Inverted Micelles Research Articles

Responses of assembled structures of block polyelectrolytes to electrostatic interaction strength.

In this paper, the responses of assembled behaviors of block polyelectrolytes (PEs) to the strength of electrostatic interactions are studied through molecular dynamic simulations. The results show that the assembled structures closely depend on the electrostatic strength. It should be noted that PE coacervation can outweigh the nucleation of hydrophobic blocks and invert the micelle structures at strong electrostatic strengths, leading to the formation of inverted micelles of PE cores and hydrophobic coronas. In the poor solvent condition for neutral block, diverse anisotropic micelles are presented; candy-like conventional micelles of hydrophobic cores and PE patches coexist with inverted candy-like micelles of PE cores and hydrophobic patches and with Janus micelles of semi-neutral aggregate and semi-PE cluster in the presence of divalent and trivalent counterions. The formation of conventional or inverted micelle is largely determined by the type of micellar fusion, which results from the nucleation competition between electrostatic correlation and hydrophobic interaction. The merge of micelles mediated by hydrophobic attraction leads to conventional hydrophobic cores, and the fusion induced by electrostatic correlations results in PE cores micelles. At strong electrostatic strengths, the PE chains exhibit rich conformations at trivalent counterions, ranging from a fully collapsed state to a rod-like state, and parallel alignment of PE chains is found.

Multifactorial drug carrier system bringing both chemical and physical therapeutics to the treatment of tumor heterogeneity

Tumor heterogeneity and drug resistance have been invincible features of cancer for its complete cure. Despite the advent of immunotherapy, the expansion and diversification of cancer cells evolved even in the absence or presence of drug treatment discourage additional therapeutic interventions. For the eradication of cancer cells, therefore, an ‘all-at-once’ strategy is required, which exploits both target-selective chemotherapy and non-selective physicotherapy. Multifactorial microcapsules comprising gold nanoparticles (AuNPs) and a self-assembly protein of α-synuclein (αS) were fabricated, in which hydrophobic and hydrophilic drugs could be separately encapsulated by employing lipid-based inverted micelles (IMs). Their combined physico-chemical therapeutic effects were examined since they also contained both membrane-disrupting IMs and heat-generating AuNPs upon irradiation as physicotherapeutic agents. For the optimal enclosure of IMs containing hydrophilic drugs, a porous inner skeleton made of poly(lactic-co-glycolic acid) was introduced, which would play the roles of not only compartmentalizing the internal space but also enhancing proteolytic disintegration of the microcapsules to discharge and stabilize IMs to the outside. In fact, hydrophobic paclitaxel and hydrophilic doxorubicin showed markedly enhanced drug efficacy when delivered in the IM-containing microcapsules exhibiting the ‘quantal’ release of both drugs into the cells whose integrity could be also affected by the IMs. In addition, the remnants of αS-AuNP microcapsules produced via proteolysis also caused cell death through photothermal effect. The multifactorial microcapsules are therefore considered as a promising anti-cancer drug carrier capable of performing combinatorial selective and non-selective chemical and physical therapies to overcome tumor heterogeneity and drug resistance.

Cationic Proteins Rich in Lysine Residue Trigger Formation of Non-bilayer Lipid Phases in Model and Biological Membranes: Biophysical Methods of Study.

Cationic membrane-active toxins are the most abundant group of proteins in the venom of snakes and insects. Cationic proteins such as cobra venom cytotoxin and bee venom melittin are known for their pharmacological reactions including anticancer and antimicrobial effects which arise from the toxin-induced alteration in the dynamics and structure of plasma membranes and membranes of organelles. It has been established that these cationic toxins trigger the formation of non-bilayer lipid phase transitions in artificial and native mitochondrial membranes. Remarkably, the toxin-induced formation of non-bilayer lipid phase increases at certain conditions mitochondrial ATP synthase activity. This observation opens an intriguing avenue for using cationic toxins in the development of novel drugs for the treatment of cellular energy deficiency caused by aging and diseases. This observation also warrants a thorough investigation of the molecular mechanism(s) of lipid phase polymorphisms triggered by cationic proteins. This article presents a review on the application of powerful biophysical methods such as resonance spectroscopy (31P-, 1H-, 2H-nuclear magnetic resonance, and electron paramagnetic resonance), luminescence, and differential scanning microcalorimetry in studies of non-bilayer lipid phase transitions triggered by cationic proteins in artificial and biological membranes. A phenomenon of the triggered by cationic proteins the non-bilayer lipid phase transitions occurring within 10-2-10-11s is discussed in the context of potential pharmacological applications of cationic proteins. Next to the ATP dimer is an inverted micelle made of cardiolipin that serves as a vehicle for the transport of H+ ions from the intra-crista space to the matrix. It is proposed that such inverted micelles are triggered by the high density of H+ ions and the cationic proteins rich in lysine residue which compete with the conserved lysine residues of the ATP synthase rotor for binding to cardiolipin in the inner mitochondrial membrane and perturb the bilayer lipid packing of cristae. Phospholipids with a blue polar head represent cardiolipin and those with a red polar head represent other phospholipids found in the crista membrane.

Overlapping Properties of the Short Membrane-Active Peptide BP100 With (i) Polycationic TAT and (ii) α-helical Magainin Family Peptides.

BP100 is a short, designer-made membrane-active peptide with multiple functionalities: antimicrobial, cell-penetrating, and fusogenic. Consisting of five lysines and 6 hydrophobic residues, BP100 was shown to bind to lipid bilayers as an amphipathic α-helix, but its mechanism of action remains unclear. With these features, BP100 embodies the characteristics of two distinctly different classes of membrane-active peptides, which have been studied in detail and where the mechanism of action is better understood. On the one hand, its amphiphilic helical structure is similar to the pore forming magainin family of antimicrobial peptides, though BP100 is much too short to span the membrane. On the other hand, its length and high charge density are reminiscent of the HIV-TAT family of cell penetrating peptides, for which inverted micelles have been postulated as translocation intermediates, amongst other mechanisms. Assays were performed to test the antimicrobial and hemolytic activity, the induced leakage and fusion of lipid vesicles, and cell uptake. From these results the functional profiles of BP100, HIV-TAT, and the magainin-like peptides magainin 2, PGLa, MSI-103, and MAP were determined and compared. It is observed that the activity of BP100 resembles most closely the much longer amphipathic α-helical magainin-like peptides, with high antimicrobial activity along with considerable fusogenic and hemolytic effects. In contrast, HIV-TAT shows almost no antimicrobial, fusogenic, or hemolytic effects. We conclude that the amphipathic helix of BP100 has a similar membrane-based activity as magainin-like peptides and may have a similar mechanism of action.

OPTIMIZING THE STRUCTURE OF AMPHIPHILIC INVERTIBLE POLYMERS (AIPs) MADE OF PEGs AND FATTY COMPOUND SEGMENTS TO OBTAIN A SINGLE CRITICAL MICELLE CONCENTRATION

Amphiphilic biopolyesters containing hydrophilic segments (PEGs) and hydrophobic blocks (silicon fatty from a castor oil derivative) showed the ability to self-assembly in inverted micelles. Due to their capability to form also direct micelles, these biopolyesters could be classified as amphiphilic invertible polymers AIPs. The micellar concentrations CMC and ICMC corresponding to the direct and inverted micelles respectively precisely correlated with PEG length. The methodology used in this investigation allowed to determine the PEG length needed to obtain the adequate structural biopolyester able to self-assembly in direct and inverted micelles from a unique concentration. Inverted micelle diameters, determined by DLS analysis, increased as the molecular polarity of the biopolyesters decreased. No individual inverted micellar were observed by TEM technique due to the concentration change during the sample preparation, however micellar macromolecular aggregations were revealed.

Can Polarity-Inverted Surfactants Self-Assemble in Nonpolar Solvents?

We investigate the self-assembly process of a surfactant with inverted polarity in water and cyclohexane using both all-atom and coarse-grained hybrid particle-field molecular dynamics simulations. Unlike conventional surfactants, the molecule under study, proposed in a recent experiment, is formed by a rigid and compact hydrophobic adamantane moiety, and a long and floppy triethylene glycol tail. In water, we report the formation of stable inverted micelles with the adamantane heads grouping together into a hydrophobic core and the tails forming hydrogen bonds with water. By contrast, microsecond simulations do not provide evidence of stable micelle formation in cyclohexane. Validating the computational results by comparison with experimental diffusion constant and small-angle X-ray scattering intensity, we show that at laboratory thermodynamic conditions the mixture resides in the supercritical region of the phase diagram, where aggregated and free surfactant states coexist in solution. Our simulations also provide indications as to how to escape this region to produce thermodynamically stable micellar aggregates.

Microfluidic Preparation of Liposomes Using Ethyl Acetate/n-Hexane Solvents as an Alternative to Chloroform

Although liposomes have been used as a nutrient delivery carrier in the pharmaceutical, cosmetic, and food industries, they still suffer from the critical issue caused by the use of halogenated solvents (e.g., chloroform), which may be harmful to humans. Nonhalogenated solvents have been screened as candidate substitutes for chloroform based on their physicochemical properties. However, none of the candidates examined to date could form stable inverted micelles when used alone. Here, to obtain physicochemical properties similar to chloroform, combined mixtures were prepared using various ratios of each candidate. Based on the results of random combination trials with numerous candidates, ethyl acetate: n-hexane = 4 : 1(v/v) was selected as the optimum ratio because it could form stable inverted micelles and a transparent liposome solution without phase separation. The ethyl acetate and n-hexane mixture are a potential substitute for chloroform, which may resolve concerns regarding the toxicity of residual halogenated solvents in lipid nanovesicles.

The Microstructure of Calcium Sulfonate Complex Lubricating Grease and Its Change in the Presence of Water

ABSTRACTCalcium sulfonate complex grease is often selected for rolling bearing lubrication if there is a risk for water ingress, because it is reported throughout literature that it can absorb large quantities of water. In this article, atomic force microscopy (AFM) measurements have been performed on a commercially available grease with and without water to investigate the microstructural change under the influence of water. From the results it is clear that the formation of large (inverted) micelles, which can be up to a few micrometers in diameter, is the main mechanism responsible for the absorption water. These results can be used to explain the earlier reported effect of water on the rheological and lubricating properties of these grease types. It is shown here that the size distribution of the micelle structure is a function of the amount of water mixed into the bulk grease.

A Nafion‐filled Polycarbonate Track‐Etched Composite Membrane with Enhanced Selectivity for Direct Methanol Fuel Cells

AbstractThe high proton conductivity of Nafion© membranes in direct methanol fuel cells is attributed to a random three dimensional 3D network of elongated ion channels formed by bundles of rod‐like inverted micelles. However, this network is also responsible for high methanol crossover. In addition, its conductivity is impaired at temperatures 120 °C and above due to ion channel rearrangement, thus limiting the operational temperature to 60–80 °C. Here we report a composite proton exchange membrane prepared by filling the pores of polycarbonate track‐etched membrane with Nafion, which promote channel orientation roughly normal to the surface. The proton conductivity of this geometry is significantly enhanced, presumably due to the restricted swelling, resulting in a better ion channel connectivity and realignment in the axial pore direction upon hydration. The permeability of sodium chloride and methanol, though, is suppressed, presumably due to formation of regions of closely packed sulfonic groups, which facilitate proton transfer but strongly exclude other solutes. Composite membranes with improved conductivity and selectivity based on the principle presented here are expected to allow operating direct methanol fuel cells at higher temperatures and with higher methanol concentrations, thus reducing costs and increasing the efficiency.

Synthesis and characterization of asymmetrical gemini surfactants.

The effect of variation in the length of surfactant hydrocarbon tail groups was tested in a series of dissymmetric gemini surfactants (N1-alkyl N1,N1,N3,N3-tetramethyl-N3-(6-pyren-6yl)-hexyl)propane-1,3-diammonium dibromide designated as CmC3CnBr, with m = hexyl pyrene, and n = 8, 12, 14, 16, and 18. The aggregation properties of these surfactants have been investigated by means of 1H NMR, fluorescence spectroscopy, surface tension and electrical conductivity measurements. The critical micelle concentration (CMC) was determined using surface tension and confirmed using the specific conductance method. Krafft temperatures and the degree of micelle ionization (α) were obtained from specific conductance measurements. With an increase of the dissymmetry (m/n) ratio, the CMC decreased linearly and an increase in the Krafft temperatures was observed for all of the gemini surfactants. α values for the dissymmetric GS were higher than those of the m-3-m counterparts, which may be attributed to enhanced micelle-micelle interactions that arise from increased hydrophobicity of the hydrocarbon chains. The introduction of the bulky pyrenyl tail group resulted in much lower CMC values compared to their symmetrical counterparts affecting the packing of these surfactants at the air/water interface, which resulted in high-ordered structures (lamellar and inverted micelles). This in turn affected the thermodynamic parameters of the micellization.

Rotary motion of a micro-solid particle under a stationary difference of electric potential.

The periodic rotary motion of spherical sub-millimeter-sized plastic objects is generated under a direct-current electric field in an oil phase containing a small amount of anionic or cationic surfactant. Twin-rotary motion is observed between a pair of counter-electrodes; i.e., two vortices are generated simultaneously, where the line between the centers of rotation lies perpendicular to the line between the tips of the electrodes. Interestingly, this twin rotational motion switches to the reverse direction when an anionic surfactant is replaced by a cationic surfactant. We discuss the mechanism of this self-rotary motion in terms of convective motion in the oil phase where nanometer-sized inverted micelles exist. The reversal of the direction of rotation between anionic and cationic surfactants is attributable to the difference in the charge sign of inverted micelles with surfactants. We show that the essential features in the experimental trends can be reproduced through a simple theoretical model, which supports the validity of the above mechanism.

A Novel Composite Nafion/Anodized Aluminium Oxide Proton Exchange Membrane

AbstractThe high proton conductivity of proton exchange membranes (PEMs) made of Nafion® is attributed to a random 3D network of elongated water channels formed by bundles of rod‐like inverted micelles. Alignment of bundles, e.g., by stretching, is known to significantly enhance the in‐plane conductivity, yet achieving alignment normal to the membrane surface, desired for most applications, is challenging. A few attempts to obtain such alignment by confining Nafion in nanometric trans‐membrane pores of solid anodized aluminium oxide (AAO) membranes were reported, so far with limited success. Here we demonstrate that considerable pore filling of AAO with 200 nm pores by Nafion could be achieved through (i) use of Nafion concentrations below the threshold concentration C*, above which Nafion molecules form large aggregates; and (ii) control of filling rate through a combination of thermal and vacuum evaporation of Nafion solution through the membrane. The proton conductivity and NaCl diffusion permeability (sodium chloride diffusivity) tested by electrochemical impedance spectroscopy demonstrated superior intrinsic conductivity and selectivity of the composite membrane as compared to commercial Nafion membranes.

Spectral features of 4,4-diaminodiphenyl sulfone in anionic and cationic inverted micelles

This Letter reports the photophysics of 4,4-diaminodiphenyl sulfone in anionic and cationic reverse micelles (RM). Decreased fluorescence intensity with significant blue shift of intramolecular charge transfer (ICT) fluorescence maximum and longer emission lifetime of the entrapped probe in motionally restricted water nano-pool of anionic RM could be observed. Bi-exponential decay in anionic RM appears due to polarity heterogeneity in the pool. In a nut shell, experiments establish that the probe is anchored in the micellar head group region of anionic RM vis-à-vis far away from the core in cationic RM. Increasing pool size show the opposite effect to the probe.

Emergence of a thread-like pattern with charged phospholipids on an oil/water interface

The spontaneous formation of a thread-like pattern with negatively charged lipids on an oil/water interface is reported. An analysis of the time-dependent change at the interface observed by fluorescence microscopy revealed that the thread-like pattern is generated through a two-step mechanism. First, inverted lipid micelles in the bulk-oil phase gradually diffuse onto the oil/water interface. Next, the micelles are adsorbed on the interface and self-assemble to form the thread-like pattern. The essential characteristics of this pattern formation are theoretically reproduced by a simple Monte Carlo simulation that takes into account the kinetics in the coalescence of charged micelles on a 2D interface.

Violaxanthin and diadinoxanthin de-epoxidation in various model lipid systems.

The xanthophyll cycle is an important photoprotective process functioning in plants. One of its forms, the violaxanthin (Vx) cycle, involves interconversion between: Vx, antheraxanthin (Ax) and zeaxanthin (Zx). Another kind of the xanthophyll cycle is the diadinoxanthin (Ddx) cycle in which interconversion between Ddx and diatoxanthin (Dtx) occurs. In this study an information on molecular mechanism and regulation of these two types of the xanthophyll cycle is presented. The influence of lipids on the de-epoxidation of the xanthophyll cycle pigments was investigated, with special focus put on the significance of physical properties of the aggregates formed by inverted lipid micelles, which are necessary for activity of the xanthophyll cycle enzymes. In particular, thickness of the hydrophobic fraction of the aggregates, size of the inverted micelles, suggested by mathematical description of the structures and solubility of Vx and Ddx in various kind of lipids were studied. Obtained results show that the rate of de-epoxidation is strongly dependent on the physicochemical properties of the lipids used. The key role for enzyme activation play non-bilayer lipids and the parameters of inverted micelles such as thickness, fluidity of hydrophobic core and their diameter. The presented results show that MGDG and other non-lamellar lipids like different forms of phosphatidylethanolamine are necessary for the Vx and Ddx de-epoxidation because they provide the three-dimensional structures, which are needed for the binding of de-epoxidases and for the accessibility of Vx and Ddx to these enzymes.

Violaxanthin and diadinoxanthin cycles as an important photoprotective mechanism in photosynthesis

The molecular mechanism and regulation of violaxanthin (Vx) and diadinoxanthin (Ddx) cycle are discussed. The influence of lipids on the de-epoxidation of the xanthophyll cycle pigments was investigated. Experiments on the significance of physical properties of the aggregates formed by inverted lipid micelles, which are necessary for de-epoxidation, on the conversion of Vx into antheraxanthin (Ax) and zeaxanthin (Zx) and diadinoxanthin (Ddx) to diatoxanthin (Dtx) were performed. Thickness of the hydrophobic fraction of the aggregates, size of the inverted micelles, suggested by mathematical description of the structures, and solubility of Vx and Ddx in various kinds of lipids were the next tested parameters. Obtained results show that the rate of de-epoxidation was strongly dependent on physicochemical properties of lipids. The key role for enzyme activation play non-bilayer lipids and the parameters of inverted micelles created by them, such as thickness, molecular dynamics of hydrophobic core, and their diameter. Additionally the influence of thylakoid lipids on the de-epoxidation of Vx, associated with the light-harvesting complex of PSII (LHCII) were carried out. Almost complete Vx de-epoxidation in the LHCII fractions containing high amounts of endogenous monogalactosyldiacylglycerol (MGDG) was observed in in vitro assays. LHCII preparations with low concentrations of MGDG exhibited a strongly reduced Vx de-epoxidation, which could be increased by addition of exogenous, pure MGDG. The presented results showed that MGDG and other nonlamellar lipids are necessary for the solubilization of Vx and Ddx and they provide also the three-dimensional structures, which are needed for the binding of de-epoxidases and for the accessibility of Vx and Ddx to these enzymes.

Nanoscale segregation, molecular recognition and fluorophobic effect – from molecular design towards complex mesophase morphologies

Mesomorphic structure formation of hydrogen-bonded complexes of amino substituted 1,3,5-triazines with complementary (semiperfluoro)alkoxybenzoic acids is presented. The substitution pattern of both components was modified systematically in order to elucidate the influence of molecular parameters on the mesophase morphologies of the binary mixed systems. The phase sequence of the triazines, and of their associates with the acids, spans the range from smectic layer structures to discontinuous cubic phases composed of closed inverted micelles. Columnar phases with various two-dimensional lattice symmetries and bicontinuous cubic phases were found as intermediates. The mesophase morphologies are discussed in terms of the microsegregation of rigid polar, lipophilic and fluorinated molecular blocks in different sub-spaces along with tailoring the shape of (curved) aggregates by the space requirement of incompatible molecular fragments.

Interaction of Ethanol with Biological Membranes: The Formation of Non-bilayer Structures within the Membrane Interior and their Significance

To gain a better understanding of how ethanol affects biological membranes, we have performed a series of atomic-scale molecular dynamics simulations of phospholipid membranes in aqueous solution with ethanol, whose concentration was varied from 2.5 to 30 mol % (lipid-free basis). At concentrations below the threshold value of approximately 12 mol % (30.5 v/v %) ethanol induces expansion of the membrane, accompanied by a drop in the membrane thickness as well as disordering and enhanced interdigitation of lipid acyl chains. These changes become more pronounced with increase in ethanol concentration, but the bilayer structure of the membrane is maintained. Above the threshold concentration the appearance of multiple transient defects in the lipid/water interface eventually gives rise to desorption and assembly of some of the lipids into non-bilayer structures within the membrane interior. These structures, being small and irregular, resemble inverted micelles and have a long-lived character. Furthermore, formation of the non-bilayer structures is accompanied by mixing of lipids that belong to the opposite membrane leaflets, thereby leading to irreversible changes in the membrane structure. Remarkably, this observation of the formation of non-bilayer structures within the membrane interior, being in good agreement with experimental data, is found to be robust with respect to both the simulation conditions (the system size and the presence of salt) and the type of lipids (phosphatidylcholine and phosphatidylethanolamine). We discuss the significance of these non-bilayer structures in relation with the well-known ability of ethanol to promote membrane hemifusion as well as with the possible role of the micelle-like structures as a delivery system for polar solutes and ions. The ethanol-induced "damage" to the bilayer structure also suggests that strong alcoholic beverages ( approximately 40 v/v %) might be potentially hazardous to the epithelial tissues of the human body (such as lips, mouth, throat, gullet, and stomach) that come in direct contact with high-concentrations of ethanol.

Influence of Solvent on Micellar Morphologies of Semifluorinated Block Copolymers

The influence of solvents on micellar architectures of block copolymers composed of poly(1H,1H-dihydroperfluorooctyl methacrylate) and poly(ethylene oxide) was investigated. In this study, binary solvents with desired proportions were chosen, which had remarkable influence on the morphology of the resulting micelles. With simple adjusting the composition of the binary solvent of chloroform and trichlorofluoromethane, interesting shapes of micelle-like aggregates, such as core-shell, cylinder, worm-like and inverted micelles were formed with sizes of 15, 70, 30 and 250 nm, respectively. In the case of methanol/water system, core-shell spheres and vesicles were produced by varying the proportion of the contents. The morphologies were also tuned to honeycomb-like and bowl-shaped micelles as well as large planar lamellae with holes in DMF and water binary solvent.

Nanoscale properties of polymer fuel cell materials-A selected review

The properties of the components of a membrane electrode assembly in a polymer electrolyte fuel cell (PEFC) determine its efficiency and performance. This paper aims at demonstrating the importance of nanoscale properties of PEFC membranes and electrodes and discussing the information obtained by various experimental techniques. The nanostructure and conductivity of freshly prepared as well as artificially degraded Nafion membranes and Pt/C electrodes are investigated by contact atomic force microscopy (AFM), conductive AFM, pulsed force mode (PFM)-AFM, in situ scanning tunnelling microscopy (STM), and scanning electron microscopy. The different techniques can provide complementary information on structure and conductivity. With in situ STM on Pt catalyst covered graphite, a layer of very small Pt particles between the catalyst particles is imaged, which is probably not visible with TEM and can explain a systematic discrepancy between TEM and XRD in particle size distribution. Conductive AFM is used to investigate the conductivity of Nafion. The images show a quite inhomogeneous distribution of current at the surface. The percentage of conductive surface increases with humidity, but regions without any current still present up to 80% of relative humidity (RH). Comparison with PFM-AFM images, where differences in adhesion forces are measured, indicates that hydrophobic regions are present at the surface with comparable dimensions, which are attributed to non-conductive PTFE-like polymer backbone. The changes in hydrophilic and hydrophobic parts after artificial degradation by plasma etching in air plasma can be imaged by PFM. High-resolution current images of the membrane were used to directly compare the measured nanostructure of the single conductive channels with model predictions from the literature. Recent models in the literature propose the formation of water-filled inverted micelles, with a mean diameter of 2.4 nm, and their agglomeration into clusters agrees well with the current images