Effect of urea on self-organization of sodium N-(11-acrylamidoundecanoyl)-L-valinate in water

In this paper, the hypotheses proposed for the action of urea on the perturbation of molecular assemblies have been tested through studies of the effects of urea on the aggregation properties of a chiral surfactant, sodium N-(11-acrylamidoundecanoyl)-L-valinate in water. Surface tension, fluorescence, and circular dichroism were used to characterize the solution behavior of the amphiphile in the presence of urea. Surface tension measurement indicated decrease of critical aggregation concentration (cac) with the addition of urea in the low concentration range. Fluorescence probe studies using pyrene and 1-anilinonaphthalene indicated solubilization of urea molecules near the aggregate-water interface. Fluorescence anisotropy measurements using 1,6-diphenylhexatriene as probe molecule suggested increase of packing of the hydrocarbon chains of the amphiphiles upon addition of low concentration of urea. Dynamic light scattering measurements showed an increase of the hydrodynamic radius (R(h)) in the presence of increased concentration of urea. At higher concentrations of urea, the R(h) value decreased. Circular dichroism spectra showed the presence of chiral aggregates even in the presence of high concentration of urea.     

Spontaneously formed nonequilibrium vesicles of cetyltrimethylammonium bromide and sodium octyl sulfate in aqueous dispersions

It is well-known that vesicles form in mixtures of cationic and anionic surfactants. We have investigated mixtures of cetyltrimethylammonium bromide (CTAB) and sodium octyl sulfate (SOS) with the latter in excess over a long time, about 500 days. We have followed the growth of the aggregates by light scattering and checked the morphologies by cryogenic transmission electron microscopy (cryoTEM). All samples showed a monotonic growth with decreasing rate (the change of size was about linear on a logarithmic time scale). In series of samples with weight ratio 30:70 of CTAB/SOS and total surfactant concentration between 0.5 and 3 wt %, the size increased with the surfactant concentration up to 2 wt % and decreased thereafter; cryoTEM examination revealed that the samples contained a majority of open bilayer structures at the highest concentrations. Part of the sample at 2 wt % was diluted to 0.5 wt % after 60 days. The size measured after dilution was slightly smaller than before but well above that found in the directly prepared 0.5 wt % sample, and the particle size in the three samples continued to grow in parallel. Structures other than unilamellar vesicles were observed also in samples at 2 wt % total surfactant concentration at CTAB/SOS ratios close to the borders of the vesicle lobe in the (quasi) ternary phase diagram as published (Yatcilla, M. T.; Herrington, K. L.; Brasher, L. L.; Kaler, E. W.; Chiruvolu, S.; Zasadzinski, J. A. J. Phys. Chem. 1996, 100, 5874). The results clearly show that the spontaneous vesicle populations do not represent equilibrium populations. They also suggest that the vesicle lobes in the phase diagram mainly represent areas where a lamellar phase is easily dispersed in the form of vesicles in an aqueous solution.     

Characterization of polymeric vesicles of poly(sodium 11-acrylamidoundecanoate) in water

A polysoap poly(sodium 11-acrylamidoundecanoate) was synthesized from sodium 11-acrylamidoundecanoate in water. The molecular weight of the polymer was determined by gel permeation chromatography and static light scattering techniques. Fluorescence probe studies in water have suggested the formation of hydrophobic domains within the same polymer chain. The microenvironment of the hydrophobic domains is highly ordered. The packing of the hydrocarbon chains in the hydrophobic domains formed by intra-chain association increases upon decrease of pH. The transmission electron micrograph revealed large vesicular aggregates in dilute aqueous solution. Temperature-dependent fluorescence anisotropy of the 1,6-diphenyl-1,3,5-hexatriene probe demonstrated stability of the vesicles.     

Spontaneous formation of vesicles and chiral self-assemblies of sodium N-(4-dodecyloxybenzoyl)-L-valinate in water

A novel N-acylamino acid surfactant, sodium N-(4-dodecyloxybenzoyl)-L-valinate (SDLV), has been synthesized. The aggregation behavior of the surfactant in aqueous solution has been studied by surface tension, fluorescence probe, microscopy, and dynamic light scattering (DLS) techniques. The amphiphile has a very low critical aggregation concentration (cac). These studies have suggested formation of large bilayer structures in water. The mean apparent hydrodynamic radius, RH, of the self-assemblies in dilute aqueous solution obtained from DLS measurements confirmed formation of large aggregates. The FT-IR spectra of the amphiphile have indicated strong intermolecular amide hydrogen bonding in the self-assemblies in aqueous solution. The microenvironment of the fluorescence probes is highly nonpolar and viscous in nature. The circular dichroism (CD) spectra of SDLV were recorded in water and in a 1:1 water-methanol mixture. The CD spectra have indicated the presence of chiral aggregates in aqueous solution above the cac. The microstructure of the aggregates has been studied by use of optical and transmission electron microscopy. Both types of micrographs have shown the presence of a variety of morphologies including giant spherical vesicles, tubules, twisted ribbons, and helical strands in aqueous solutions.     

Effect of hydrogen-bonding interactions on the self-assembly formation of sodium N-(11-acrylamidoundecanoyl)-L-serinate, L-asparaginate, and L-glutaminate in aqueous solution

Aggregation behavior of three N-acyl amino acid surfactants, sodium N-(11-acrylamidoundecanoyl)-l-serinate (SAUS), sodium N-(11-acrylamidoundecanoyl)-l-asparaginate (SAUAS), and sodium N-(11-acrylamidoundecanoyl)-l-glutaminate (SAUGL), was studied in aqueous solution by use of surface tension, fluorescence, dynamic light scattering, and transmission electron microscopic techniques. The amphiphiles have been shown to initially form flexible bilayer structures, which upon increase of surfactant concentration transform into closed spherical vesicles. The transmission electron micrographs of the aqueous solutions of the surfactants confirmed the existence of spherical vesicles. Dynamic light scattering measurements were performed to obtain hydrodynamic radii of the vesicles. Circular dichroism spectra of the amphiphiles indicated formation of chiral helical aggregates in the case of SAUS. The self-assembly formation of the amphiphiles has been discussed in light of the intermolecular hydrogen bonding interaction of the amide groups.     

Spontaneously formed unilamellar vesicles with path-dependent size distribution

We observe the spontaneous formation of path-dependent monodisperse and polydisperse phospholipid unilamellar vesicles (ULV) from two different equilibrium morphologies specifically, disklike micelles and extended lamellae, respectively. On heating beyond a temperature Tc, low temperature disklike micelles, or so-called bicelles, transform into lamellae. Dilution of the lamellar phase, at a fixed temperature, results in a complete unbinding transition and the formation of polydisperse ULV, demonstrating the instability of the lamellar phase. On the other hand, heating of a dilute bicellar phase above Tc results in monodisperse ULV, which on cooling revert back to bicelles for lipid concentrations phi > or = 0.5 wt % and transform into oblate ellipsoids for phi = 0.1 wt %, a morphology not previously seen in "bicellar" lipid mixtures. Monodisperse ULV reform on heating of the oblate ellipsoids.     

Effect of urea on self-organization of sodium N-(11-acrylamidoundecanoyl)-l-valinate in water

In this paper, the hypotheses proposed for the action of urea on the perturbation of molecular assemblies have been tested through studies of the effects of urea on the aggregation properties of a chiral surfactant, sodium N-(11-acrylamidoundecanoyl)-L-valinate in water. Surface tension, fluorescence, and circular dichroism were used to characterize the solution behavior of the amphiphile in the presence of urea. Surface tension measurement indicated decrease of critical aggregation concentration (cac) with the addition of urea in the low concentration range. Fluorescence probe studies using pyrene and 1-anilinonaphthalene indicated solubilization of urea molecules near the aggregate-water interface. Fluorescence anisotropy measurements using 1,6-diphenylhexatriene as probe molecule suggested increase of packing of the hydrocarbon chains of the amphiphiles upon addition of low concentration of urea. Dynamic light scattering measurements showed an increase of the hydrodynamic radius (R(h)) in the presence of increased concentration of urea. At higher concentrations of urea, the R(h) value decreased. Circular dichroism spectra showed the presence of chiral aggregates even in the presence of high concentration of urea.     

Gelation of spontaneously formed catanionic vesicles by water soluble polymers

The gelation of two spontaneously formed charged catanionic vesicles by four water soluble polymers was systematically studied by tube inversion method and rheology. Eight phase maps were successfully documented for the catanionic vesicle–polymer mixtures. The experimental results, as represented by the relaxation time and the storage modulus at 1 Hz, revealed that the catanionic vesicle–polymer interactions at play were of electrostatic and hydrophobic origin. Firstly, no association between charged catanionic vesicles and the polymer without charge/hydrophobic modification was observed due to lack of both electrostatic and hydrophobic effects. Secondly, hydrophobic interactions accounted for the association between the hydrophobically modified polymer without charge and charged catanionic vesicles with hydrophobic grafts of the polymer inserting in the catanionic vesicle bilayer. Thirdly, the positively charged polymer without hydrophobic modification could interact with negatively charged catanionic vesicles through electrostatic force on one hand but could not interact with positively charged catanionic vesicles on the other hand. Finally, the positively charged polymer with hydrophobic modification could interact both electrostatically and hydrophobically with negatively charged catanionic vesicles, resulting in the formation of strong gels. The hydrophobic interaction might even overcome the unfavorable electrostatic interaction between the positively charged vesicles and the polymer with positive charge/hydrophobic modification.     

N-(11-羧基十一烷基)马来酰亚胺及其三聚体的合成

以顺丁烯二酸酐和12-氨基十二酸为原料,硫酸、三乙胺为脱水催化剂,经两步反应合成了N-(11-羧基十一烷基)马来酰亚胺.再在三苯基膦和苯酚作用下,N-(11-羧基十一烷基)马来酰亚胺进一步发生三聚反应合成了相应的马来酰亚胺三聚体.采用红外光谱和核磁共振谱对三聚体的结构进行了表征.     

Spontaneously formed trans-anethol/water/alcohol emulsions: mechanism of formation and stability

We studied the spontaneous emulsification and droplet growth mechanism in trans-anethol/water/ethanol solutions, also known as the beverage ouzo, using dynamic light scattering spectroscopy. This simple ternary mixture is a generic example of a system that forms microemulsions spontaneously when brought into the two-phase region. The volume fraction of the dispersed phase was found to profoundly affect the growth rates of the droplets, which is a new finding that has not been predicted by the Lifshitz-Slyozov-Wagner theory. Time-dependent measurements show that the droplet growth is governed by Ostwald ripening (OR), and no coalescence was observed. Furthermore, the OR rates increase with increasing oil concentration at low alcohol content. We attribute this behavior to enhanced droplet-droplet interactions. At high ethanol concentrations, we found that the measured rates decreased as the oil concentration increased. The OR growth mechanism completely correlates with changes in droplet size. The kinetics of droplet growth shows that the ripening has a saturation limit at a droplet radius of about 1.5 mum. Thus, formed emulsions remain stable for months.     

Dynamic surface properties of sodium N-acryloyl-11-amimoundecanoate and poly(sodium N-acryloyl-11-aminoundecanoate)

Adsorption layers of sodium N-acryloyl-11-amimoundecanoate and poly(sodium N-acryloyl-11-aminoundecanoate) (PAAU-Na) are studied using surface dilatational rheology measurements. It is established that the dynamic surface elasticity values of the studied systems are different, while their surface tension isotherms are almost the same. PAAU-Na solutions containing excess indifferent electrolyte (NaCl) exhibit a conformational transition in a surface layer due to the formation of loops and tails, which penetrate the bulk phase. Slow variations in the surface properties of PAAU-Na solutions with time seem to be caused by the aggregation of macromolecules in the bulk phase. The aggregation process is investigated by scanning probe microscopy.     

Spontaneous formation of vesicles by sodium 2-dodecylnicotinate in water

The surface activity and aggregation behavior of a synthesized nicotinic acid based anionic surfactant, sodium 2-dodecylnicotinate, were studied in aqueous solution. The self-assembly formation was investigated by use of a number of techniques, including surface tension and conductivity measurements, fluorescence spectroscopy, dynamic light scattering measurement, gel permeation chromatography, and microscopy. The amphiphile exhibits two breaks in the surface tension vs concentration plot, indicating stepwise aggregate formation and thus producing two values of the aggregation concentration. Stepwise aggregation of the amphiphile was further confirmed by steady-state fluorescence spectroscopy using pyrene as a probe molecule, and also the micropolarity of the aggregates was determined. The rigidity of the microenvironment was estimated by determining steady-state fluorescence anisotropy using 1,6-diphenyl-1,3,5-hexatriene as a fluorescence probe molecule. The average hydrodynamic radius and size distribution of the aggregate suggest formation of larger aggregates in aqueous solution. The formation of vesicles in water was established by conductivity measurement and a dye entrapment experiment. The entrapment of a small solute and the release capability have also been examined to demonstrate these bilayers form enclosed vesicles. Transmission electron micrographs revealed the existence of closed vesicles and closed tubules in aqueous solution. Therefore, for the first time, it has been observed that this simple single-chain nicotinic acid based amphiphile spontaneously assembles to vesicles in aqueous solution.     

Stable vesicle formation through intra- and inter-chain aggregation of poly[sodium N-(11-acrylamidoundecanoyl)-l-valinate] in aqueous solution

The vesicle-forming surfactant, sodium N-(11-acrylamidoundecanoyl)-l-valinate was polymerized to obtain corresponding polysoap. Light scattering and fluorescence probe techniques were used to characterize the polysoap. Fluorescence probe studies suggested that the polymer forms intra-chain as well as inter-chain aggregates. The microenvironment of the aggregates was studied by fluorescence measurements using 1-anilinonaphthalene, pyrene, and 1,6-diphenylhexatriene (DPH) as probe molecules. Fluorescence anisotropy studies by use of DPH have indicated a high local viscosity of the aggregates formed by the polysoap in water. The pH-induced change of the aggregate structure has been studied. The phase transition temperature of the polysoap was determined from temperature dependence of fluorescence anisotropy of DPH. Dynamic light scattering measurements were performed to determine the mean size of the aggregates. Transmission electron micrographs revealed closed vesicles in water.     

Stereoselective synthesis of 3,4-disubstituted pyroglutamates by ring transformation of 5-ylidene-1,3-dioxan-4-ones with N-(diphenylmethylene)-glycinate

N-(Diphenylmethylene)-glycinate gives stereoselective conjugate addition to readily available (E) and (Z)-5-ylidene-1,3-dioxan-4-ones. Hydrolytic cleavage of the imine functionality of the resulting Michael-adducts causes ring transformation to new, optically active 3,4-disubstituted pyroglutamates.     

Unusual course of the reaction of N-(tosylmethyl)thiourea and N-(azidomethyl)thiourea with sodium enolate of dimedone

The end product of the reaction of N-(tosylmethyl)thiourea or N-(azidomethyl)thiourea with sodium enolate of dimedone is bis(2-hydroxy-4,4-dimethyl-6-oxocyclohex-1-enyl)methane (methylenebisdimedone) instead of the expected 8a-hydroxy-7,7-dimethyl-2-thioxoperhydroquinazolin-5-one.M. V. Lomonosov State Academy of Fine Chemical Technology, Moscow 117571, Russia; Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 70–72, January, 2000.     

Soft vesicles formed by diblock codendrimers of poly(benzyl ether) and poly(methallyl dichloride)

The synthesis of a block codendrimer (g3-PBE-b-g3-PMDC), composed of a third-generation poly(benzyl ether) (PBE) monodendron and an aliphatic polyether (PMDC) monodendron is reported. In THF/diiospropyl ether (1:1) the PMDC block functions as a "hydrophilic" block, while the PBE acts as a "hydrophobic" block. The codendrimer can form interdigitated layers leading to vesicle formation. Tapping mode atomic force microscopy (AFM), dynamic light scattering (DLS), and transmission electron microscopy (TEM) were used to characterize the vesicles. The effect of molecular architecture on the formation of the interdigitated layers and vesicles was studied.     

Rheological behavior in water of complexes formed from poly(sodium 2-(acrylamido)-2-methylpropanesulfonate) and positively charged rodlike micelles

The viscoelastic behavior of aqueous solutions of an ionic complex formed from poly(sodium 2-(acrylamido)-2-methylpropanesulfonate) and rodlike mixed micelles of dimethyloleylamine oxide (DMOAO) and hexadecyltrimethylammonium chloride (CTAC) was investigated under oscillatory conditions. The DMOAO/CTAC mixed micelles exhibited high zero-shear viscosities (eta0) depending on the mole fraction of CTAC in the mixed micelle (Y) in the range 0Y0.25. The addition of the polyanion had no effect on the rheological behavior of the mixed micelles when Y<0.02 at an ionic strength (mu) of 0.2. However, when Y was increased to a certain level (Yc), eta0 decreased drastically; Yc depended on mu but not on the polymer concentration. These observations indicate the formation of an ionic complex between the polymer and micelle when YYc. The reciprocal of steady-state compliance (Je(-1)) began to decrease gradually at Y approximately Yc and then leveled off at Y>0.06. The relaxation time (tau) was found to be more strongly dependent on Y. Thus, the large decrease in eta0 was attributed mainly to a decrease in tau while the number density of junctions decreased only slightly. Therefore, it is concluded that polymer-micelle complex maintains a rodlike structure with some entanglements remaining at Y<0.12.     

Mannich-type reactions in a colloidal solution formed by sodium tetrakis(3,5-trifluoromethylphenyl)borate as a catalyst in water

Sodium tetrakis(3,5-trifluoromethylphenyl)borate efficiently catalyzed the one-pot, three-component Mannich reaction of ketones with aromatic aldehydes and different anilines in water at an ambient temperature and afforded the corresponding β-amino carbonyl compounds in good to excellent yields.     

Rhodium-catalyzed asymmetric arylation of N-(tert-butanesulfinyl)imines with sodium tetraarylborates

A diastereoselective rhodium-catalyzed arylation of N-(tert-butanesulfinyl)imines with sodium tetraarylborates is described. This method is general for constructing various chiral α-branched amines and 2-substituted pyrrolidines with high diastereoselectivity. A practical asymmetric approach to access chiral amines has been developed involving the use of air-stable Rh catalysts and reagents and in the absence of an external ligand.