. The combination of two wisely chosen types of compounds such as biocompatible non-polar solvents and ionic liquids (ILs) with amphiphilic character (surface-active ionic liquids, SAILs) can be used to generate organized systems that perfectly align with the Green Chemistry concepts. Thus, we describe the current state of SAILs (protic and aprotic) to prepare RMs using non-polar but safe solvents such as esters derived from fatty acids, among others. Moreover, the use of the biocompatible solvents as the external phase in RMs and microemulsions/nanoemulsions with the other commonly used biocompatible surfactants is detailed showing the diversity of preparations and important applications. As shown by multiple examples, the properties of the RMs can be modified by changes in the type of surfactant and/or external solvents but a key fact to note is that all these modifications generate novel systems with dissimilar properties. These interesting properties cannot be anticipated or extrapolated, and deep analysis is always required. Finally, the works presented provide valuable information about the use of biocompatible RMs, making them a green and promising alternative toward efficient and sustainable chemistry.

Potentiometric Study of Carbon Nanotube/Surfactant Interactions by Ion-Selective Electrodes. Driving Forces in the Adsorption and Dispersion Processes.

The interaction (adsorption process) of commercial ionic surfactants with non-functionalized and functionalized carbon nanotubes (CNTs) has been studied by potentiometric measurements based on the use of ion-selective electrodes. The goal of this work was to investigate the role of the CNTs' charge and structure in the CNT/surfactant interactions. Non-functionalized single- (SWCNT) and multi-walled carbon nanotubes (MWCNT), and amine functionalized SWCNT were used. The influence of the surfactant architecture on the CNT/surfactant interactions was also studied. Surfactants with different charge and hydrophobic tail length (sodium dodecyl sulfate (SDS), octyltrimethyl ammonium bromide (OTAB), dodecyltrimethyl ammonium bromide (DoTAB) and hexadecyltrimethyl ammonium bromide (CTAB)) were studied. According to the results, the adsorption process shows a cooperative character, with the hydrophobic interaction contribution playing a key role. This is made evident by the correlation between the free surfactant concentration (at a fixed [CNT]) and the critical micellar concentration, cmc, found for all the CNTs and surfactants investigated. The electrostatic interactions mainly determine the CNT dispersion, although hydrophobic interactions also contribute to this process.

Influence of the AOT Counterion Chemical Structure on the Generation of Organized Systems.

The impact of the imidazolium counterion structure on the organized systems formed by the surfactant 1,4-bis-2-ethylhexylsulfosuccinate, AOT, both in aqueous solutions and in nonpolar solvents is investigated. With this in mind, we investigated if the ionic liquid-like (IL-like) surfactant 1-ethyl-3-methylimidazolium 1,4-bis-2-ethylhexylsulfosuccinate, emim-AOT, forms direct micelles or vesicles in water. Dynamic light scattering, zeta potential, conductivity, fluorescence spectroscopy, and UV-visible spectroscopy measurements were performed to characterize the organized systems in aqueous solutions. We also studied the self-aggregation of emim-AOT, 1-butyl-3-methylimidazolium 1,4-bis-2-ethylhexylsulfosuccinate, bmim-AOT, and of 1-hexyl-3-methylimidazolium 1,4-bis-2-ethylhexylsulfosuccinate, hmim-AOT, in nonpolar solvents. The results obtained showed that the IL-like surfactant emim-AOT forms direct micelles in water, as sodium 1,4-bis-2-ethylhexylsulfosuccinate (Na-AOT) does. However, emim-AOT aggregates are larger, have a lower surface charge, are more stable, and have a more polar and less fluid micellar interface than Na-AOT micelles. It was also observed that emim-AOT and hmim-AOT form reverse micelles in nonpolar solvents. The size of the imidazolium cations dramatically influences the size of the reverse micelles and their ability to solubilize water.

Use of Ionic Liquids-like Surfactants for the Generation of Unilamellar Vesicles with Potential Applications in Biomedicine.

The goal of this work is to understand the influence of the counterion nature on the organized systems formed by 1,4-bis-2-ethylhexylsulfosuccinate surfactants in aqueous solutions and how these aggregates will influence the deoxyribonucleic acid (DNA)-surfactant interactions. With this in mind, two ionic liquid-like surfactants were investigated: 1-butyl-3-methylimidazolium 1,4-bis-2-ethylhexylsulfosuccinate (bmim-AOT) and 1-hexyl-3-methylimidazolium 1,4-bis-2-ethylhexylsulfosuccinate (hmim-AOT). Measurements of dynamic light scattering, ζ-potential, transmission electron microscopy, and fluorescence and UV-visible spectroscopy were performed to study the characteristics of the vesicles formed by bmim-AOT and hmim-AOT. Regarding the determination of the interaction of the surfactants with DNA, circular dichroism was used. The results obtained showed that bmim-AOT and hmim-AOT ionic liquid-like surfactants spontaneously form unilamellar vesicles in water at very low surfactant concentrations. The characteristics of these aggregates are dependent on the length of the tail of the counterions. The length of the hydrophobic chains of the counterions also influences the DNA-surfactant interactions through hydrophobic effects.

Interfacial properties modulated by the water confinement in reverse micelles created by the ionic liquid-like surfactant bmim-AOT.

The behavior of the interfacial water entrapped in reverse micelles (RMs) that were formed by the ionic liquid-like surfactant 1-butyl-3-methylimidazolium 1,4-bis-2-ethylhexylsulfosuccinate (bmim-AOT) was investigated with the use of UV-Vis absorption spectroscopy and nuclear magnetic resonance (NMR) relaxometry. The solvatochromism of two molecular probes, namely, 1-methyl-8-oxyquinolinium betaine (QB) and N,N,N',N'-tetramethylethylenediamine copper(ii)acetylacetonate tetraphenylborate ([Cu(acac)(tmen)][B(C6H5)4]), was investigated. As a comparison, the analog RMs formed by sodium 1,4-bis-2-ethylhexylsulfosuccinate (Na-AOT) were also explored. By varying the water content inside the RMs and consequently the different magnitude of the water-surfactant interactions at the interface, interesting properties were observed by comparing bmim-AOT and Na-AOT RMs. From the solvatochromic behavior of ([Cu(acac)(tmen)][B(C6H5)4]), we found that the interface in bmim-AOT RMs shows a smaller electron donating capacity than that in Na-AOT RMs. QB revealed that the interfacial region is a weaker hydrogen bond donor and less polar than the corresponding Na-AOT RMs. NMR experiments showed that the molecular motion of water in bmim-AOT RMs is less restricted than that of the water molecules confined in Na-AOT RMs. In summary, the results show how the nature of the bmim+ cation affects the interaction between the entrapped water and the RM interface, greatly modifying the interfacial water structure in comparison with the results known for Na-AOT.

How the cation 1-butyl-3-methylimidazolium impacts the interaction between the entrapped water and the reverse micelle interface created with an ionic liquid-like surfactant.

The behavior of the interfacial water entrapped in reverse micelles (RMs) formed by the ionic liquid-like surfactant 1-butyl-3-methylimidazolium 1,4-bis-2-ethylhexylsulfosuccinate (bmim-AOT) dissolved in benzene (or chlorobenzene) was investigated using noninvasive techniques such as dynamic light scattering (DLS), static light scattering (SLS), FT-IR and (1)H NMR. The DLS and SLS results reveal the formation of discrete spherical and non-interacting water droplets stabilized by the bmim-AOT surfactant. Moreover, since the droplet size increases as the W0 (W0 = [water]/[surfactant]) value increases, water interacts with the RM interface. From FT-IR and (1)H NMR data, a weaker water-surfactant interaction in bmim-AOT RMs in comparison with the RMs created by sodium 1,4-bis-2-ethylhexylsulfosuccinate (Na-AOT) is detected. Consequently, there are less water molecules interacting with the interface in bmim-AOT RMs, and their hydrogen bond network is not completely disrupted as they are in Na-AOT RMs. The results show how the nature of the new cation impacts the interaction between the entrapped water and the RM interface, modifying the interfacial water structure in comparison with the results known for Na-AOT.