Micellar aggregation for ionic surfactant in pure solvent and electrolyte solution: nonextensive thermodynamics approach

We show in this study that the concepts of nonextensive thermodynamics introduced and applied in a series of previous studies can be used to describe the behaviour of ionic surfactant solutions at concentrations higher than the critical micelle concentration (cmc) in pure solvents and in the presence of electrolytes. We supposed that the aggregated amphiphiles and their counter ions form two interpenetrated nonextensive phases of the same thermodynamic dimension, m, characterised by two parameters A(am) and A(CI) related to the aggregated amphiphile and the counter ion, respectively. Our experimental results and those published in the literature indicate that logarithms of the activities of the amphiphile and of its counterion vary with the quantity of aggregated monomer according to a power law. Thus, we demonstrate a linear relation between the logarithms of the activities of the two ions beyond the cmc in pure solvents ("micellization product"). An original relation, different from the Corrin-Harkins relation, can thus be established to describe the effects of salt on the cmc of ionic surfactants. According to this relation the cmc of charged surfactant in some systems can increase in the presence of an electrolyte with a common ion.     

油酸钠层状液晶体系的聚合

将十六烷增溶于油酸钠／水体系层状液晶的油层,共聚单体二乙烯基乙二醇增溶于油酸钠／水体系层状液晶的两亲层,将共聚限制在同一两亲层内油酸钠的双键与共聚单体之间进行。得到了具有层状结构,并具有较好表面活性的共聚物。     

Lamellar liquid crystal polymerization of sodium oleate/oleic acid/octadiene/water system

In the lamellar liquid crystallization (LLC) phase of NaOL/ OLA/H2O system, the small angle X-ray diffraction measurements show that the oleic acid is solubilized in the oil layer at first and then into the amphiphile layer. The octadiene added is also located partly in the oil layer and partly in the amphiphile layer in the LLC. With the addition of octadiene as cross-Unking agent, the LLC phase of NaOL/OIA/H2O system was polymerized under the initiation of AIBN with the protection of pure nitrogen at 60℃. Most of the double bond absorption of the monomers in IR spectra disappeared after polymerization. The polymerization takes place not only in the middle of the amphiphile layer between the double bonds of NaOL or OLA and those of octadiene, but also in the oil layer of LLC between the double bonds of OLA and those of octadiene. Interlayer spacing measurements on the copolymer proved d values decreased by about 1-2 nm compared with those of the corresponding system before the polymerization, indicati     

油酸钠／水／十六烷／4-烯丙基-4羟基-1,6-庚二烯体系层状液晶的聚合

将十六烷增溶于油酸钠 /水体系层状液晶的油层 ,共聚单体 4 烯丙基 4 羟基 1 ,6 庚二烯增溶于油酸钠 /水体系层状液晶的两亲层 ,在同一两亲层内进行共聚反应 ,得到了具有层状结构、并具有较好表面活性的共聚物     

Shapes of Micelles and Molecular Geometry Synthesis and Studies on the Phase Behaviour, Surface Tension and Rheology of Rigid Rod-Like Surfactants in Aqueous Solutions

Amphiphiles with rigid rod-like hydrophobic moieties have been synthesized in order to investigate the effect of the packing restraints of such moieties on the micellar association behaviour of amphiphiles in aqueous solution. Investigations of the phase behaviour of amphiphile/water mixtures reveal that liquid-crystalline phases exist in defined temperature and concentration regimes and that they are all lamellar, regardless of the hydrophilic-hydrophobic balance of the amphiphile. For these lyotropic liquid-crystalline phases a polymorphism is observed which is similar to the polymorphism of thermotropic smectic liquid crystals. Surface tension measurements indicate critical micelle concentrations of the amphiphiles in dilute solutions which are similar to those of conventional surfactants. From rheological measurements it can be assumed that the variation of temperature and/or concentration of the solution does not influence the micellar shape. This is in contrast to the behaviour of non-ionic surfactants having a flexible hydrophobic group.     

Polymerisation in lyotropic liquid-crystalline phases of dioctadecyldimethylammonium bromide

The polymerisation of styrene in lyotropic liquid-crystalline (LC) phases of dioctadecyldimethylammonium bromide (DODAB) in water is explored. Amphiphile concentrations between 20 and 50 wt % are employed. The study is set out as a model study for polymerisation reactions in nonstabilised, nonfunctional bilayer systems. X-ray characterisation was used to assess the phase behaviour of the lyotropic mesophases before, during and after polymerisation. The DODAB/water system forms the lamellar phase within the concentration range considered. Addition of styrene to the lamellar phase of DODAB at an equimolar ratio induces a phase shift to a bicontinuous cubic phase at elevated temperatures near the phase-transition temperature. Upon polymerisation within this cubic phase, the phase structure is maintained if the system is kept at constant temperature; however, if the polymer/amphiphile phase is cooled, the lamellar phase, being typical of the DODAB/water system, is restored. It is concluded that, as a result of phase separation between the polymer and the amphiphile phase, the polymerisation in lyotropic LC phases does not provide a stable copy of the templating amphiphile phase. This is in analogy to the observations for polymerisations in other lyotropic phases. Received: 16 March 2000 Accepted: 1 July 2000     

Photoinduced morphism of gemini surfactant aggregates

The photochemical behaviour of an azobenzene chromophore inserted in a gemini surfactant imparts photocontrol to the resulting amphiphile assemblies, including the collapse, upon irradiation, of the multi lamellar vesicles formed in aqueous solution.     

Pyridinyloxazolidines: versatile scaffolds for chiral catalyst construction

Pyridinyloxazolidines are structurally versatile chiral ligand frameworks that are easily made and coordinated to Pd(II); the resulting complexes, which show significant steric and electronic differences from their oxazoline counterparts, as well as intermolecular H-bonding in the solid state, can be isolated in diastereomerically pure form and are remarkably resistant to hydrolysis.     

Structural and dielectric behaviour of non-aqueous lyotropic mixtures: influence of amphiphile chain lengths and counter ions

This study highlights the effects of amphiphile chain length and counter ions on the self-assembly and dielectric behaviour of non-aqueous lyotropic liquid crystals. Two-dimensional hexagonal mesophase is seen for short-chain length sodium dodecyl sulphate, while lamellar and multiwall lamellar mesophases are noticed for long-chain length cetyltrimethylammonium bromide and polyoxyethylene (20) sorbitan monolaurate amphiphiles in the non-aqueous domains of ethylene glycol. A strong influence of amphiphile counter ions is seen on static dielectric constant, loss factor, relaxation frequency and relaxation time of these lyotropic mixtures. Refractive indices of these lyotropic phases are also highlighted.     

Water incorporation into a micellar-lamellar phase (dodecyl maltoside-water)

Many alkylated sugars are surfactants, and show lamellar phases which prove to be identical to those of more conventional surfactants. Most, if not all, previous investigations focus on the behaviour of these compounds in pure form. Dodecyl maltoside shows the same lamellar phase as when dry, but on the addition of water the layer spacing expands, and on addition of more water, a hexagonal phase forms. The area per head group increases substantially with water addition, indicating that the water is incorporated into the layers, possibly at the head groups. We suggest that the hexagonal phase is the system's answer to the frustration caused by a large head group area compared with that of the tails.     

Cross-linked normal hexagonal and bicontinuous cubic assemblies via polymerizable gemini amphiphiles

The synthesis and lyotropic liquid-crystalline (LLC) phase behavior of a homologous series of intrinsically cross-linkable gemini surfactants are described. These novel bis(alkyl-1,3-diene)-based phosphonium gemini amphiphiles exhibit "normal" hexagonal (H(I)), Type I bicontinuous cubic (Q(I)), and lamellar (L(alpha)) phases in water, and can be photocross-linked with retention of phase architecture in each case. On the basis of their locations on the phase diagram, their powder X-ray diffraction profiles, and the physical properties of the cross-linked materials, the Q(I) phases formed by these gemini monomers are consistent with four possible bicontinuous cubic architectures with P or I space group symmetry that have been identified previously for small molecule amphiphiles. The extent of polymerization (i.e., the degree of diene conversion) achieved in the LLC phases was determined to be in the 23% to 71% range using UV-vis spectrometry, which is more than sufficient to extensively stabilize the systems. The resulting cross-linked H(I), L(alpha), and Q(I) phases are stable up to 300 degrees C in air. To our knowledge, these reactive amphiphiles constitute the first example of a polymerizable gemini surfactant, and the first example of a cross-linkable amphiphile system that can be polymerized in both the H(I) and a Q(I) mesophase with retention of phase microstructure.     

Effects of solvent, pH and β-cyclodextrin on the fluorescent behaviour of lomustine

Fluorescent behaviour of lomustine, a DNA cross-linking agent, was investigated in different solvents, pH and in the presence of β-cyclodextrin (β-CD). The solvents in which fluorescence spectra were observed play a major role in determining the spectral intensity of fluorophore, since it was found to exhibit new fluorescent properties essentially influenced by intermolecular interactions, particularly by intermolecular H-bonding formed with solvents. The pH-dependence profile was typically U-shape with a maximum at pH between 3.51 and 6.58. It was corroborated that the fluorescence emission band of lomustine is significantly intensified in the presence of β-CD. From the changes in the fluorescence spectra, it was concluded that β-CD forms a 1:1 inclusion complex with lomustine and its association constant was calculated.     

Ordered 2-D and 3-D nanostructured amphiphile self-assembly materials stable in excess solvent

Amphiphile lyotropic liquid crystalline self-assembly materials are being used for a diverse range of applications. Historically, the most studied lyotropic liquid crystalline phase is probably the one-dimensional (1-D) lamellar phase, which has been employed as a model system for biomembranes and for drug delivery applications. In recent years, the structurally more complex 2-D and 3-D ordered lyotropic liquid crystalline phases, of which reversed hexagonal (H(2)) and reversed cubic phases (v(2)) are two prominent examples, have received growing interest. As is the case for the lamellar phase, these phases are frequently stable in excess water, which facilitates the preparation of nanoparticle dispersions and makes them suitable candidates for the encapsulation and controlled release of drugs. Integral membrane protein crystallization media and templates for the synthesis of inorganic nanostructured materials are other applications for 2-D and 3-D amphiphile self-assembly materials. The number of amphiphiles identified as forming nanostructured reversed phases stable in excess solvent is rapidly growing. In this article, different classes of amphiphiles that form reversed phases in excess solvent are reviewed, with an emphasis on linking phase behavior to amphiphile structure. The different amphiphile classes include: ethylene oxide-, monoacylglycerol-, glycolipid-, phosphatidylethanolamine-, and urea-based amphiphiles.     

Side reactions in controlling the quality, yield, and stability of high quality colloidal nanocrystals

Effects of side reactions during the formation of high quality colloidal nanocrystals were studied using ZnO as a model system. In this case, an irreversible side reaction, formation of esters, was identified to accompany formation of ZnO nanocrystals through the chemical reaction between zinc stearate and an excess amount of alcohols in hydrocarbon solvents at elevated temperatures. This irreversible side reaction made the resulting nanocrystals stable and with nearly unity yield regardless of their size, shape, and size/shape distribution. Ostwald ripening and intraparticle ripening were stopped due to the extremely low solubility/stability of the possible monomers because all free ligands in the solution were consumed by the side reaction. However, focusing on size distribution and 1D growth that are needed for the growth of high quality nanocrystals could still occur for high yield reactions. Upon the addition of a small amount of stearic acid or phosphonic acid, immediate partial dissolution of ZnO nanocrystals took place. Although the excess alcohol could not react with the resulting zinc phosphonic acid salt, it could force the newly formed zinc stearate gradually but completely back onto the existing nanocrystals. The results in this report indicate that side reactions are extremely important for the formation of high quality nanocrystals by affecting their quality, yield, and stability under growth conditions. Due to their lack of information in the literature and obvious practical advantages, studies of side reactions accompanying formation of nanocrystals are important for both fundamental science related to crystallization and industrial production of high quality nanocrystals.     

Synthesis of self-doped conducting polyaniline bearing phosphonic acid

As a self-doped conducting polyaniline bearing phosphonic acid, poly(2-methoxyaniline-5-phosphonic acid) (PMAP) was synthesized via oxidative polymerization of 2-methoxyaniline-5-phosphonic acid. The pyridinium salt of thus-obtained PMAP was water-soluble and its film exhibited conductivity.     

Protonation of polyaniline with lightly sulfonated polystyrene

Protonation of polyaniline base with lightly sulfonated polystyrene in polar solvents such as dimethyl sulfoxide and N-methyl-2-pyrrolidone was investigated by UV-Vis absorption spectra. As the molar ratio of sulfonated polystyrene/polyaniline increases, the conversion from polyaniline base form to salt form is observed owing to increased protonation. The isosbestic point clearly shows that quinoid unit and semiquinoid unit are in equilibrium. They are functions of the sulfonic acid concentration and solvent media.     

Structure/property relationships for the thermotropic behavior of lysine-based amphiphiles: from hexagonal to smectic phases

Amino acid-derived gemini surfactants arise as a potentially good alternative to the more conventional lipid and synthetic catanionic systems in view of their enhanced interfacial properties, increased chemical stability, and low toxicity. The presence of an amino acid as the polar headgroup allows toxicity reduction, with the simultaneous increase of biodegradability. For these compounds, the establishment of structure/function relationships from the assessment of their basic aggregation properties is therefore of the utmost interest, e.g., in the design of operative self-assembled systems (e.g., liposomes, nanotubes, etc). In this context, the study of the thermal phase behavior of the dry surfactants is a natural, straightforward first step, the more so as thermotropic liquid crystals are also relevant for practical applications. In this work, several lysine-based amphiphiles with a gemini-like configuration have been synthesized, with the amino acid side chain as the spacer group. The molecules are either esters (neutral, with C6-C12 even chains) or sodium carboxylates (anionic, with C6-C12 even chains). Upon increasing the temperature, different crystalline (cr) and liquid-crystalline (lc) phases have been detected and the corresponding thermodynamic and structural parameters determined by a combination of differential scanning calorimetry, polarizing light microscopy and small-angle X-ray scattering. The phase behavior of the amphiphiles is highly dependent on both the chain length and the presence of charge on the headgroup, with significant differences occurring within and between each group of molecules. The C6 and C8 esters form reverse hexagonal cr and lc phases, while C10 and C12 self-assemble into smectic cr and lc structures, with C10 showing also a reverse hexagonal lc phase prior to isotropization. All the carboxylate derivatives form smectic lc phases at high enough temperature prior to isotropization. The rationalization of the phase behavior and phase transition energetics of the compounds has been put forth on the basis of the intermolecular interactions at stake (van der Waals, H-bonding, electrostatic, and packing) and the molecular shape of the amphiphile.     

Phase behaviour of lithium and sodium salts of phenylstearic acid

Phenylstearic acid, prepared from oleic acid and benzene, using the Friedel-Crafts reaction, has been confirmed to be a reproducible mixture of twelve positional isomers. Lithium and sodium salts of this acid are semi-crystalline solids which behave in many ways like pure single substances. The thermotropic polymorphism of these soaps has been studied using DSC and polarizing microscopy (as well as X-ray diffraction and ⁷Li NMR spectroscopy for the former soap). Both soaps exhibit characteristic stepwise melting behaviour and form stable reversed hexagonal mesophases at elevated temperatures, in contrast to the lamellar phases exhibited by the unsubstituted soaps.     

Neutralization of 1-(Aminoethyl)phosphonic Acid and Protonation of Its Salt Anion. Processing Dilatometric Data with the CPESSP Program

Volume changes resulting from neutralization of 1-(aminoethyl)phosphonic acid and protonation of the anion of its bis(tetraethylammonium) salt were determined by the dilatometric method. Protonation constants, apparent molar volumes of the acid and its ionized forms, and volume changes on neutralization of the acid and protonation of its salt were calculated. The presence of the betaine form of the acid in solutions was detected. The rule of the constancy of the sum of the volume effects of the protonation and neutralization reactions was shown to be valid for conjugate acid-base pairs of dibasic acids.     

Unusually stable aqueous lyotropic gyroid phases from gemini dicarboxylate surfactants

Aqueous lyotropic liquid crystal (LLC) assemblies with bicontinuous cubic morphologies (Q-phases) have shown promise in applications ranging from selective chemical separations to ion transporting media, yet universal design criteria for amphiphiles that adopt these unique structures remain elusive. Recent reports have demonstrated that cationic gemini surfactants exhibit a tendency to form bicontinuous cubic LLCs as compared to single-tail amphiphiles; however, the universality of this surfactant design motif in stabilizing Q-phases remains untested. Herein, we report the modular synthesis of a new class of anionic gemini surfactants derived from aliphatic carboxylic acids and demonstrate their unexpectedly strong propensity to form gyroid LLC phases with unprecedented stability between 25 and 100 °C over amphiphile concentration windows up to 20 wt % wide. By systematically varying the alkyl spacer length and surfactant counterions (Na(+), K(+), and (CH(3))(4)N(+)), we identify molecular motifs that favor formation of technologically useful bicontinuous cubic LLC morphologies.