Micelle-like Structure Research Articles

Charge-controlled nano-structuring in partially collapsed star-shaped macromolecules.

Hydrophobic polyelectrolytes exhibit intra-molecular nano-scale self-organization instead of macroscopic phase separation because of the interplay between short-range hydrophobic attraction and long-range electrostatic repulsion. We aim to unravel how the morphology of the intra-molecular nanostructures can be controlled through the topology of the macromolecule on one hand and by adjustable ionization on the other hand. Specifically, we focus on hydrophobic star-branched polyelectrolytes, composed of either strong or weak acidic monomers. While both collapse in a globule when uncharged, and expand to full stretching of arms at high ionization, they exhibit quite different intermediate scenarios. For the strong ones, we observe the formation of bundles of arms as the main structural motif, and for the weak ones the intramolecular micelle-like structure is found at the same overall charge of the macromolecule. Here intramolecular disproportionation leaves some arms in a collapsed virtually neutral core, while others are substantially ionized and stretched in the corona.

Coarse grained study of pluronic F127: Comparison with shorter co-polymers in its interaction with lipid bilayers and self-aggregation in water

The aim of this work is to understand the interactions of the poloxamer Pluronic F127, with lipid bilayers and its ability to self-associate in an aqueous environment. Molecular dynamics simulations at the coarse-grain scale were performed to address the behavior of single Pluronic F127 and shorter poloxamers unimers in palmitoyl-oleoyl-phosphatidyl-choline model membranes. According to the initial conditions and the poly-ethylene oxide/poly-propylene oxide composition, in water phase the unimer chain collapses into a coil conformation or adopts an interphacial U-shaped – or membrane spanning – distribution. A combination of poly-propylene oxide length, and the poly-ethylene oxide ability to cover poly-propylene oxide, is determinant for the conformation adopted by the unimer in each phase. Results of the simulations showed molecular evidence of strong interaction between Pluronic F127 and model membranes both in stable U-shaped and span conformations. The knowledge of this interaction could contribute to improve drug permeation. Additionally, we investigated the aggregation of one hundred Pluronic F127 unimers in water forming a micelle-like structure, suitable to be used as drug delivery system models.

Influence of PEGylation on the ability of carboxymethyl-dextran to form complexes with α-lactalbumin

Electrostatic interactions between α-lactalbumin (α-lac) and carboxymethyldextran (CMD) in acidic solutions lead to phase-separated complexes. By adding a non-ionic poly(ethylene glycol) (PEG) chain onto the reducing end of CMD, forming carboxymethyl-dextran-block-poly(ethylene glycol) (CMD-b-PEG), the PEG block was hypothesized to reduce interactions with α-lac and promote formation of a micelle-like complex structure. Formation of complexes between α-lac and CMD-b-PEG or α-lac and CMD was determined following acidification by light scattering and electrophoretic mobility. Phase separation, size, and structure of α-lac/CMD-b-PEG complexes were characterized by turbidimetry, dynamic light scattering, and electron microscopy, respectively. Complexes of α-lac/CMD-b-PEG formed at pH values near pH 6, while α-lac/CMD complexes formed at pH 5.5. Both CMD and CMD-b-PEG decreased the charge of α-lac below pH 5.5 and led to phase separation below pH 5. Shift in charge and the critical pH of phase separation were both sensitive to the α-lac to CMD ratio, while the relative amount of CMD-b-PEG did not significantly influence either. Hydrodynamic radii of α-lac/CMD-b-PEG complexes was between 11 and 20nm, which increased with increasing α-lac to CMD-b-PEG ratio and with decreasing pH. Spheroidal structures of ∼10nm were also observed in micrographs that were attributed to α-lac/CMD-b-PEG complexes.

Towards a microstructural model of bitumen ageing behaviour

When it comes to describe the mechanical behaviour of hot mix asphalt (HMA), the change of the mechanical properties over time due to environmental impacts known as ageing has to be considered. Hardening and embrittlement of bitumen lead to a reduced resistance against cryogenic cracks and premature formation of fatigue cracks in bituminous layers. Within this work, the microstructure of bitumen is investigated by conducting static shear creep tests on artificially composed bitumen with asphaltene contents varying between 0 vol-% and 26.71 vol-% as well as on a paving grade bitumen 70/100. Both are considered in unaged and laboratory-aged (rolling thin-film oven test + pressure ageing vessel) conditions to be able to identify and describe ageing effects. While the properties of the considered material phases of bitumen (identical to saturates, aromatics, resins and asphaltenes (SARA) fractions) seem to remain unaffected, an increase of the asphaltene content due to ageing can be observed. A micromechanical model is proposed that allows a prediction of the consequences of these microstructural changes on the mechanical behaviour of bitumen. Atomic force microscopy and environmental scanning electron microscopy images confirm a composition consisting of a micelle-like structure in a contiguous matrix, a structural representative volume element concept based on SARA fractions is suggested, extending an existing multiscale model for HMA. A very good accordance between model predictions and experimental results indicates the model's ability to reproduce as well as to describe the effects related to ageing.

PAMAM Dendron Lipid Assemblies That Undergo Structural Transition in Response to Weakly Acidic pH and Their Cytoplasmic Delivery Capability.

Dendron lipids designed to consist of amine-terminated polyamidoamine G1 dendron and two octadecyl chains were used for the preparation of pH-responsive molecular assemblies having phase structures that are changed through their dynamic molecular shape. The dendron lipid contains two primary amines and two tertiary amines in the dendron moiety, changing its charged state in the pH region between pH 10 and pH 4. The assemblies were shown to take a vesicle structure at neutral and alkaline pHs, but their structure changed to a micelle-like structure below pH 6.4. Because this pH region corresponds to one in which tertiary amines of the dendron lipid became protonated, protonation of tertiary amines in addition to primary amines in the dendron moiety might affect its dynamic molecular shape, resulting in a sharp pH response of the assemblies. The assemblies tended to form aggregates when taking on a vesicle form with a gel phase, but incorporation of a poly(ethylene glycol)-lipid provided dendron lipid vesicles with both sharp pH response and high colloidal stability. The poly(ethylene glycol)-incorporated dendron lipid vesicles tightly retained ovalbumin molecules in their internal aqueous space but released them almost completely at pH 6.0. In addition, the vesicles were shown to achieve efficient ovalbumin delivery into cytosol of DC2.4 cells (mouse dendritic cell line) after internalization through endocytosis.

Assessment of the adsorptive color removal of methylene blue dye from water by activated carbon sorbent-immobilized-sodium decyl sulfate surfactant

Sodium decyl sulfate (SDeS) as an anionic surfactant was used for the surface modification of activated carbon (AC). Micelle-like structure was formed on the surface of AC sorbent-modified surfactant (AC-SDeS). The modified sorbent was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and thermal gravimetric analysis. The AC-SDeS sorbent was proved to have high enhanced removal capability for methylene blue (MB), a cationic dye, from various water matrices. The adsorptive removal process of MB dye was investigated and monitored using the batch equilibrium technique. Adsorptive removal of MB dye by AC-SDeS sorbent was examined in presence of various controlling parameters such as pH, contact time, sorbent dosage, initial dye concentration, and different interfering substances. The results showed that the optimum pH range for removal of MB dye from aqueous solutions (120 mg L−1) is pH 7.0–13.0 and the determined percentage values of removal were 92.25–94.50%. The percentage of dye removal decreased upon increasing the initial dye concentration and addition of interfering substances. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption models were applied to describe the equilibrium isotherms, and the experimental data were found to agree with the Langmuir isotherm model. The pseudo first-order, pseudo-second-order, intraparticle diffusion and Elovich kinetic models were used to examine the kinetic data and determine the rate constants. The results were found to fit well with the pseudo-second-order kinetic model. The efficiency of AC-SDeS for adsorptive removal of MB dye from tap water and real wastewater was also studied and excellent results were obtained as 95.90–96.20 ± 2.0–4.0%.

The cytotoxicity of BAMLET complexes is due to oleic acid and independent of the α-lactalbumin component

Lipid–protein complexes comprised of oleic acid (OA) non-covalently coupled to human/bovine α-lactalbumin, named HAMLET/BAMLET, display cytotoxic properties against cancer cells. However, there is still a substantial debate about the role of the protein in these complexes. To shed light into this, we obtained three different BAMLET complexes using varying synthesis conditions. Our data suggest that to form active BAMLET particles, OA has to reach critical micelle concentration with an approximate diameter of 250nm. Proteolysis experiments on BAMLET show that OA protects the protein and is probably located on the surface, consistent with a micelle-like structure. Native or unfolded α-lactalbumin without OA lacked any tumoricidal activity. In contrast, OA alone killed cancer cells with the same efficiency at equimolar concentrations as its formulation as BAMLET. Our data show unequivocally that the cytotoxicity of the BAMLET complex is exclusively due to OA and that OA alone, when formulated as a micelle, is as toxic as the BAMLET complex. The contradictory literature results on the cytotoxicity of BAMLET might be explained by our finding that it was imperative to sonicate the samples to obtain toxic OA.

Synthesis and controlled self-assembly of UV-responsive gold nanoparticles in block copolymer templates.

We demonstrate the facile synthesis of gold nanoparticles (GNPs) functionalized by UV-responsive block copolymer ligands, poly(styrene)-b-poly(o-nitrobenzene acrylate)-SH (PS-b-PNBA-SH), followed by their targeted distribution within a lamellae-forming poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer. The multilayer, micelle-like structure of the GNPs consists of a gold core, an inner PNBA layer, and an outer PS layer. The UV-sensitive PNBA segment can be deprotected into a layer containing poly(acrylic acid) (PAA) when exposed to UV light at 365 nm, which enables the simple and precise tuning of GNP surface properties from hydrophobic to amphiphilic. The GNPs bearing ligands of different chemical compositions were successfully and selectively incorporated into the PS-b-P2VP block copolymer, and UV light showed a profound influence on the spatial distributions of GNPs. Prior to UV exposure, GNPs partition along the interfaces of PS and P2VP domains, while the UV-treated GNPs are incorporated into P2VP domains as a result of hydrogen bond interactions between PAA on the gold surface and P2VP domains. This provides an easy way of controlling the arrangement of nanoparticles in polymer matrices by tailoring the nanoparticle surface using UV light.

Interconnected Macroporous Polymers Synthesized from Silica Particle Stabilized High Internal Phase Emulsions

n-Octadecyltrimethoxysilane (ODS)-modified silica particles were used as sole Pickering stabilizer to prepare water-in-oil Pickering high internal phase emulsions (HIPEs) with an internal phase volume of 80%. After polymerization of the continuous phase of HIPEs, interconnected macroporous polymers were obtained when modified silica was initially dispersed in water to form a micelle-like structure. However, silica particles in oil phase resulted in closed-cell pores. The pore size, the pore wall morphology, and the interconnectivity of polymer foams could be adjusted finely by the grafted amounts of ODS, modified silica concentrations, and the initial location of Pickering stabilizer. The gas permeation of interconnected porous polymers increased dramatically with the increase of the hydrophobicity of silica particles from 3 to 153 mL/min.

High gene delivery efficiency of alkylated low-molecular-weight polyethylenimine through gemini surfactant-like effect.

To our knowledge, the mechanism underlying the high transfection efficiency of alkylated low-molecular-weight polyethylenimine (PEI) is not yet well understood. In this work, we grafted branched PEI (molecular weight of 1,800 Da; bPEI1800) with lauryl chains (C12), and found that bPEI1800-C12 was structurally similar to gemini surfactant and could similarly assemble into micelle-like particles. Stability, cellular uptake, and lysosome escape ability of bPEI1800-C12/DNA polyplexes were all greatly enhanced after C12 grafting. bPEI1800-C12/DNA polyplexes exhibited significantly higher transfection efficiency than Lipofectamine™ 2000 in the presence of serum. Bioluminescence imaging showed that systemic injection of bPEI1800-C12/DNA polyplexes resulted in intensive luciferase expression in vivo and bioluminescence signals that could be detected even in the head. Altogether, the high transfection efficacy of bPEI1800-C12 was because bPEI1800-C12, being an analog of gemini surfactant, facilitated lysosome escape and induced the coil–globule transition of DNA to assemble into a highly organized micelle-like structure that showed high stability.

Structure, stability, and fragmentation of sodium bis(2-ethylhexyl)sulfosuccinate negatively charged aggregates in vacuo by MD simulations.

Negatively charged supramolecular aggregates formed in vacuo by n bis(2-ethylhexyl)sulfosuccinate (AOT(-)) anions and n + n(c) sodium counterions (i.e., [AOT(n) Na(n+nc)](nc)) have been investigated by molecular dynamics (MD) simulations for n = 1 to 20 and n(c) = -1 to -5. By comparing the maximum excess charge values of negatively and positively charged AOTNa aggregates, it is found that the charge storage capability is higher for the latter systems, the difference decreasing as the aggregation number increases. Statistical analysis of physical properties like gyration radii and moment of inertia tensors of aggregates provides detailed information on their structural properties. Even for n(c) = -5, all stable aggregates show a reverse micelle-like structure with an internal core, including sodium counterions and surfactant polar heads, surrounded by an external layer consisting of the surfactant alkyl chains. Interestingly, the reverse micelle-like structure is retained also in proximity of fragmentation. Moreover, the aggregate shapes may be approximated by elongated ellipsoids whose longer axis increases with n and |n(c)|. The fragmentation patterns of a number of these aggregates have also been examined and have been found to markedly depend on the aggregate charge state. The simulated fragmentation patterns of a representative aggregate show good agreement with experimental data obtained using low collision voltages.

Revisiting the thermosensitivity of poly(acrylamide-co-diacetone acrylamide)

The lower critical solution temperature (LCST) behavior of poly(acrylamide-co-diacetone acrylamide) (poly(AM-co-DAM)) copolymer in aqueous solutions was studied. The results demonstrate the LCST linearly decreases as the molar fraction of DAM (f DAM) increases. In the range of f DAM < 0.36, the transmittance increases as f DAM decreases because the more hydrophilic copolymer chains can form looser aggregates with a lower refractive index. The transmittance exhibits a minimum when f DAM is less than 0.28 as the chains form micelle-like structure with a size smaller than the wavelength. The LCST decreases with the initial polymer concentration, but it levels off when the polymer concentration is high enough. Moreover, no hysteresis can be observed in the change of transmittance during the heating-cooling process because no additional hydrogen bonds are formed in the collapsed state due to the steric hindrance of the large side groups in DAM units.

Sensitization of europium(III) luminescence in water with β-diketone-poly(ethylene glycol) macroligand

Poly(ethylene glycol)-modified β-diketone macroligand is developed to sensitize europium(III) ions in water. High luminescence intensity characteristic of Eu3+ was achieved due to spontaneous formation of micelle-like structure in which the hydrophobic core prevents luminescence-quenching by water molecules. The pH is found to induce a quantitative ratio change in two fluorescence bands from both ligand and Eu3+.

Development of cholesteryl peptide micelles for siRNA delivery

Despite the rapid progress in the siRNA field, developing a safe and efficient delivery system of siRNA remains to be an obstacle in the therapeutical application of siRNA. The purpose of this study is to develop an efficient peptide-based siRNA delivery system for cancer therapy. To this end, cholesterol was conjugated to a series of peptides composed of lysine and histidine residues. The resultant cholesteryl peptides were characterized, and their potential for siRNA delivery was evaluated. Our results indicate that short peptides (11–21 mer) composed of various numbers of lysine and histidine residues alone are not sufficient to mediate efficient siRNA delivery. However, the amphiphilic cholesteryl peptides can self-assemble to form a micelle-like structure in aqueous solutions, which significantly promotes the siRNA condensation capability of the peptides. The cholesteryl peptides form stable complex with siRNA and effectively protect siRNA from degradation in rat serum up to three days. Furthermore, the cholesteryl peptides efficiently transfect siRNA into different cancer cells and trigger potent gene silencing effect, whereas peptides without cholesterol modification cannot deliver siRNA into the cells. In addition, one of the cholesteryl peptides Chol-H3K2s displays comparable cellular uptake and gene silencing effect but less cytotoxicity compared with branched polyethylenimine (bPEI) and Lipofectamine-2000. Our results reveal that the cholesteryl peptides possess great potential as an efficient siRNA delivery system.

Preparation of pH- and thermo-sensitive chitosan-PNIPAAm core–shell nanoparticles and evaluation as drug carriers

Environmentally sensitive polysaccharide nanoparticles (NPs) were prepared by in situ polymerization of N-isopropylacrylamide (NIPAAm) monomer in the presence of chitosan (CS) micelles. First, CS was found to develop a cationic micelle-like structure in the acetic acid solution when its concentration was increased to above the critical micelle concentration, as evidenced by fluorescence and TEM. When the NIPAAm was polymerized in the CS micelle solution by using potassium persulfate as initiator, the produced PNIPAAm with anionic chain end(s) became hydrophobic, as long as the reaction temperature was above its phase transition temperature; and therefore it would diffuse into the hydrophobic core of the CS micelles, producing CS-PNIPAAm core–shell NPs. Increasing the feeding amount of NIPAAm increased the monomer conversion and therefore the particle size; yet it decreased the surface zeta potential. Moreover, the CS-PNIPAAm NPs were sensitive to both pH value and temperature. For the study of drug release properties, doxycycline hyclate was used as a model drug and loaded into the NPs at pH 4.5 and 25 °C. The result illustrated that these NPs had a continuous drug release behavior up to 1 week, depending on the pH value and temperature. In addition, enzyme or hydrogen peroxide capable of degrading CS shell was added in the solution to facilitate the drug release.

Mass Spectrometry Study of Multiply Negatively Charged, Gas-Phase NaAOT Micelles: How Does Charge State Affect Micellar Structure and Encapsulation?

We report the formation and characterization of multiply negatively charged sodium bis(2-ethylhexyl) sulfosuccinate (NaAOT) aggregates in the gas phase, by electrospray ionization of methanol/water solution of NaAOT followed by detection using a guided-ion-beam tandem mass spectrometer. Singly and doubly charged aggregates dominate the mass spectra with the compositions of [Na(n-z)AOT(n)](z-) (n = 1-18 and z = 1-2). Solvation by water was detected only for small aggregates [Na(n-1)AOT(n)H(2)O](-) of n = 3-9. Incorporation of glycine and tryptophan into [Na(n-z)AOT(n)](z-) aggregates was achieved, aimed at identifying effects of guest molecule hydrophobicity on micellar solubilization. Only one glycine molecule could be incorporated into each [Na(n-z)AOT(n)](z-) of n ≥ 7, and at most two glycine molecules could be hosted in that of n ≥ 13. In contrast to glycine, up to four tryptophan molecules could be accommodated within single aggregates of n ≥ 6. However, deprotonation of tryptophan significantly decrease its affinity towards aggregates. Collision-induced dissociation (CID) was carried out for mass-selected aggregate ions, including measurements of product ion mass spectra for both empty and amino acid-containing aggregates. CID results provide a probe for aggregate structures, surfactant-solute interactions, and incorporation sites of amino acids. The present data was compared with mass spectrometry results of positively charged [Na(n+z)AOT(n)](z+) aggregates. Contrary to their positive analogues, which form reverse micelles, negatively charged aggregates may adopt a direct micelle-like structure with AOT polar heads exposed and amino acids being adsorbed near the micellar outer surface.

Effects of dissolved state of aminoalkyl methacrylate copolymer E/HCl on solubility enhancement effect for poorly water-soluble drugs

Eudragit® E/HCl salt (E–SD) displays a good antireprecipitation effect on solid dispersion formulations of poorly water-soluble drugs. To elucidate the mechanism underlying the antireprecipitation effect of E–SD, a study on supersaturation was conducted using a dissolution test method with test fluids at varying pH and ionic strength values. Both pH and ionic strength of the test fluid were shown to influence the antireprecipitation effect of E–SD; a strong antireprecipitation effect was observed at a neutral pH (pH 6∼7) and an ionic strength of 0.1 to 1.0. To investigate E–SD in its dissolved state in each test fluid, fluorescence measurement using pyrene as a probe molecule and dynamic light-scattering (DLS) measurement were conducted. The total fluorescence intensity of pyrene increased with increasing E–SD concentrations. Further, small nanoparticles were observed using DLS measurement. These results suggest that E–SD may form a micelle-like structure in the dissolved test fluid.

Adsorption of Solvent Cations on Au(111) and Au(100) in Alkylimidazolium-Based Ionic Liquids – Worm-Like versus Micelle-Like Structures

Abstract By employing high resolution in-situ STM, the adsorption of alkylimidazolium-based cations of EMI + , PMI + , BMI + and OMI + on Au(111) and Au(100) surfaces are investigated systematically. The cation adsorption on both Au(111) and Au(100) are composed of double rows arising from counter-facing imidazolium-based cation pairs. On Au(100), the double rows associated with the four cations show micelle-like appearance along the two √ 2 directions of the Au(100) surface lattice units. The width of the double rows varies depending on the side chain length of the cations, but is constrained by the periodicity along the √ 2 directions. Anions of BF 4 - , PF 6 - , CF3SO 3 - and Tf2N - do not influence the micelle-like adsorption structure. On Au(111), the double rows are formed only when the terraces are etched to several atoms wide. Most likely, the underneath Au surface experiences restructuring to accommodate the double row structure, and the worm-like orientation of the double rows is the consequence of strain release. Both the micelle-like and worm-like adsorption structures would be lifted upon cathodic potential excursions when the surfaces are driven to undergo ordinary Au(100)-hex and Au(111)-(√ 3 × 22) reconstructions. These results reveal that the ordered micelle-like structure on Au(100) and the irregular worm-like structure on Au(111) are of the same nature.

The preparation of a complex of insulin–phospholipids and their interaction mechanism

Subcutaneous injections of insulin remain the standard treatment for insulin-dependent diabetic patients, and noninvasive routes are studied but with little success. One of the reasons is that insulin is a hydrophilic compounds and is difficult to cross the mucosa barrier. In this paper, we developed a novel technique to fabricate the insulin-phospholipids complex by a solvent evaporation method with the aim of improving the lipophilicity of insulin. A systematic study on the preparation conditions of the insulin-phospholipids complex is reported in the present work. The formation mechanism and the physicochemical properties of the complex are studied. The associated efficiency of the phospholipids and insulin can be up to 100% when their mass ratio is 7.5 : 1 or more, and the solubility of the complex is improved more than 40 000 times compared with that of insulin alone in the n-octyl alcohol. The results of the insulin content in the complex and hypoglycemic effects in diabetic mice indicated that insulin was able to withstand the preparation procedure. The stability results showed that the complex was stable for 1 year at -20 °C. The interaction mechanism of this formation is that the peptide bonds of insulin interact with the water-soluble head of phospholipids, forming a reverse micelle-like structure. This novel complex will be of great importance in the drug delivery system for insulin via noninvasive routes. This method is cost effective, scalable, and can be used in many other peptide drugs.

Fabrication of hollow core carbon spheres with hierarchical nanoarchitecture for ultrahigh electrical charge storage

A simple and reproducible sol–gel synthesis strategy was developed to fabricate hollow core carbon spheres (HCCSs) with hierarchical nanoarchitecture through the hydrolysis, self-assembly and co-condensation of bis-[3-(triethoxysilyl)propyl]disulfide (TESPDS) and octadecyltrimethoxysilane (C18TMS). This synthesis route allows one to fabricate thioether-bridged organosilica (TBOS) with tailored spherical structure and particle size which can be further converted to HCCS upon calcination under N2 flow. It is assumed that hydrophobic octadecyl chains of hydrolyzed C18TMS first form a micelle-like self-assembly structure with hydrophilic trihydroxysilyl groups as heads, and a reactive core is then expanded by the base-catalyzed co-condensation of TESPDS and/or C18TMS over the C18TMS self-assembly structure. The organic moieties of TESPDS and C18TMS not only serve as a porogen during the formation of TBOS but also as a carbon precursor for transformation of TBOS into HCCS during the carbonization. Due to its unique hierarchical nanostructure composed of hollow macroporous core and meso/microporous shell, which facilitates fast mass transport, along with large surface area for electrical charge storage, the HCCS for the first time exhibits ultrahigh specific capacitance and energy, good cycling performance and rate capability.