Single-chain Amphiphiles Research Articles

Delivery of siRNA via cationic Sterosomes to enhance osteogenic differentiation of mesenchymal stem cells

Noggin is a specific antagonist of bone morphogenetic proteins (BMPs) that can prevent the interaction of BMPs with their receptors. RNA interfering molecules have been used to downregulate noggin expression and thereby stimulate BMP signaling and osteogenesis. Cationic liposomes are considered one of the most efficient non-viral systems for gene delivery. In the past decade, non-phospholipid liposomes (Sterosomes) formulated with single-chain amphiphiles and high content of sterols have been developed. In particular, Sterosomes composed of stearylamine (SA) and cholesterol (Chol) display distinct properties compared with traditional phospholipid liposomes, including increased positive surface charges and enhanced particle stability. Herein, we report SA/Chol Sterosome and small interfering RNA (siRNA) complexes that significantly enhanced cellular uptake and gene knockdown efficiencies in adipose derived mesenchymal stem cells with minimal cytotoxicity compared with commercially available lipofectamine 2000. Furthermore, we confirmed osteogenic efficacy of these Sterosomes loaded with noggin siRNA in in vitro two- and three-dimensional settings as well as in a mouse calvarial defect model. The delivery of siRNA via novel SA/Chol Sterosomes presents a powerful method for efficient gene knockdown. These distinct nanoparticles may present a promising alternative approach for gene delivery.

Chain-Length Heterogeneity Allows for the Assembly of Fatty Acid Vesicles in Dilute Solutions

A requirement for concentrated and chemically homogeneous pools of molecular building blocks would severely restrict plausible scenarios for the origin of life. In the case of membrane self-assembly, models of prebiotic lipid synthesis yield primarily short, single-chain amphiphiles that can form bilayer vesicles only at very high concentrations. These high critical aggregation concentrations (cacs) pose significant obstacles for the self-assembly of single-chain lipid membranes. Here, we examine membrane self-assembly in mixtures of fatty acids with varying chain lengths, an expected feature of any abiotic lipid synthesis. We derive theoretical predictions for the cac of mixtures by adapting thermodynamic models developed for the analogous phenomenon of mixed micelle self-assembly. We then use several complementary methods to characterize aggregation experimentally, and find cac values in close agreement with our theoretical predictions. These measurements establish that the cac of fatty acid mixtures is dramatically lowered by minor fractions of long-chain species, thereby providing a plausible route for protocell membrane assembly. Using an NMR-based approach to monitor aggregation of isotopically labeled samples, we demonstrate the incorporation of individual components into mixed vesicles. These experiments suggest that vesicles assembled in dilute, mixed solutions are depleted of the shorter-chain-length lipid species, a finding that carries implications for the composition of primitive cell membranes.

Impact of interfacial cholesterol-anchored polyethylene glycol on sterol-rich non-phospholipid liposomes

HypothesisLiposomes made of single-chain amphiphiles and a large amount of sterols display several advantages including a limited permeability. In the present paper, we examine the possibility to prepare such non-phospholipid liposomes with interfacial polyethylene glycol (PEG) in order to improve their circulation in the blood stream. Cholesterol (Chol) was chosen as the PEG anchor. ExperimentsThe phase behavior of mixtures of palmitic acid (PA) and cholesterol including various proportions of PEGylated cholesterol (PEG-Chol) was characterized. In conditions leading to the formation of fluid bilayers, properties of the resulting liposomes were assessed. FindingsUp to 20mol% of PEGylated cholesterol could be introduced without significant perturbations in fluid bilayers made of PA and cholesterol. With 10mol% PEG-Chol, PA/Chol/PEG-Chol liposomes showed a very limited permeability to calcein and doxorubicin. Doxorubicin could be actively loaded in PA/Chol/PEG-Chol liposomes with a high drug loading efficiency and a high drug to lipid ratio. Pharmaco-kinetic experiments in rats indicated that interfacial PEG reduced the clearance of PA/Chol liposomes compared to the naked ones. However the lifetime of these non-phospholipid liposomes in the blood circulation was considerably shorter than that observed for control PEGylated phospholipid liposomes, a phenomenon associated with the negative interfacial charge of the PA/Chol/PEG-Chol liposomes.

Lamellar self-assemblies of single-chain amphiphiles and sterols and their derived liposomes: Distinct compositions and distinct properties

Typically, single-chain amphiphiles and sterols do not form fluid lamellar phases once hydrated individually. Most of the single-chain amphiphiles form actually micelles in aqueous environments, while sterols display a very limited solubility in water. However, under certain conditions, mixtures of single-chain amphiphiles and sterols lead to the formation of stable fluid bilayers. Over the past decade, several of these systems leading to fluid lamellar self-assemblies have been identified and this article reviews the current knowledge relative to these non-phospholipid bilayers made of single-chain amphiphiles and sterols. It presents an integrated view about the molecular features that are required for their stability, the properties they share, and the origin of these characteristics. It was also shown that these lamellar systems could lead to the formation of unilamellar vesicles, similar to phospholipid based liposomes. These vesicles display distinct properties that make them potentially appealing for technological applications; they display a limited permeability, they are stable, they are formed with molecules that are relatively chemically inert (and relatively cheap), and they can be readily functionalized. The features of these distinct liposomes and their technological applications are reviewed. Finally, the putative biological implications of these non-phospholipid fluid bilayers are also discussed.

Liver Fatty Acid-binding Protein Binds Monoacylglycerol in Vitro and in Mouse Liver Cytosol

Liver fatty acid-binding protein (LFABP; FABP1) is expressed both in liver and intestinal mucosa. Mice null for LFABP were recently shown to have altered metabolism of not only fatty acids but also monoacylglycerol, the two major products of dietary triacylglycerol hydrolysis (Lagakos, W. S., Gajda, A. M., Agellon, L., Binas, B., Choi, V., Mandap, B., Russnak, T., Zhou, Y. X., and Storch, J. (2011) Am. J. Physiol. Gastrointest. Liver Physiol. 300, G803-G814). Nevertheless, the binding and transport of monoacylglycerol (MG) by LFABP are uncertain, with conflicting reports in the literature as to whether this single chain amphiphile is in fact bound by LFABP. In the present studies, gel filtration chromatography of liver cytosol from LFABP(-/-) mice shows the absence of the low molecular weight peak of radiolabeled monoolein present in the fractions that contain LFABP in cytosol from wild type mice, indicating that LFABP binds sn-2 MG in vivo. Furthermore, solution-state NMR spectroscopy demonstrates two molecules of sn-2 monoolein bound in the LFABP binding pocket in positions similar to those found for oleate binding. Equilibrium binding affinities are ∼2-fold lower for MG compared with fatty acid. Finally, kinetic studies examining the transfer of a fluorescent MG analog show that the rate of transfer of MG is 7-fold faster from LFABP to phospholipid membranes than from membranes to membranes and occurs by an aqueous diffusion mechanism. These results provide strong support for monoacylglycerol as a physiological ligand for LFABP and further suggest that LFABP functions in the efficient intracellular transport of MG.

Self-Assembly of Monotethered Single-Chain Nanoparticle Shape Amphiphiles.

Shape amphiphiles with distinct shapes and amphiphilic properties can be used as fundamental building blocks in the fabrication of novel structures and advanced materials. In this research synthesis and self-assembly of monotethered single-chain nanoparticle shape amphiphiles are reported. Poly(2-(dimethylamino)ethyl methacrylate)-block-polystyrene (PDMAEMA-b-PS) was synthesized by two-step reversible addition-fragmentation chain transfer (RAFT) polymerization. The PDMAEMA blocks were intramolecularly cross-linked by 1,4-diiodobutane (DIB) at significantly low concentrations, and PS-tethered PDMAEMA single-chain nanoparticles were prepared. Gel permeation chromatograph, 1H NMR and transmission electron microscopy results all indicated successful synthesis of the structures. The controlled self-assembly of the shape amphiphiles in selective solvents was investigated. Depending on the size of the single-chain nanoparticles, the shape amphiphiles self-assemble into strawberry-like micelles, a structure with single-chain nanoparticles in the corona and PS in the core, or vesicles in aqueous solutions. Similar to the self-assembled structures in aqueous solution, the morphology of the aggregates in methanol changes from micellar structure to vesicular structure with the decrease of the PDMAEMA single-chain nanoparticles size. In cyclohexane, the shape amphiphiles self-assemble into bunchy micelles with single-chain nanoparticles in the cores and linear PS in the coronae.

The yin of exofacial protein sulfhydryls and the yang of intracellular glutathione in in vitro transfection with SS14 bioreducible lipoplexes

Although redox-sensitive transfectants have been considered hitherto as the Holy Grail of gene delivery because of their ability to restrict the release of nucleic acids to intracellular compartments, the reasons for their sometimes lackluster performance do not seem likewise clear. To ascertain the possible influence of extracellular soluble thiols, exofacial protein sulfhydryls (EPTs) and glutathione (GSH) on the overall efficacy of bioreducible lipoplexes, we utilized a cationic gemini surfactant – SS14 – in which the two single-chain amphiphiles are held together by a suitable redox-sensitive linkage. We herein draw a big picture whereby the interaction of bioreducible lipoplexes with cells and their internalization are tightly coupled events that ultimately do affect transfection. Specifically, we provide evidence that EPTs entail the reduction-triggered disruption of SS14 lipoplexes in plain Dulbecco's Modified Eagle Medium (DMEM), thereby resulting in a considerable waste (ca. 30%) of nucleic acids and low transgene expression. The DNA release from bioreducible lipoplexes can be blunted to ca. 16% by transfecting cells in complete medium and fully reverted by preincubating them for 1h before delivery in the same culture supernatant (i.e. preconditioning), thus significantly increasing transfection by ca. 3-fold and 10-fold, respectively. These results lead to the proposal of the protein corona as the central mediator in shielding SS14 bioreducible lipoplexes from the action of EPTs in the early phase of delivery and provide a smart solution as to how to increase their efficacy. Besides, we pinpoint associations between intracellular GSH levels and the extent of transfection. All these issues were unique to bioreducible lipoplexes.

Assembly of Lipid Bilayers on Silica and Modified Silica Colloids by Reconstitution of Dried Lipid Films

A method is presented for the assembly of lipid bilayers on silica colloids via reconstitution of dried lipid films solvent-cast from chloroform within packed beds of colloids ranging from 100 nm to 10 μm in diameter. Rapid solvent evaporation from the packed bed void volume results in uniform distribution of dried lipid throughout the colloidal bed. Fluorescence measurements indicate that significant, if not quantitative, retention of DOPC or DPPC films cast between sub-bilayer and multilayer quantities occurs when the colloids are redispersed in aqueous solution. Phospholipid bilayers assembled in this manner are shown to effectively passivate the surface of 250 nm colloids to nonspecific adsorption of bovine serum albumin. The method is shown to be capable of preparing supported bilayers on colloid surfaces that do not generally support vesicle fusion such as poly(ethylene glycol) (PEG) modified silica colloids. Bilayers of lipids that have not been reported to self-assemble by vesicle fusion, including gel-phase lipids and single-chain diacetylene amphiphiles, can also be formed by this method. The utility of the solid-core support is demonstrated by the facile assembly of supported lipid bilayers within fused silica capillaries to generate materials that are potentially suitable for the analysis of membrane interactions in a microchannel format.

Dominance of long-chain N,O-diacylated ethanolamine in mixed amphiphilic acid amide monolayers

The main characteristics of Langmuir monolayers of acid amide amphiphiles with one and two alkyl chains are fundamentally different. This is demonstrated by comparison of surface pressure–area ( π– A) isotherms, the mesoscopic morphology, and the two-dimensional lattice structure of the condensed phases in the case of the single-chain acid amides with N-myristoyl ethanolamine (TDAHA) and 3-hydroxy-N-tridecyl propanoic acid amide (HTPA) as well as in the case of the double-chain acid amide with N,O-dimyristoyl ethanolamine (TAOAE). The studies of the binary mixtures TDAHA/TAOAE, HTPA/TDAHA, HTPA/TAOAE (1:1) and ternary mixtures TAOAE/TDAHA/HTPA (1:1:1) performed at 5 °C and 25 °C allow the comparison with the single components. The results indicate convincingly that all binary 1:1 monolayers and the ternary 1:1:1 monolayer exist as homogeneously mixed systems. The dominance of the double-chain TAOAE in the binary and ternary monolayers mixed with single-chain acid amide amphiphiles TDAHA and HTPA in mesoscopic and molecular scale can be unequivocally concluded from the GIXD and BAM measurements. The probability for the presence of N,O-diacylated ethanolamine, such as TAOAE, as impurity in N-acylated ethanolamine, e.g. TDAHA, is high so that in such systems the most important interfacial characteristics are dominated by the impurity.

Interactions between Catalysts and Amphiphilic Structures and their Implications for a Protocell Model

One of the essential elements of any cell, including primitive ancestors, is a structural component that protects and confines the metabolism and genes while allowing access to essential nutrients. For the targeted protocell model, bilayers of decanoic acid, a single-chain fatty acid amphiphile, are used as the container. These bilayers interact with a ruthenium-nucleobase complex, the metabolic complex, to convert amphiphile precursors into more amphiphiles. These interactions are dependent on non-covalent bonding. The initial rate of conversion of an oily precursor molecule into fatty acid was examined as a function of these interactions. It is shown that the precursor molecule associates strongly with decanoic acid structures. This results in a high dependence of conversion rates on the interaction of the catalyst with the self-assembled structures. The observed rate logically increases when a tight interaction between catalyst complex and container exists. A strong association between the metabolic complex and the container was achieved by bonding a sufficiently long hydrocarbon tail to the complex. Surprisingly, the rate enhancement was nearly as strong when the ruthenium and nucleobase elements of the complex were each given their own hydrocarbon tail and existed as separate molecules, as when the two elements were covalently bonded to each other and the resulting molecule was given a hydrocarbon tail. These results provide insights into the possibilities and constraints of such a reaction system in relation to building the ultimate protocell.

Spontaneous insertion of lipopolysaccharide into lipid membranes from aqueous solution

Lipopolysaccharide (LPS), one of the main components of outer membranes of Gram-negative bacteria, consists of a hydrophobic lipid (lipid A) with six hydrocarbon chains and a large hydrophilic polysaccharide chain. LPS plays endotoxic roles and can stimulate macrophages and B cells. To elucidate the mechanism of the interaction of LPS with various cell membranes, it is important to investigate the interaction of wild type LPS in a buffer with lipid membranes. In this report we investigated the interaction of low concentrations of LPS in a buffer with giant unilamellar vesicles (GUVs) of dioleoylphosphatidylcholine (DOPC) membrane in the liquid-crystalline (Lα) phase and sphingomyelin (SM)/cholesterol(chol) (molar ration; 6/4) membrane in the liquid-ordered (lo) phase. We found that low concentrations (less than critical micelle concentration) of LPS in aqueous solution induced the shape changes such as the transformation from a prolate to a two-spheres-connected by a very narrow neck in the DOPC-GUVs and also in the SM/chol (6/4)-GUVs above their threshold concentrations. The analysis of the shape changes of the GUVs indicates that the monomers of LPS can insert spontaneously into the external monolayer of the lipid membranes of these GUVs from the aqueous solution. Moreover, higher concentrations of LPS induced the vesicle fission of SM/chol(6/4)-GUVs above its higher threshold concentration. The vesicle fission of GUVs is similar to those induced by single long chain amphiphiles such as lysophosphatidylcholine. On the basis of these results, we discuss the interaction of wild type LPS with lipid membranes and cell membranes. These results suggest that LPS molecules can insert spontaneously into the external monolayer of the plasma membranes composed of the Lα phase-membrane and the microdomain in the lo phase.

Self-assembly based on hydrotropic counterion—single-chain amphiphile ion pairs

We investigate the effect of organic hydrotropic counterions on the self-assembled structures formed by pure counterion—single-chain amphiphile ion pairs. The effect of inorganic counterions on single-chain amphiphiles has been studied for years, taking into account the Hofmeister series that directly affects the micellization. Here, hexadecyldimethylbenzylammonium salicylate (C16Sal) in aqueous solution is used as a model for the influence of organic counterions, and the results have been compared with those previously published for inorganic counterions, specifically hexadecyldimethylbenzylammonium chloride (C16Cl). The studies have been performed by using conductivity, dynamic light scattering, as well as atomic force microscopy. We demonstrate the formation of vesicles and suggest the presence of a vesicle-to-micelle transition at higher concentrations. The Gibbs free energy associated with the self-assembly process has been estimated on the basis of the well-known mass-action model. The main conclusion is that the use of hydrotropic counterions instead of classical inorganic ions dramatically changes the packing parameter of single-chain amphiphiles to higher values, resulting in bilayer structures. We propose that these systems are good and cheap alternatives to double-chain amphiphiles for forming more complex structures like vesicles.

Chemical Evolution of Amphiphiles: Glycerol Monoacyl Derivatives Stabilize Plausible Prebiotic Membranes

The self-assembly of simple amphiphiles like fatty acids into cell-like membranous structures suggests that such structures were available on prebiotic Earth to support the origin of cellular life. However, the composition of primitive membranes remains unclear because the physical properties of the aqueous environment in which they assembled are relatively unconstrained in terms of temperature, pH, and ionic concentrations. It seems likely that early membranes were composed of mixtures of various amphiphiles in an aqueous medium warmed by geothermal activity prevalent in the Archean era. To better understand the properties of mixed bilayers formed by binary mixtures of single-chain amphiphiles under these conditions, we conducted stability experiments, using membranes composed of various fatty acids having hydrocarbon chain length between 8 and 18 carbons, in mixtures with their glycerol monoacyl amphiphile derivatives (GMAs). The parameters investigated were critical vesicle concentration (CVC), encapsulation, and temperature-dependent stability. We found that hydrocarbon chain length and the presence of GMAs were major factors related to membrane stability. As chain length increased, GMA additions decreased the CVC of the mixtures 4- to 9-fold. Encapsulation ability also increased significantly as a function of chain length, which reduced permeation of small marker molecules. However, long exposures to temperatures in excess of 60 degrees C resulted in a total release of encapsulated solutes and extensive mixing of the membrane components between vesicles. We conclude that GMAs can significantly increase the stability of mixed amphiphile membranes, but further studies are required to establish model membranes that are stable at elevated temperatures.

Formation of Protocell-like Vesicles in a Thermal Diffusion Column

Many of the properties of bilayer membranes composed of simple single-chain amphiphiles seem to be well-suited for a potential role as primitive cell membranes. However, the spontaneous formation of membranes from such amphiphiles is a concentration-dependent process in which a significant critical aggregate concentration (cac) must be reached. Since most scenarios for the prebiotic synthesis of fatty acids and related amphiphiles would result in dilute solutions well below the cac, the identification of mechanisms that would lead to increased local amphiphile concentrations is an important aspect of defining reasonable conditions for the origin of cellular life. Narrow, vertically oriented channels within the mineral precipitates of hydrothermal vent towers have previously been proposed to act as natural Clusius−Dickel thermal diffusion columns, in which a strong transverse thermal gradient concentrates dilute molecules through the coupling of thermophoresis and convection. Here we experimentally demonstrate that a microcapillary acting as a thermal diffusion column can concentrate a solution of oleic acid. Upon concentration, self-assembly of large vesicles occurs in regions where the cac is exceeded. We detected vesicle formation by fluorescence microscopy of encapsulated dye cargoes, which simultaneously concentrated in our channels. Our findings suggest a novel means by which simple physical processes could have led to the spontaneous formation of cell-like structures from a dilute prebiotic reservoir.

Dicarboxylic acid esters as transdermal permeation enhancers: Effects of chain number and geometric isomers

A series of transdermal permeation enhancers based on dicarboxylic acid esters was studied. Single-chain amphiphiles were markedly more effective than the double-chain ones. Monododecyl maleate, that is a cis derivative, was a more potent enhancer than its trans isomer, while the activity of succinates strongly depended on the donor vehicle. No difference between diastereoisomeric tartaric and meso-tartaric acid derivatives was found.

Thermostability of model protocell membranes

The earliest cells may have consisted of a self-replicating genetic polymer encapsulated within a self-replicating membrane vesicle. Here, we show that vesicles composed of simple single-chain amphiphiles such as fatty acids, fatty alcohols, and fatty-acid glycerol esters are extremely thermostable and retain internal RNA and DNA oligonucleotides at temperatures ranging from 0 degrees C to 100 degrees C. The strands of encapsulated double-stranded DNA can be separated by denaturation at high temperature while being retained within vesicles, implying that strand separation in primitive protocells could have been mediated by thermal fluctuations without the loss of genetic material from the protocell. At elevated temperatures, complex charged molecules such as nucleotides cross fatty-acid-based membranes very rapidly, suggesting that high temperature excursions may have facilitated nutrient uptake before the evolution of advanced membrane transporters. The thermostability of these membranes is consistent with the spontaneous replication of encapsulated nucleic acids by the alternation of template-copying chemistry at low temperature with strand-separation and nutrient uptake at high temperature.

A project‐based biochemistry laboratory promoting the understanding and uses of fluorescence spectroscopy in the study of biomolecular structures and interactions

A laboratory project for a first semester biochemistry course is described, which integrates the traditional classroom study of the structure and function of biomolecules with the laboratory study of these molecules using fluorescence spectroscopy. Students are assigned a specific question addressing the stability/function of lipids, proteins, or nucleic acids, and asked to design an experiment to answer the question using fluorescence methodologies. Students study phase equilibria and determine the critical micelle concentration of single chain amphiphiles, the melting point of multilamellar vesicles, and the melting points and thermodynamic constants (K(eq) , ΔG(0) , ΔH(0) and ΔS(0) ) for denaturation of ds-DNA and proteins. In addition, they examine binding properties of proteins. These laboratory experiments are designed to support student learning of the major themes of structure and function in the course.

Vesicle Fission of Giant Unilamellar Vesicles of Liquid-Ordered-Phase Membranes Induced by Amphiphiles with a Single Long Hydrocarbon Chain

Vesicle fissions are very important processes of biomembranes in cells, but their mechanisms are not clear and are controversial. Using the single giant unilamellar vesicle (GUV) method, we recently found that low concentrations (less than the critical micelle concentration (CMC)) of lysophosphatidylcholine (lyso-PC) induced the vesicle fission of GUVs of dipalmitoylphosphatidylcholine/cholesterol(6/4) (DPPC/chol(6/4)) membranes and sphingomyelin/cholesterol membranes (6/4) in the liquid-ordered (lo) phase. In this report, to elucidate its mechanism, we have investigated the effect of low concentrations (much less than their CMC) of other amphiphiles with a single long hydrocarbon chain (i.e., single long chain amphiphiles) on DPPC/chol(6/4) GUVs as well as the effect of the membrane composition on the lyso-PC-induced vesicle fission. We found that low concentrations of single long chain amphiphiles (lyosophosphatidic acid, octylglucoside, and sodium dodecyl sulfate) induced the shape change from a prolate to two spheres connected by a very narrow neck, indicating that the single long chain amphiphiles can be partitioned into the external monolayer in the lo phase of the GUV from the aqueous solution. As the single long chain amphiphile concentrations were increased, all of them induced vesicle fission of DPPC/chol(6/4) GUVs above their threshold concentrations. To elucidate the role of cholesterol in the single long chain amphiphile-induced vesicle fission, we investigated the effect of lyso-PC on GUVs of dioleoyl-PC (DOPC)/chol(6/4) membranes in the Lalpha phase; no vesicle fission occurred, indicating that cholesterol in itself did not play an important role in the vesicle fission. Finally, to elucidate the effect of the inclusion of DOPC in the lo-phase membrane of GUVs on the lyso-PC-induced vesicle fission of the DPPC/chol(6/4) GUV, we investigated the effect of low concentrations of lyso-PC on GUVs of DPPC/DOPC/chol membranes. With an increase in DOPC concentration in the membrane, the threshold concentration of lyso-PC increased. At and above 30 mol % DOPC, no vesicle fission occurred. On the basis of these results, we have proposed a hypothesis of the mechanism of the single long chain amphiphile-induced vesicle fission of a GUV of a lo-phase membrane.

The dioctadecylamine monolayer: Textures, phase transitions, and dendritic growth

The phase diagram of dioctadecylamine Langmuir monolayer has been determined from pressure–area isotherms and from direct observations of the monolayer using Brewster angle microscopy. We describe the observed domains, textures, and phase boundaries for the mesophases presented by this system between 5 °C and 45 °C, at pH=3. The phases were named as G, LE, S1, and S2 according to their apparent texture. Contrast between domains of condensed phases is quite low, indicating small tilting of the amine tails. The G–S1, G–S2, G–LE, and LE–S1 transitions seem to be of first order; meanwhile, the S1–S2 transition seems to be of second order. We observed how the froths changed when the area density increases at constant pressure, along the G–L, G–S1, and G–S2 phase transitions. In the L–S1 transition, the shape of the domains of the emerging phase is of sixfold dendrites. The phase diagram obtained is very different from those obtained for single chain amphiphiles. In this system, the extent of the phases depends on the acid used to fix the pH. In addition, all our observations indicate that dioctadecylamine does not form a monolayer above pH∼3.9.

Self-assembly and film stability of a micelle of a single-chain quaternary ammonium amphiphile containing azobenzene on mica

The self-assembling behavior of a single-chain quaternary ammonium amphiphile bearing azobenzene (C 12AzoC 6N +) on freshly cleaved mica sheet has been investigated by atomic force microscopy (AFM) method. Confocal microscopic Raman spectra confirm the adsorption of the self-assembled monolayer structure. Ex-situ AFM reveals that C 12AzoC 6N + forms branch-like stripes indicating the fusion and reorganization of the micelles during drying in air as the in-situ AFM has revealed that surfactant forms spherical micelles on the mica surface. The nano-sized surface structure is strongly dependent on the change of molecular structure, which resulted from photo-induced isomerization. The nano-sized stripe is quite stable even being annealed at 90 °C for 4 h.