Polyelectrolyte-induced vesicle formation in lamellar liquid-crystalline model systems

 The object of the research was to investigate the influence of a semiflexible polyanion (carboxymethylcellulose) in the absence and presence of a more flexible cationic polyelectrolyte [poly(diallyldimethyl-ammonium chloride)] on structure formation in liquid-crystalline model systems consisting of sodium dodecyl sulfate (SDS)/ decanol/water. Small-angle X-ray measurements in combination with electron microscopic investigations show the adsorption of the polycation on the SDS head groups. These polymer-modified lamellae form multilamellar vesicles. The semiflexible polyanion was embedded into the liquid crystal without macroscopic phase separation and multivesicular vesicles were formed on the supramolecular level. In combination the oppositely charged polyelectrolytes induce the formation of multivesicular structures where two lamellar structures coexist. Received: 15 July 1999/Accepted in revised form: 22 September 1999     

On the orientation of lamellar block copolymer phases under shear

Self-assembled lamellar structures composed of block copolymers are simulated by molecular dynamics. The response of a bulk system to external shear is investigated, in particular, the average energy, the entropy production, and the stability of the lamellae's orientation. We distinguish two orientations, a parallel orientation in which the normal to the lamellae sheets lies in the direction of the shear gradient, and a perpendicular orientation in which the normal lies perpendicular to the shear gradient and shear direction. The perpendicular phase is stable throughout all shear rates. The parallel phase has higher internal energy and larger entropy production than the perpendicular phase and moreover becomes unstable at relatively small shear rates. The perpendicular orientation should therefore be more stable at any finite shear rate. Surface effects are probably responsible for the stability of the parallel phase observed experimentally at small shear rates.     

Shear-induced topology changes in liquid crystals of the soybean lecithin/DDAB/water system

The viscoelastic behavior of the two different liquid crystalline lamellar phases and the liquid crystalline cubic phase of the mixed soybean lecithin/DDAB system in water was studied through rheology, with mechanical parameters studied as a function of composition. The swollen or diluted lamellar region is formed by vesicles, and its characteristic flow curve presents two-power law regions separated by a region where viscosity passes through a maximum. Yield stress and shear-dependent flow behavior were also observed. The microstructure suffers transformation under shear stress, and rheological response shifts from thixotropic to antithixotropic loops. Similar rheological behavior has been observed for samples in the collapsed or concentrated lamellar region, at the water-rich corner of the phase diagram. Vesicle formation may therefore occur by shearing the initial stacked and open bilayers. However, concentrated lamellar samples in the water-poor part of the phase diagram are less sensitive to shear effects and show plastic behavior and thixotropy. All lamellar samples manifest high elasticity. The dynamic responses of both lamellar topologies, i.e., vesicles and open bilayers, are comparable and exhibit an infinite relation time. The bicontinuous cubic, liquid crystalline phase is highly viscous. Its dynamic response cannot be modeled by a Maxwell model.     

Structural studies of lamellar surfactant systems under shear

Recent experimental studies on concentrated surfactant systems are reviewed. Particular attention is focused on the transformation from planar lamellar sheets to multilamellar vesicles. It is discussed whether both of these states are thermodynamic stable, or if the MLV is an artifact of shear induced factors. Recent studies includes the dependence on shear, and dependence on salt and cosurfactants, and thereby related lamellar defects. The review include moreover the demonstration that polymeric amphiphiles dramatically enhance the quality of classical surfactants.     

Phase behavior of the lecithin/water/isooctane and lecithin/water/decane systems

The isothermal pseudo-ternary-phase diagram was determined at 25 degrees C for systems composed oflecithin, water, and, as oil, either isooctane or decane. This was accomplished by a combination of polarizing microscopy, small-angle X-ray scattering, and NMR techniques. The lecithin-rich region of the phase diagram is dominated by a lamellar liquid-crystalline phase (Lalpha). For lecithin contents less than 60% and low hydration (mole ratio water/lecithin = W0 < 5.5), the system forms a viscous gel of branched cylindrical reverse micelles. With increase in the water content, the system phase separates into two phases, which is either gel in equilibrium with essentially pure isooctane (for lecithin < 25%) or a gel in equilibrium with Lalpha (for lecithin > 25%). These two-phase regions are very thin with respect to water dilution. For 8 < W0 < 54 very stable water-in-oil emulsions form. It is only after ripening for more than 1 year that the large region occupied by the emulsion reveals a complex pattern of stable phases. Moving along water dilution lines, one finds (i) the coexistence of gel, isooctane and Lalpha, (ii) equilibrium between reverse micelles and spherulites, and, finally, (iii) disconnected reverse micelles that fail to solubilize water for W0 > 54. This results in a Winsor II phase equilibrium at low lecithin content, while for lecithin > 20% the neat water is in equilibrium with a reverse hexagonal phase and an isotropic liquid-crystalline phase. The use of the decane as oil does not change the main features of the phase behavior.     

Phase diagrams and structures of lecithin/water systems with branched lecithin components

The influence of chain branching on the phase transition parameters and structures of the homologous series of 1-(x-methylpalmitoyl)-2-hexadecyllecithins in the water-saturated two-phase region (50 wt.% water) were studied by differentialscanning-calorimetry as a function of the position x of methyl branching. With increasing x a linear decrease in the enthalpies and alternating temperatures of main transition were observed. The phase diagram of the ternary system 1-(3-methyl-palmitoyl)-2-hexadecyllecithin/1,2-dipalmitoyllecithin/water (50 wt.% water) showed that both components are completely miscible within the high-temperature phase (L -phase). However, in the low-temperature phase (gel phase), the components are partially miscible only. It follows that gel phases with interdigitated chains and those with tilted chains are not completely miscible. The phase diagram of the ternary system 1,2-di-(8-methylpalmitoyl)-lecithin/1,2-dipalmitoyllecithin/water (50 wt.% water) showed that both components are completely miscible within the high-temperature phase and low-temperature phase. Within the concentration range between the mole fraction x=0.91 and x=0.97, a drop-like course in the phase diagram was obtained.     

Alignment of lamellar diblock copolymer phases under shear: insight from dissipative particle dynamics simulations

Sheared self-assembled lamellar phases formed by symmetrical diblock copolymers are investigated through dissipative particle dynamics simulations. Our intent is to provide insight into the experimental observations that the lamellar phases adopt parallel alignment at low shear rates and perpendicular alignment at high shear rates and that it is possible to use shear to induce a transition from the parallel to perpendicular alignment. Simulations are initiated either from lamellar structures prepared under zero shear where lamellae are aligned into parallel, perpendicular, or transverse orientations with respect to the shear direction or from a disordered melt obtained by energy minimization of a random structure. We first consider the relative stability of the parallel and perpendicular phases by applying shear to lamellar structures initially aligned parallel and perpendicular to the shear direction, respectively. The perpendicular lamellar phase persists for all shear rates investigated, whereas the parallel lamellar phase is only stable at low shear rates, and it becomes unstable at high shear rates. At the high shear rates, the parallel lamellar phase first transforms into an unstable diagonal lamellar phase; and upon further increase of the shear rate, the parallel lamellar phase reorients into a perpendicular alignment. We further determine the preferential alignment of the lamellar phases at low shear rate by performing the simulations starting from either the initial transverse lamellar structure or the disordered melt. Since the low shear-rate simulations are plagued by the unstable diagonal lamellar phases, we vary the system size to achieve the natural spacing of the lamellae in the simulation box. In such cases, the unstable diagonal lamellar phases disappear and lamellar phases adopt the preferential alignment, either parallel or perpendicular. In agreement with the experimental observations, the simulations show that the lamellar phase preferentially adopts the parallel orientation at low shear rates and the perpendicular orientation at high shear rates. The simulations further reveal that the perpendicular lamellar phase has lower internal energy than the parallel lamellar phase, whereas the entropy production of the perpendicular lamellar phase is higher with respect to the parallel lamellar phase. Values of the internal energy and entropy production for the unstable diagonal lamellar phases lie between the corresponding values for the parallel and perpendicular lamellar phases. These simulation results suggest that the relative stability of the parallel and perpendicular lamellar phases at low shear rates is a result of the interplay between competing driving forces in the system: (a) the system's drive to adopt a structure with the lowest internal energy and (b) the system's drive to stay in a stationary nonequilibrium state with the lowest entropy production.     

Interfacial ternary complex DNA/Ca/lipids at anionic vesicle surfaces

The electroporative transfer of gene DNA and other bioactive substances into tissue cells by electric pulses gains increasing importance in the new disciplines of electrochemotherapy and electrogenetherapy. The efficiency of the electrotransfer depends crucially on the adsorption of the gene DNA and oligonucleotides to the plasma cell membranes. Here it is shown that the adsorption of larger oligonucleotides such as fragments (ca. 300 bp) of sonicated calf-thymus DNA, to anionic lipids of unilamellar vesicles (diameter Phi=300+/-90 nm) is greatly enhanced by divalent cations such as Ca(2+)-ions. Applying centrifugation, bound and free DNA are monitored optically at the wavelength lambda=260 nm. Using arsenazo III as a Ca(2+)-indicator and atomic absorption spectroscopy (AAS), Ca(2+)-titrations of DNA and vesicles yield the individual equilibrium constants of Ca(2+)- and DNA-binding not only for the binary complexes: Ca/lipids, Ca/DNA and DNA/lipids, respectively, but also for the various processes to form the ternary complex DNA/Ca/lipids. The data provide the basis for goal-directed optimization protocols for the adsorption and thus efficient electrotransfer of oligonucleotides and polynucleotides into cells.     

Magnetic resonance study on lamellar phases of ammonium perfluorooctanoate

The aggregation properties of ammonium perfluorooctanoate (NH₄-PFO) in concentrated aqueous phases have been investigated by magnetic resonance techniques and have been compared with the aggregation properties in dilute solutions. Magnetic resonance methods indicated that NH₄-PFO—water systems with surfactant concentrations below 45% (w/w) behaved as isotropic purely micellar solutions in the temperature range 285–340 K. For higher concentrations the system exhibited a rather complex structure, having both isotropic and anisotropic components. The nematic nature of the anisotropic fraction was demonstrated by ¹⁹F NMR studies. The ¹⁹F NMR and EPR of nitroxides (TempTMA⁺, 5- and 16-DXSA) inserted as paramagnetic probes into the concentrated NH₄-PFO—water systems allowed us to establish that the lamellar phase could be mechanically oriented between quartz slides. The EPR investigation also gave details concerning the dynamics of both the oriented and non-oriented structures.     

Hexagonal liquid crystalline phases formed in ternary systems of Brij 97-water-ionic liquids

Phase diagrams of two ionic liquids: hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate (bmim-PF(6)) and relatively hydrophilic 1-butyl-3-methylimidazolium tetrafluoroborate (bmim-BF(4)) in aqueous solutions of Brij 97 were determined at 25 degrees C. Two hexagonal liquid crystalline phases formed in bmim-PF(6)- and bmim-BF(4)-containing ternary systems were investigated by means of small-angle X-ray scattering (SAXS) and rheological techniques, with comparison of composition and temperature effects. From analysis of the SAXS data, bmim-PF(6) is dominantly penetrated between the oxyethylene chains of surfactant molecules, whereas bmim-BF(4) is mainly located in the water layer of hexagonal phases. The strength of the network of hexagonal phase formed in the Brij 97/water/bmim-BF(4) system is appreciably stronger than that of the Brij 97/water/bmim-PF(6) system, indicated by the smaller area of the surfactant molecule at the interface and the higher moduli (G', G' '). Temperature has a converse effect on the lattice parameters of the two hexagonal phases.     

Mixed vesicle formation on a ternary surfactant system: didodecyldimethylammonium bromide/dodecylethyldimethylammonium bromide/water

The formation of mixed aggregates has been investigated on a ternary system consisting of two cationic surfactants with similar polar heads and two and/or one 12 carbon atom hydrophobic tail, respectively, didodecyldimethylammonium bromide and dodecylethyldimethylammonium bromide and water. The study has been carried out by means of conductivity, zeta potential, and cryogenic transmission electronic microscopy (cryo-TEM) experiments on the very diluted region. A variety of mixed aggregates, microaggregates, vesicles, and micelles has been found, depending on system composition and total surfactant concentration. Mixed critical microaggregate concentration and mixed critical vesicle concentration have been determined from conductivity data. Furthermore, zeta potential and cryo-TEM experiments allow for the characterization of the aggregates/solution interface and of the shape and size of the aggregates. This experimental evidence has also been analyzed in terms of the theoretical packing parameter, P.     

Influence of ionic charges on the bilayers of lamellar phases

The influence of ionic charges on the mesophases in the ternary system of C(12-16)E(6) (LA 070), ethylhexylglycerid (EHG), and water was studied. The charge was introduced by adding the ionic surfactant SDS (sodium dodecyl sulfate). The single lamellar phase (5 wt % LA 070 and 240 mM EHG in water) yields a bluish homogeneous solution. With the addition of SDS, the samples become more and more clear. Rheology measurements indicate that increased charge density increases the storage modulus G', and the lamellar phases show typical behavior of a viscoelastic fluid with a yield stress at higher SDS concentration. SAXS measurements show that the interlamellar distance D decreases with SDS concentration. The addition of ionic surfactants suppresses the Helfrich undulations, flattens the bilayers, and decreases interbilayer spacing due to electrostatic repulsions of the ionic surfactant head groups. Furthermore, the L(alpha) phase transforms into vesicle phases as the SDS concentration is increased. Second, it is shown that with added NaCl electrolyte the phase with charged surfactant behaves again in the same way as the initial uncharged system. The addition of salt screens the electrostatic interaction, which leads to a higher flexibility of the bilayers and a decrease of the storage modulus G'. Theoretical calculations show that the shear moduli of the L(alpha) phases are much smaller than the osmotic pressure of the systems. Several models are proposed for the explanation of the shear moduli. The model due to Lekkerkerker for the electric contribution of the bending constant of the bilayer seems to yield good results for the transition to vesicles.     

Coexisting lamellar phases in water-oil-surfactant systems induced by the addition of an amphiphilic block copolymer

We report here a pioneering study using quadrupolar splitting NMR to detect new phases and phase compositions in the quasi-ternary microemulsion system water-decane-C(10)E(4)/PEP5-PEO5. The striking observation is that at certain compositions the polymer is apparently no longer incorporated into the membranes of the lamellar phase due to space restrictions. The polymer therefore induces a phase separation into two different lamellar phases L(alpha)(1) and L(alpha)(2) such that it fits into L(alpha)(1) while the excess surfactant forms a polymer-free L(alpha)(2) phase.     

Effective enhancement of peroxydisulfate electrochemiluminescence on C60/DDAB films

Effective enhancement of electrochemiluminescence (ECL) of peroxydisulfate on a C₆₀/didodecyldimethyl ammonium bromide (C₆₀/DDAB) film coated glassy carbon electrode (GCE) surface is reported in this paper. The C₆₀/DDAB film gave lower cathodic current in the presence of peroxydisulfate than that from a bare GCE. To our surprise, electrochemiluminescent intensity from peroxydisulfate reduction was effectively enhanced on the C₆₀/DDAB film, which was 50 times and 250 times higher than those from a DDAB film coated and bare GCE, respectively. Moreover, the ECL onset potential on the C₆₀/DDAB film was about −0.9 V, which positively shifted 200 mV compared with that from the bare GCE. Dissolved oxygen and the applied potential also affected the electrochemiluminescent intensity. The presence of oxygen decreased the intensity, and the intensity reached maximum at the applied potential of −1.7 V. The unique property will greatly enrich ECL studies and applications based on fullerenes.     

Chiral induction of micellar cholesterics from lamellar phases

It is shown for the first time that induced micellar cholesterics can be obtained from lamellar phases within the sequence: lamellar—micellar nematic—micellar cholesteric—biphasic region—isotropic phase. The pitch is shortened by over 50 per cent when the temperature is raised within the cholesteric range of about 15 K.     

Atomic force microscopy images of lyotropic lamellar phases

For the very first time, atomic force microscope images of lamellar phases were observed combined with a freeze fracture technique that does not involve the use of replicas. Samples are rapidly frozen, fractured, and scanned directly with atomic force microscopy, at liquid nitrogen temperature and in high vacuum. This procedure can be used to investigate micro-structured liquids. The lamellar phases in Sodium bis(2-ethylhexyl) sulfosuccinate (AOT)/water and in C12E5/water systems were used to asses this new technique. Our observations were compared with x-ray diffraction measurements and with other freeze fracture methods reported in the literature. Our results show that this technique is useful to image lyotropic lamellar phases and the estimated repeat distances for lamellar periodicity are consistent with those obtained by x-ray diffraction.     

Disconnected lamellar phases (Lalpha) in pseudobinary water-non-ionic surfactant systems: a general phenomenon

This study provides new experimental evidence for the disconnection of the lamellar phase (L(alpha)) in pseudobinary water-non-ionic surfactant systems. To prove that the disconnection is indeed a general phenomenon the phase behavior of the pseudobinary system water-pentaethylene glycol dodecyl ether/hexaethylene glycol dodecyl ether (H(2)O-C(12)E(5)/C(12)E(6)) was investigated as a function of the surfactant composition delta and the total surfactant concentration gamma. At a fixed gamma of 0.10 the extension of the highly diluted L(alpha) phase shrank continuously with increasing amount of C(12)E(6), i.e., increasing delta, until it disappeared at delta=0.60. The gamma-T phase diagram of this particular surfactant mixture was found to have a disconnected L(alpha) phase. For the first time, SAXS measurements were carried out to monitor structural changes related to the disconnection. For this purpose the interlayer spacing d and the effective cross-sectional area a(s) were determined from the SAXS data along characteristic paths through the L(alpha) phase.     

Miscibility behavior of ternary lipidphospholipid/water systems

Differential-scanning-calorimetry was applied to study the lyotropic and thermotropic properties of the two ternary systems dimyristoylcephaline (di-(C14:0)-PE)/Palmitic acid (C₁₅COOH)/water (H₂O) and dimyristoylcephaline (di-(C14:0)-PE)/palmitic acid methyl ester (C₁₅COOMe)/water (H₂O) in dispersions with excess water (50 wt.%).The phase diagrams of both systems showed that the two systems differ in their miscibility behavior. The system di-(C14:0)-PE/C₁₅COOH/H₂O is completely miscible in its high-temperature phase. In the low-temperature phase the mixing gap was found within the concentration range of C₁₅COOH and was also indicated by a maximum value of the transition enthalpy of the pseudo-binary mixtures.In the pseudo-binary system di-(C14:0)-PC/C₁₅COOMe/H₂O, the tendency towards demixing is much more pronounced. It was observed that the incorporated C₁₅COOMe melted above its normal melting point, but below the transition temperature of di(C14:0)-PE/H₂O system; therefore, the phase transition started at lower temperature. In the low-temperature phase, both lipids are partially miscible. The demixing range of the phase diagram lies within the concentration region of C₁₅COOMe. Up to the mole fraction ofXC₁₅COOMe=0.43, C₁₅COOMe can be incorporated into theL-phase of the system di-(C14:0)-PE/H₂O.     

Growth of new ternary intermetallic phases from Ca/Zn eutectic flux

The eutectic 7.3:2.7 molar ratio mixture of calcium and zinc metal melts at 394 °C and was explored as a solvent for the growth of new intermetallic phases for potential use as hydrogen storage materials. The reaction of nickel in this molten mixture produces two new phases—the CaCu₅-related structure CaNi₂Zn₃ (P6/mmm, a=8.9814(5) Å, c=4.0665(5) Å) and a new cubic structure Ca₂₁Ni₂Zn₃₆ (Fd-3m, a=21.5051(4) Å). Palladium-containing reactions produced CaPd_0.85Zn_1.15 with the orthorhombic TiNiSi structure type (Pnma, a=7.1728(9) Å, b=4.3949(5) Å, c=7.7430(9) Å). Reactions of platinum in the Ca/Zn mixture produce Ca₆Pt₃Zn₅, with an orthorhombic structure related to that of W₃CoB₃ (Pmmn, a=13.7339(9) Å, b=4.3907(3) Å, c=10.7894(7) Å).