Shear-induced Multilamellar Vesicle Research Articles

Ferrihydrite nanoparticles entrapped in shear-induced multilamellar vesicles

HypothesisFerrihydrite (Fh) nanoparticles are receiving considerable scientific interest due to their large reactive surface areas, crystalline structures, and nanoparticle morphology. They are of great importance in biogeochemical processes and have the ability to sequester hazardous and toxic substances. Here, the working hypothesis was to entrap fractal-like Fh nanoparticles, with a radius of gyration of 6.2 nm and a primary building block of polydisperse spheres with a radius of 0.8 nm, in a shear-induced multilamellar vesicle (MLV) state using a 40 wt% polyethylene glycol dodecyl ether surfactant. ExperimentsSmall- and Wide- Angle X-ray scattering revealed the equilibrium state of the non-ionic planar lamellar phase, the Fh dispersion, and their mixture. The MLV state was induced by using a shear flow in a Taylor-Couette geometry of a rheometer. FindingsThe nonionic surfactant initially exhibited a lamellar gel phase with two distinct d-spacings of 11.0 and 9.7 nm, which collapsed into the MLV state under shear flow. The Fh nanoparticles induced bilayer attraction by suppressing lamellar layer undulations, decreasing the d-spacing. These results are helpful in the understanding of the relationship between nanoparticle size and nanoparticle-bilayers interactions and provides insight on Fh encapsulations in a kinetically stable MLVs state.

Effect of interlamellar interactions on shear induced multilamellar vesicle formation.

Shear-induced multilamellar vesicle (MLV) formation has been studied by coupling the small-angle neutron scattering (SANS) technique with neutron spin echo (NSE) spectroscopy. A 10% mass fraction of the nonionic surfactant pentaethylene glycol dodecyl ether (C12E5) in water was selected as a model system for studying weak inter-lamellar interactions. These interactions are controlled either by adding an anionic surfactant, sodium dodecyl sulfate, or an antagonistic salt, rubidium tetraphenylborate. Increasing the charge density in the bilayer induces an enhanced ordering of the lamellar structure. The charge density dependence of the membrane bending modulus was determined by NSE and showed an increasing trend with charge. This behavior is well explained by a classical theoretical model. By considering the Caillé parameters calculated from the SANS data, the layer compressibility modulus B¯ is estimated and the nature of the dominant inter-lamellar interaction is determined. Shear flow induces MLV formation around a shear rate of 10 s-1, when a small amount of charge is included in the membrane. The flow-induced layer undulations are in-phase between neighboring layers when the inter-lamellar interaction is sufficiently strong. Under these conditions, MLV formation can occur without significantly changing the inter-lamellar spacing. On the other hand, in the case of weak inter-lamellar interactions, the flow-induced undulations are not in-phase, and greater steric repulsion leads to an increase in the inter-lamellar spacing with shear rate. In this case, MLV formation occurs as the amplitude of the undulations gets larger and the steric interaction leads to in-phase undulations between neighboring membranes.

Multi-lamellar vesicle formation in a long-chain nonionic surfactant: C16E4/D2O system

The temperature dependent rheological and structural behavior of a long-chain C16E4 (tetraethylene glycol monohexadecyl ether) surfactant in D2O has been studied within the regime of low shear range. In the absence of shear flow, the system forms a lamellar liquid crystalline phase at relatively high temperatures. The present paper reports on the shear-induced multi-lamellar vesicle (MLV) formation in C16E4/D2O at 40wt.% of surfactant in the temperature range of 40–55°C. The transition from planar lamellar structure to multi-lamellar vesicles has been investigated by time-resolved experiments combining rheology and nuclear magnetic resonance (rheo-NMR), rheo small-angle neutron scattering (rheo-SANS) and rheometry. The typical transient viscosity behavior of MLV formation has been discovered at low shear rate value of 0.5s−1.

Homogeneous length scale of shear-induced multilamellar vesicles studied by diffusion NMR

A recently developed protocol for pulsed gradient spin echo (PGSE) NMR is applied for the size determination of multilamellar vesicles (MLVs). By monitoring the self-diffusion behavior of water, the technique yields an estimate of the homogeneous length scale λ hom, i.e. the maximum length scale at which there is local structural heterogeneity in a globally homogeneous material. A cross-over between local non-Gaussian to global Gaussian diffusion is observed by varying the experimentally defined length- and time-scales. Occasional observation of a weak Bragg peak in the PGSE signal attenuation curves permits the direct estimation of the MLV radius in favorable cases, thus yielding the constant of proportionality between λ hom and radius. The microstructural origin of the Bragg peak is verified through Brownian dynamics simulations and a theoretical analysis based on the center-of-mass diffusion propagator. λ hom is decreasing with increasing shear rate in agreement with theoretical expectations and results from 2H NMR lineshape analysis.

Effect of Shear Rates on the MLV Formation and MLV Stability Region in the C12E5/D2O System: Rheology and Rheo-NMR and Rheo-SANS Experiments

At high temperatures, pentaethylene glycol monododecyl ether (C12E5) in D2O forms a swollen lamellar phase. This letter reports the shear-induced multilamellar vesicle (MLV) formation in a sample that contains 40 wt % C12E5 dissolved in D2O at 55 °C. This transition has been investigated by time-resolved rheo-nuclear magnetic resonance, rheo small-angle neutron scattering, and rheometry. The typical transient viscosity behavior of MLV formation has been discovered at 1 s(-1). For the first time, it has been found that MLVs are not stable over time when subjected to high shear rates. Our results show that the MLV stability is confined in a narrow region in the range 1-10 s(-1) shear rates. This is not observed for other CnEm surfactants.

二分子膜系ラメラ相における流動誘起多層膜ベシクル構造形成

Shear-induced instability of bilayer membrane systems has attracted much attention. One of the most interesting shear effects is a shear-induced structural transition from the lamellar to the multilamellar vesicle. In this review, we show two topics related to the non-equilibrium structural formation phenomena under shear; the influence of the triblock copolymer on the shear-induced multilamellar vesicle formation, and the shear quench-induced discontinuous size change of the multilamellar vesicle. In the first topic, we study the effect of the triblock copolymer on the shear-induced lamellar-to-multilamellar vesicle formation. Shear-induced multilamellar vesicle formation behavior is quite sensitive to the interaction between grafted polymer chains and surfactant bilayer membranes. Entropy based contribution to the modulus of bilayer controls the shear-induced multilamellar vesicle formation behavior. In the second topic, we study how the kinetic pathway on the size change process of the multilamellar vesicle is decided under shear. These studies will give us a hint how the soft matter systems change their structure under non-equilibrium states.

Size Determination of Shear-Induced Multilamellar Vesicles by Rheo-NMR Spectroscopy

A model for analyzing the deuterium ((2)H) NMR line shapes of D(2)O in surfactant multilamellar vesicle (MLV, "onion") systems is proposed. The assumption of the slow exchange of water molecules between adjacent layers implies that the (2)H NMR line shape is simply given by a sum of Lorentzians if the condition of motional narrowing is also fulfilled. Using the classical two-step model for the NMR relaxation in structured fluids allows us to calculate how the NMR line shape depends on the MLV size. The model is tested on two different MLV systems for which the NMR line shapes are measured as a function of the applied shear rate using rheo-NMR. The MLV sizes obtained are in good agreement with previous data from rheo-small-angle light scattering.

Influence of a Triblock Copolymer on Phase Behavior and Shear-Induced Topologies of a Surfactant Lamellar Phase

The influence of a triblock copolymer, poly(ethylene oxide)20-b-poly(propylene oxide)70-b-poly(ethylene oxide)20 (Pluronic P123) on the phase behavior and on the shear-induced multilamellar vesicle (MLV, also called Onion) formation in the lyotropic lamellar phase of the nonionic surfactant C10E3 was investigated by means of rheology, small-angle neutron scattering (SANS), and microscopy. Added triblock copolymer shifted the Lalpha-L3 phase transition to lower temperatures. In the presence of triblock copolymer, MLV structure was not stable and easily transformed back into the lamellar phase with increasing polymer concentration and temperature. In the study of the shear-induced MLV formation, we found an increase of the critical shear rate for the onset of the shear-thickening, which also indicates the instability of MLV in the presence of the triblock copolymer. No MLV formation was observed at high polymer concentration. Suppression of the shear-induced MLV formation might be attributed to the enhancement of the effective surface tension originating from the excluded volume effect between polymers adsorbed onto the membranes.

Shear-Induced Transitions between a Planar Lamellar Phase and Multilamellar Vesicles: Continuous versus Discontinuous Transformation

The shear-induced transitions between an oriented lamellar phase and shear-induced multilamellar vesicles (MLVs) in a nonionic surfactant system were studied by deuterium rheo-NMR spectroscopy as a function of time in start-up experiments at several temperatures and shear rates. By starting from an initial state of oriented lamellae and observing the transformation to the final steady state of MLVs and vice-versa, two different mechanisms were found, depending on the direction of the transition and the initial state. The transition is continuous when MLVs are formed, starting from the oriented lamellar phase. On the other hand, a discontinuous nucleation-and-growth process with a coexistence region is observed when transforming MLVs into an oriented lamellar phase.

Measurement of multilamellar onion dimensions under shear using frequency domain pulsed gradient NMR

We present a simple method by which the dimensions of shear-induced multilamellar vesicles (MLVs), also known as onions, can be measured during the shearing process itself. This approach is based on the use of a closely spaced train of magnetic field gradient pulses applied during a CPMG echo sequence. The CPMG train compensates flow effects while the frequency-dependence of apparent diffusion can reveal the onion size. We present here a simple phenomenological model for restricted diffusion in multilamellar vesicles, which may be used to interpret the resulting diffusion spectrum. We demonstrate this approach with MLVs formed from the lamellar phase of sodium dodecyl sulfate (SDS) in water and octanol.

Vorticity banding during the lamellar-to-onion transition in a lyotropic surfactant solution in shear flow

We report on the rheology of a lyotropic lamellar surfactant solution (SDS/dodecane/pentanol/ water), and identify a discontinuous transition between two shear thinning regimes which correspond to the low-stress lamellar phase and the more viscous shear-induced multilamellar vesicle, or "onion" phase. We study in detail the flow curve, stress as a function of shear rate, during the transition region, and present evidence that the region consists of a shear-banded phase where the material has macroscopically separated into bands of lamellae and onions stacked in the vorticity direction. We infer very slow and irregular transformations from lamellae to onions as the stress is increased through the two-phase region, and identify distinct events consistent with the nucleation of small fractions of onions that coexist with sheared lamellae.

Effect of Hydrophobically Modified Polymers on Shear-Induced Multilamellar Vesicles

The effects of polymer concentration, polymer molecular weight, and hydrophobe substitution level of modified poly(acrylic acid) polymers on the formation, size, and viscoelastic properties of shear-induced multilamellar vesicles (onions) are studied by rheology and light diffraction. The onions are close-packed, space-filling vesicles formed by shearing aqueous lamellar phases of C12E5 surfactant to produce phases with sufficient order and size uniformity (O(1-3 microm)) to diffract light. The addition of hydrophobically modified polymers enhances the rate of formation, uniformity, and stability independent of hydrophobe substitution level. Onion size decreases with increasing shear rate as observed for pure surfactant onion systems, but the shear-rate dependence is changed by the polymer. The onion phase has a plateau modulus that increases with polymer concentration but is independent of hydrophobe substitution level or molecular weight. The model presented by Panizza et al. that relates the plateau modulus of the onion phase to membrane rigidity and the compression modulus is consistent with independent measurements of membrane properties from SANS.

Reversible size of shear-induced multi-lamellar vesicles

We have investigated the reversibility in the shear-induced multi-lamellar vesicle (MLV) size during stepwise cycling of the shear rate by employing common rheometry, polarized light microscopy and rheo-optic techniques. We thus address the question whether there is a true MLV steady state, irrespective of history. The system studied, was the nonionic surfactant triethylene glycol decyl ether (C10E3) with a concentration of 40 wt.% in (DO)-O-2 and a constant temperature of 25 degrees C. It was found that the MLV size varies reversibly with varying shear rate, and hence there exists a true steady state in the presence of shear flow. The experimental observations of reversibility are however restricted to higher shear rates. Because the transformation of the size results from the shear strain, the process is very slow at lower shear rates, where the steady state cannot be reached within a reasonable experimental time.

Multilamellar vesicles in a commercial surfactant system

AbstractThe manufacture of concentrated detergent granules in the detergent industry can be achieved by the incorporation of surfactant pastes, such as linear alkylbenzene sulfonate paste (LAS)—a lamellar liquid crystalline material (surfactant concentration of ca. 78 wt. %). LAS paste was processed at 25°C and 60°C, in both the absence and presence of sodium disilicate (Na2O:2SiO2) additive, and the effect on the formation of shear‐induced multilamellar vesicle (MLV) microstructures was studied. Our results suggest that LAS pastes of high hardness and stiffness are always associated with MLV microstructures and vice versa—these are known as “structured” pastes in industry, and also appear nonadhesive. MLVs are able to form from “pure” LAS at 25°C, although, at 60°C, sodium disilicate is necessary. With increased processing time, the size of the MLVs decreases and becomes more uniform—pastes are also increasingly hard and stiff. When stored, “structured” pastes eventually revert back to being soft and sticky, reflecting the metastable nature of the MLVs.

Nonionic Amphiphilic Bilayer Structures under Shear

The effect of shear on the lamellar phase of amphiphilic systems has been widely studied in a variety of amphiphilic systems as a function of shear rate. In this investigation, we fixed the shear rate and performed temperature scan experiments on a two-component (C10E3−water) system. We observed a sequence of phases, from the low to high temperature range: multilamellar vesicle to planar lamellar to sponge phase. The shear-induced multilamellar vesicle (MLV) phase exhibited the most interesting behavior and is the main focus of the present study. Small-angle neutron and light scattering techniques were used to elucidate the microstructure, to determine the bilayer orientation, and to characterize the size of these structures. The interlamellar spacing was observed to be the same in the lamellar as in the MLV phase, and the MLV phase exhibited symmetrical scattering in the neutral and flow directions, indicating that the layers in the vesicles are spherically shaped at the selected shear rate (γ = 100 s-...

Preparation of Indium−Tin Oxide Particles in Shear-Induced Multilamellar Vesicles (Spherulites) as Chemical Reactors

Spherulites, spherical multilamellar vesicles (300−10 000 nm in diameter), were formed by applying shear force to the mixture of two lamellar phases, containing inorganic salts (indium nitrate and tin chloride) in one lamellar phase (I) and a precipitating agent (ammonium hydroxide) in another lamellar phase (II). These spherulites were employed as a reaction medium to prepare the indium−tin hydroxide nanoparticles. The chemical reaction for the formation of indium−tin hydroxide particles took place in the hydrophilic layers of lamellar phase I in spherulites composed of AOT (dioctyl sulfosuccinate sodium salt), because the vesicle wall is selectively permeable to the anions but practically impermeable to cations. Inorganic salts were encapsulated within the hydrophilic layers of spherulites. Indium−tin hydroxide particles were collected by breaking the spherulite structures by adding acetone after reaction, and spherical indium−tin oxide (ITO) particles of about 10−30 nm in size were obtained after calci...