Surfactant Assemblies Research Articles

Fluorescent Ionic Liquid Aggregates: A Self-Assembled Approach for Pesticide Detection and Catalysis.

The unregulated use of pesticides, industrial discharge of heavy metals, waste, and agricultural runoff may contaminate surface water and groundwater, consequently threatening ecosystems and human health. Thus, the sensitive detection and degradation of pesticides are essential for safety. In this context, herein, we have developed benzimidazolium-based fluorescent surfactant assemblies TA-1/SDS and TA-2/SDBS, which exhibit aggregation-induced emission enhancement in an aqueous medium. The aggregates (TA-1/SDS and TA-2/SDBS) displayed a turn-on emission response upon interaction with carbendazim and azamethiphos with limits of detection 7.5 and 7.8 nM, respectively. The FE-SEM and AFM studies revealed that TA-1/SDS and TA-2/SDBS undergo self-assembly with the addition of AZA and CBZ, resulting in the formation of dendritic structures. In addition to the quantification of AZA and CBZ, TA-1/SDS and TA-2/SDBS have also been evaluated to degrade both pesticides and validated using 31P NMR spectroscopy and LC-MS spectrometry.

Interfacial Cooperative Assembly of Surfactants and Opposite Wettability Nanoparticles Stabilizes Water-in-Oil Emulsions at High Temperature.

Pickering emulsions have promising applications in the development of unconventional oil and gas resources. However, the high-temperature environment of the reservoir is not conducive to the stabilization of Pickering emulsions. In addition, the preparation of Pickering emulsions under low-energy emulsification and low-concentration emulsifier conditions is a difficult challenge. Here, we report a high-temperature resistant water-in-paraffin oil Pickering emulsion, which is synergistically stabilized by polyglycerol ester (PGE) and nanoparticles with opposite wettability (lipophilic silica and hydrophilic alumina). This emulsion can be prepared under mild stirring (500 rpm) conditions and can be stable at 140 °C for at least 30 days. The synergistic effects of surfactant, silicon nanoparticles (MSNPs) with different wettability, and alumina nanoparticles (AONPs) on the stability of both emulsions and water-oil interfacial membranes were investigated through bottle experiments, cryogenic scanning electron microscopy (cryo-SEM), optical microscopy, fluorescence microscopy, etc. The results showed that both hydrophobic MSNPs and hydrophilic AONPs are adsorbed together at the water-oil interface to stabilize the W/O emulsion, which can be prepared by 500 rpm stirring. The stability of emulsions strongly depends on the wettability of MSNPs, and the MSNP with moderate hydrophobicity (for example, aqueous phase contact angle of 136°) makes the emulsion exhibit the highest stability against aggregation and settling at elevated temperatures. The emulsion stabilization mechanism was revealed in terms of the adsorption capacity of the surfactant by MSNPs, the adsorption morphology and desorption energy of nanoparticles at the water-oil interface adsorption layer, and emulsion rheology. These findings demonstrate a novel and simple strategy to prepare Pickering W/O emulsions with high-temperature stability at low shear strength.

Surface Tension Manipulation with Visible Light through Sensitized Disequilibration of Photoswitchable Amphiphiles.

Azoarene isomerization lies at the heart of numerous applications, from catalysis or energy storage to photopharmacology. While efficient switching between their E and Z isomers predominantly relies on UV light, a recent study by Klajn and co-workers introduced visible light sensitization of E azoarenes and their subsequent isomerization as a tool coined disequilibration by sensitization under confinement (DESC) to obtain high yields of the Z isomer. This host-guest approach is, however, still constrained to minimally substituted azoarenes with limited applicability in advanced molecular systems. Herein, we expand DESC for the assembly of surfactants at the air-water interface. Leveraging our expertise with photoswitchable amphiphiles, we induce substantial alterations of the water surface tension through reversible arylazopyrazole isomerization. After studying the binding of charged surfactants to the host, we find that the surface activity differences upon visible light switching for both isomers are comparable to those obtained by UV light excitation. The method is demonstrated on a large concentration range and can be activated using green or red light, depending on the sensitizer chosen. The straightforward implementation of photoswitch sensitization in a complex molecular network showcases how DESC enables the improvement of existing systems and the development of novel applications driven by visible light.

Surface Tension Manipulation with Visible Light through Sensitized Disequilibration of Photoswitchable Amphiphiles

Azoarene isomerization lies at the heart of numerous applications from catalysis or energy storage to photopharmacology. While efficient switching between their E and Z isomers predominantly relies on UV light, a recent study by Klajn and co‐workers introduced visible light sensitization of E azoarenes and subsequent isomerization as a tool coined disequilibration by sensitization under confinement (DESC) to obtain high yields of the Z isomer. This host‐guest approach is, however, still constrained to minimally substituted azoarenes with limited applicability in advanced molecular systems. Herein, we expand DESC for the assembly of surfactants at the air‐water interface. Leveraging our expertise with photoswitchable amphiphiles, we induce substantial alterations of water’s surface tension through reversible arylazopyrazole isomerization. After studying the binding of charged surfactants to the host, we find that the surface activity differences upon visible light irradiation for both isomers are comparable to those obtained by UV light excitation. The method is demonstrated on a large concentration range and can be activated using green or red light, depending on the sensitizer chosen. The straightforward implementation of photoswitch sensitization in a complex molecular network showcases how DESC enables the improvement of existing systems and the development of novel applications driven by visible light.

Gemini Surfactant-Induced Cysteine-Capped Copper Nanoclusters Self-Assembly with Enhanced Peroxidase-Like Activity and Colorimetric Glutathione Sensing.

We have prepared a novel assembly with copper nanoclusters (CuNCs) and imidazolium-based gemini surfactants (different chain lengths). These novel mimic enzymes formed through the assembly of nanocluster-gemini surfactants have been utilized in creating colorimetric sensors to detect biomolecules. Yet, understanding the method for detecting glutathione (GSH) and its sensing mechanism using this specific assembly-based colorimetric sensor poses a significant challenge. Because of the role of surface ligands, the complexes of cysteine-capped CuNCs (Cys-CuNCs) and gemini surfactants exhibit strong amphiphilicity, enabling them to self-assemble like a molecular amphiphile. We have investigated the kinetics and catalytic capabilities of this Cys-CuNCs@gemini surfactant assembly through peroxidase-like activity. Additionally, a sensitive and simple-to-use colorimetric sensing approach for glutathione (GSH) is also disclosed here, demonstrating a low limit of detection, by using this peroxidase-like activity of Cys-CuNCs@gemini surfactant assemblies. Thus, the remarkable advantages of the Cys-CuNCs@gemini surfactant nanozyme make it suitable for the precise colorimetric detection of GSH, demonstrating excellent sensitivity and reliable selectivity. Additionally, it performs well in detecting GSH in various soft drinks.

Determining the Role of Surfactant on the Cytosolic Delivery of DNA Cross-Linked Micelles.

Nucleic Acid Nanocapsules (NANs) are nucleic acid nanostructures that radially display oligonucleotides on the surface of cross-linked surfactant micelles. Their chemical makeup affords the stimuli-responsive release of therapeutically active DNA-surfactant conjugates into the cells. While NANs have so far demonstrated the effective cytosolic delivery of their nucleic acid cargo, as seen indirectly by their gene regulation capabilities, there remain gaps in the molecular understanding of how this process happens. Herein, we examine the enzymatic degradation of NANs and confirm the identity of the DNA-surfactant conjugates formed by using mass spectrometry (MS). With surface enhanced (resonance) Raman spectroscopy (SE(R)RS), we also provide evidence that the energy-independent translocation of such DNA-surfactant conjugates is contingent upon their release from the NAN structure, which, when intact, otherwise buries the hydrophobic surfactant tail in its interior. Such information suggests a critical role of the surfactant in the lipid disruption capability of the DNA surfactant conjugates generated from degradation of the NANs. Using NANs made with different tail lengths (C12 and C10), we show that this mechanism likely holds true despite significant differences in the physical properties (i.e., critical micelle concentration (CMC), surfactants per micelle, Nagg) of the resultant particles (C12 and C10 NANs). While the total cellular uptake efficiencies of C12 and C10 NANs are similar, there were differences observed in their cellular distribution and localized trafficking, even after ensuring that the total concentration of DNA was the same for both particles. Ultimately, C10 NANs appeared less diffuse within cells and colocalized less with lysosomes over time, achieving more significant knockdown of the target gene investigated, suggesting more effective endosomal escape. These differences indicate that the surfactant assembly and disassembly properties, including the number of surfactants per particle and the CMC can have important implications for the cellular delivery efficacy of DNA micelles and surfactant conjugates.

Coordination-Driven Templated Synthesis of Hierarchically Porous Zeolitic Imidazolate Frameworks for Cascade Enzyme Cycle Amplification Coupled Immunoassay.

Although hierarchically porous zeolitic imidazolate frameworks (HPZIFs) not only inherit the intrinsic architectural and chemical stabilities of their microporous counterparts but also afford open space for the efficient mass diffusion of the macromolecules involved, their rational design and construction are still challenging. Herein, HPZIFs with tailorable pore sizes ranging from 18 to 54 nm were successfully fabricated by using a newly developed soft-template-directed strategy. Our success rooted in the fact that the screened PS81-PVP44-PEO113 triblock copolymer could effectively coordinate with the metal precursor for the directed crystallization of ZIFs along surfactant assemblies. The advantages of continuous large pores and open structures in such HPZIFs were fully taken into account to serve as a bioreactor for the efficient immunoassay. The expanded large pores provided not only a significantly vast surface area to enhance the density of capture antibodies but also enough space for accommodating multiple conjugated biomolecules in one pore channel. In combination with a cascade enzyme cycle amplification strategy, a model biomarker of prostate-specific antigen (PSA) at the femtomolar level was checked with a limit of detection of 92 fM using the developed immunosensor. Specific screening on patients with prostate cancer or even benign prostatic hyperplasia was exemplified through accurately quantifying small changes of PSA concentration in clinical serum samples, prefiguring the great potential of the developed HPZIF-8 immunosensor platform for the early monitoring and diagnostics of diseases.

Pickering emulsion via interfacial assembly of lignin particles and cationic surfactant: Formation of robust anchoring layer

Lignin, a byproduct of the paper and pulp industry, shows promise as stabilizers for emulsions, offering potential value-added applications to direct disposal. However, utilizing particulate lignin directly as stabilizers is challenging due to limited emulsion stability. In this study, co-stabilization of Pickering emulsions is investigated by combination of lignin particles and cationic surfactants (CTAB and DDAB), wherein lignin source and oil types are optimized with a focus on emulsion stability. A battery of characterization methods, including visual appearance, microstructure, droplet size, zeta potential, etc., is employed to evaluate emulsion stability. The findings reveal that kraft lignin nanospheres (LNS) are the optimal stabilizing particles. The incorporation of cationic surfactants via electrostatic adsorption enhances the stabilizing effect of LNS, and the use of DDAB is found to significantly enhance emulsion stability compared to CTAB, attributing to higher charge shielding capability of DDAB, as well as the formation of a more robust and compact nonpolar anchoring layer. The surfactant-assisted LNS can be used to stabilize a range of oil types, with tridecane as the optimal oil. This research presents a straightforward, efficient, and scalable approach for producing highly stable lignin-based Pickering emulsions, showing potential applications in recycling and value enhancement of waste lignin.

Myelin Surfactant Assemblies as Dynamic Pathways Guiding the Growth of Electrodeposited Copper Dendrites.

Self-organization of inorganic matter enables bottom-up construction of materials with target shapes suited to their function. Positioning the building blocks in the growth process involves a well-balanced interplay of the reaction and diffusion. Whereas (supra)molecular structures have been used to template such growth processes, we reasoned that molecular assemblies can be employed to actively create concentration gradients that guide the deposition of solid, wire-like structures. The core of our approach comprises the interaction between myelin assemblies that deliver copper(II) ions to the tips of copper dendrites, which in turn grow along the Cu2+ gradient upon electrodeposition. First, we successfully include Cu2+ ions among amphiphile bilayers in myelin filaments, which grow from tri(ethylene glycol) monododecyl ether (C12E3) source droplets over air-water interfaces. Second, we characterize the growth of dendritic copper structures upon electrodeposition from a negative electrode at the sub-mM Cu2+ concentrations that are anticipated upon release from copper(II)-loaded myelins. Third, we assess the intricate growth of copper dendrites upon electrodeposition, when combined with copper(II)-loaded myelins. The myelins deliver Cu2+ at a negative electrode, feeding copper dendrite growth upon electrodeposition. Intriguingly, the copper dendrites follow the Cu2+ gradient toward the myelins and grow along them toward the source droplet. We demonstrate the growth of dynamic connections among electrodes and surfactant droplets in reconfigurable setups─featuring a unique interplay between molecular assemblies and inorganic, solid structures.

Structure design and performance optimization of PVDF-CTFE nanofibrous composite nanofiltration membrane modified by C–Cl active site grafting

The substrate membrane plays a crucial role in determining the performance of composite nanofiltration membranes prepared by interfacial polymerization (IP). In this study, persistent hydrophilic modification of polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-CTFE) was achieved by incorporating N-methylglucamine (N-MG) without altering the membrane's morphology or pore size. Moreover, thin-film nanofibrous composite (TFNC) nanofiltration membranes were prepared using the surfactant assembly regulated interfacial polymerization (SARIP) method with the modified PVDF-CTFE@N-MG nanofibrous membrane as the substrate. The effect of N-MG addition on the substrate membrane's hydrophilicity and the structure and performance of the polyamide (PA) separation layer was investigated. The results showed that the addition of N-MG significantly improved the hydrophilicity of the PVDF-CTFE nanofibrous membrane. The TFNC-5 membrane, prepared with the modified PVDF-CTFE@N-MG nanofibrous membrane as the substrate, exhibited permeability exceeding 13.5 L m−2 h−1·bar−1 for various dye solutions at 3 bar pressure, with rejection rates above 98 %. It also demonstrated excellent selective separation performance (separation factor for NaCl/Orange G reaching 97.38) and long-term operational stability. This work provides a method for the preparation of low-pressure, high-flux nanofiltration membranes, which is applicable to seawater desalination and dye wastewater treatment.

Thermal Welding of Liquids.

Welding of thermoplastics is a common practice in many industrial sectors, but it has yet to be realized with fluids. Here, the thermal welding of liquids by using the assembly and jamming of nanoparticle surfactants (NPSs) at liquid-liquid interfaces is reported. By fine-tuning the dynamic interaction strength within NPSs, the interfacial activity of NPSs, as well as the binding energy of NPSs to the interface can be precisely controlled, leading to a dynamic exchange of NPSs, maximizing the reduction in the interfacial energy. With NPSs jammed at the interface, the structures of liquids can be manipulated to complex geometries by applying an external force and, due to the temperature responsiveness of NPSs, when bringing liquids into contact and heating the system, welding of liquids can be achieved. This work provides a straightforward strategy for the construction of modular all-liquid fluidics, opening up numerous opportunities in fields like biotechnology, healthcare, and materials science.

Substrate-induced assembly of cascade enzymes and catalytic surfactants: nanoarchitectonics at the oil-in-water droplet interface.

The heterogeneous distribution of lipids and lipid-bound proteins in a plasma membrane has functional advantages. Herein, in a synthetic system, we demonstrate the assembly of three enzymes involved in cascade reactions, in response to the substrate of the first enzyme at the oil-water interface being stabilized by a Zn(II)-metallosurfactant. Then we show substrate-mediated catalytically-active cluster formation of the metallosurfactant in a binary mixture with another non-catalytic surfactant at the interface. The catalytic ability can be tuned by controlling clustering through the addition of phosphate ions. Overall this work demonstrates functionally diverse supramolecular nanoarchitectonics at the oil-water interface.

Stepped copper sites coupling voltage-induced surfactant assembly to achieve efficient CO2 electroreduction to formate

Ligand modification for electrochemically formed stepped Cu sites can achieve higher formate selectivity during CO2 reduction. This study highlights the synergy of ligand effect and catalyst reconstruction at atomic and molecular levels.

Film before aggregates: an operando GISAXS study on electrochemically assisted surfactant assembly.

The process of electrochemically assisted surfactant assembly was followed in real time by grazing incidence small angle X-ray scattering with the aim to deconvolute the formation of mesoporous silica film and unwanted porous particles. The X-ray technique proved to be useful for the characterisation of this process, as it takes place at a very dynamic, solid/liquid interface. This paper shows the electrochemically driven onset and evolution of silica/surfactant structures. Additional control experiments indicate the formation of vertically aligned structures without the use of an electric field, although it seems to be beneficial for increased pore ordering.

Anisotropic Interface Successive Assembly for Bowl-Shaped Metal-Organic Framework Nanoreactors with Precisely Controllable Meso-/Microporous Nanodomains.

Colloidal metal-organic framework (MOF) nanoparticles, with tailored asymmetric nanoarchitectures and hierarchical meso-/microporosities, have significant implications in high-performance nanocatalysts, nanoencapsulation carriers, and intricate assembly architectures. However, the methodology that could achieve precise control over the anisotropic growth of asymmetric MOF particles with tailored distributions of meso- and microporous regions has not yet been established. In this study, we introduce a facile anisotropic interface successive assembly approach to synthesize asymmetric core-shell MOF (ZIF-67) nanobowls with worm-like mesopores in the core and intrinsic micropores in the shell. Our synthesis pathway relies on anisotropic nucleation of mesoporous MOF nanohemispheres on emulsion interfaces through the cooperative assembly of surfactants and MOF precursors. This is followed by the growth of microporous MOF layers on both interfaces of mesoporous cores and emulsion droplets, resulting in a hierarchically porous core-shell nanostructure. By utilizing this multi-interface-driven approach, we enable the creation of diverse geometries and distributions of mesopores and micropores in asymmetric MOF nanoarchitectures. The obtained bowl-like meso-/microporous core-shell ZIF-67 particles exhibit enhanced catalytic activity for CO2 cycloaddition, attributed to reactant accumulation within the bowl-like architecture, active site accessibility in the open mesoporous core, and improved structural stability. Overall, our study provides insights and inspiration for exploring the intricate asymmetric nanostructures of hierarchically porous MOFs with diverse potential applications.

Parabolic Viscosity Behavior of NaCl-Thickened Surfactant Systems upon Temperature Change.

The viscosity of household care products plays an important role in pleasant delivery using consumer experience at home. A novel solution to mitigate the sharp rising of viscosities at low temperatures of detergents was proposed. By designing the formulation of the surfactant blend, formulators can achieve acceptable viscosity profiles in the temperature range encountered in daily life. The verification and modulation of formulas bearing parabolic viscosity-temperature behavior were systematically studied, including in single, binary, and ternary systems, based on the modulation of sodium ethoxylated alkyl sulfate (AES) by other anions, zwitterions, and nonions. The R ratio theory was used to have a better understanding of the molecular assembly of surfactants behind the parabolic behavior exhibited in rheology analyses. One of the key findings is that the parabolic viscosity-temperature phenomenon could be easily observed in the highly hydrated ethoxylated anionic systems like AES-based systems. For those anions lacking ethoxylation, especially sodium linear alkylbenzene sulfonate (LAS), the monotonic variation of hydration affinity with temperature led to the disappearance of parabola in the observed temperature window (>0 °C). Moreover, salinity played an important role in the hydration affinity of the polar group and the interaction between the hydrophilic headgroups. A balanced salinity should be optimized to modulate the hydration affinity in a desired range so that the parabola could be easily tuned within the target temperature region. These findings provide opportunities for the formulators in the household care industry to design products with better pourability through carefully selecting a combination of surfactants and fine-tuning their ratios to improve consumer use experience, especially in winter.

Fluorescent Nanoassembly of Tetrazole-Based Dyes with Amphoteric Surfactants: Investigation of Cyanide Sensing and Antitubercular Activity.

Tetrazole-based easily synthesizable fluorogenic probes have been developed that can form self-assembled nanostructures in the aqueous medium. Though the compounds could achieve detection of cyanide ions in apolar solvents, such as, THF, significant interference was observed from other basic anions, such as F-, AcO-, H2PO4-, etc. On the other hand, a highly specific response was observed for CN- ions in the aqueous medium. However, the sensitivity was so poor that it could hardly be useful for real-life sample analysis. Interestingly, the co-assembly of such probe molecules with hydroxyethyl-anchored amphoteric surfactants could drastically improve the sensitivity toward CN- ions in water without dampening their excellent selectivity. Also, it was observed that the degree of fluorescence response for CN- ions depends on the nature of the polyaromatic scaffolds (naphthyl vs anthracenyl), the nature of the surfactant assembly (micelle vs vesicle), etc. The mechanistic investigation indicates the hydrogen bonding interaction between the tetrazole -NH group and cyanide ions in the aqueous medium, which can effectively change the electronics of the tetrazole unit, resulting in alteration in the extent of charge transfer interaction. Then, the biocompatible composite materials (dye-surfactant assemblies at different ratios) were tested for antituberculosis activity. Fortunately, in a few cases, the compositions were found to be as effective as the commercially available antituberculosis drug, ethambutol.

A cross-reactive fluorescent ensemble based on perylene derivative/surfactant assemblies for discrimination of multiple aminoglycoside antibiotics in aqueous solution

Sensitive detection and discrimination of multiple aminoglycosides (AGs) hold paramount importance in the efforts to curtail antibiotic overutilization and to monitor environmental impact. The present work provides a novel discriminative sensor ensemble based on a perylene derivative and SDS assemblies that can recognize nine different aminoglycosides. The fluorescent binary ensemble emits very weak fluorescence due to the strong aggregation of perylene-based probes in SDS pre-micelles. The addition of AGs can induce fast and remarkable fluorescence enhancement. The acquisition of fluorescence variation data at three characteristic emission wavelengths enables the generation of distinctive recognition pattern to each AG. Principal component analysis reveals that the sensor ensemble can correctly identify multiple AGs in both buffered aqueous solution and in 10% human urine. The fluorescence enhancement is attributed to the disaggregation of perylene units caused by the variation of SDS assembly from pre-micelle to micelles resulting from multi-point interaction with AGs. The strategy of modulation effect on fluorescence emission of encapsulated fluorophores by surfactant assemblies has been demonstrated to be highly effective for fabricating single system-based discriminative sensors for aminoglycosides.

Relaxing Wrinkles in Jammed Interfacial Assemblies

AbstractDynamic covalent bonding has emerged as a mean by which stresses in a network can be relaxed. Here, the strength of the bonding of ligands to nanoparticles at the interface between two immiscible liquids affect the same results in jammed assemblies of nanoparticle surfactants. Beyond a critical degree of overcrowding induced by the compression of jammed interfacial assemblies, the bonding of ligands to nanoparticles (NPs) can be broken, resulting in a desorption of the NPs from the interface. This reduces the areal density of nanoparticle surfactants at the interface, allowing the assemblies to relax, not to a fluid state but rather another jammed state. The relaxation of the wrinkles caused by the compression reflects the tendency of these assemblies to eliminate areas of high curvature, favoring a more planar geometry. This enabled the generation of giant vesicular and multivesicular structures from these assemblies.

Relaxing Wrinkles in Jammed Interfacial Assemblies.

Dynamic covalent bonding has emerged as a mean by which stresses in a network can be relaxed. Here, the strength of the bonding of ligands to nanoparticles at the interface between two immiscible liquids affect the same results in jammed assemblies of nanoparticle surfactants. Beyond a critical degree of overcrowding induced by the compression of jammed interfacial assemblies, the bonding of ligands to nanoparticles (NPs) can be broken, resulting in a desorption of the NPs from the interface. This reduces the areal density of nanoparticle surfactants at the interface, allowing the assemblies to relax, not to a fluid state but rather another jammed state. The relaxation of the wrinkles caused by the compression reflects the tendency of these assemblies to eliminate areas of high curvature, favoring a more planar geometry. This enabled the generation of giant vesicular and multivesicular structures from these assemblies.