Shear-Induced Ordering of Nanopores and Instabilities in Concentrated Surfactant Mesh Phases.

Mixed surfactant systems with strongly bound counterions show many interesting phases such as the random mesh phase consisting of a disordered array of defects (water-filled nanopores in the bilayers). The present study addresses the non-equilibrium phase transition of the random mesh phase under shear to an ordered mesh phase with a high degree of coherence between nanopores in three dimensions. In situ small-angle synchrotron X-ray study under different shear stress conditions shows sharp Bragg peaks in the X-ray diffraction, successfully indexed to the rhombohedral lattice with R3̅m space group symmetry. The ordered mesh phase shows isomorphic twinning and buckling at higher shear stress. Our experimental studies bring out rich non-equilibrium phase transitions in concentrated cationic surfactant systems with strongly bound counterions hitherto not well explored and provide motivation for a quantitative understanding.

Grazing Incidence X-ray Diffraction Studies of Lipid-Peptide Mixed Monolayers during Shear Flow.

Grazing incidence X-ray diffraction (GIXD) studies of monolayers of biomolecules at an air-water interface give quantitative information of in-plane packing, coherence length of crystalline domains, etc. Rheo-GIXD measurements can reveal quantitative changes in the nanocrystalline domains of a monolayer under shear. Here, we report GIXD studies of monolayers of alamethicin peptide, DPPC lipid, and their mixtures at an air-water interface under steady shear stress. The alamethicin monolayer and the mixed monolayer show a flow jamming transition. On the other hand, the pure 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayer under constant stress flows steadily with a notable enhancement of the area/molecule and coherence lengths, suggesting the fusion of nanocrystallites during flow. The DPPC-alamethicin mixed monolayer shows no significant change in the area/DPPC molecule, but the coherence lengths of the individual phases (DPPC and alamethicin) increase, suggesting that the crystallites of individual phases grow bigger by merging of domains. More phase separation occurs in the system during flow. Our results show that rheo-GIXD has the potential to explore in situ molecular structural changes under rheological conditions for a diverse range of confined biomolecules at interfaces.

Reversible shear-induced crystallization above equilibrium freezing temperature in a lyotropic surfactant system.

We demonstrate a unique shear-induced crystallization phenomenon above the equilibrium freezing temperature (T(K)°) in weakly swollen isotropic (Li) and lamellar (La) mesophases with bilayers formed in a cationic-anionic mixed surfactant system. Synchrotron rheological X-ray diffraction study reveals the crystallization transition to be reversible under shear (i.e., on stopping the shear, the nonequilibrium crystalline phase Lc melts back to the equilibrium mesophase). This is different from the shear-driven crystallization below T(K)°, which is irreversible. Rheological optical observations show that the growth of the crystalline phase occurs through a preordering of the Li phase to an La phase induced by shear flow, before the nucleation of the Lc phase. Shear diagram of the Li phase constructed in the parameter space of shear rate (γ) vs. temperature exhibits Li → Lc and Li → La transitions above the equilibrium crystallization temperature T(K)°, in addition to the irreversible shear-driven nucleation of Lc in the Li phase below T(K)°. In addition to revealing a unique class of nonequilibrium phase transition, the present study urges a unique approach toward understanding shear-induced phenomena in concentrated mesophases of mixed amphiphilic systems.

Viscoelastic behavior of human lamin A proteins in the context of dilated cardiomyopathy.

Lamins are intermediate filament proteins of type V constituting a nuclear lamina or filamentous meshwork which lines the nucleoplasmic side of the inner nuclear membrane. This protein mesh provides a supporting scaffold for the nuclear envelope and tethers interphase chromosome to the nuclear periphery. Mutations of mainly A-type lamins are found to be causative for at least 11 human diseases collectively termed as laminopathies majority of which are characterised by aberrant nuclei with altered structural rigidity, deformability and poor mechanotransduction behaviour. But the investigation of viscoelastic behavior of lamin A continues to elude the field. In order to address this problem, we hereby present the very first report on viscoelastic properties of wild type human lamin A and some of its mutants linked with Dilated cardiomyopathy (DCM) using quantitative rheological measurements. We observed a dramatic strain-softening effect on lamin A network as an outcome of the strain amplitude sweep measurements which could arise from the large compliance of the quasi-cross-links in the network or that of the lamin A rods. In addition, the drastic stiffening of the differential elastic moduli on superposition of rotational and oscillatory shear stress reflect the increase in the stiffness of the laterally associated lamin A rods. These findings present a preliminary insight into distinct biomechanical properties of wild type lamin A protein and its mutants which in turn revealed interesting differences.

Discontinuous shear thickening in confined dilute carbon nanotube suspensions.

A monotonic decrease in viscosity with increasing shear stress is a known rheological response to shear flow in complex fluids in general and for flocculated suspensions in particular. Here we demonstrate a discontinuous shear-thickening transition on varying shear stress where the viscosity jumps sharply by four to six orders of magnitude in flocculated suspensions of multiwalled carbon nanotubes (MWNT) at very low weight fractions (approximately 0.5%). Rheooptical observations reveal the shear-thickened state as a percolated structure of MWNT flocs spanning the system size. We present a dynamic phase diagram of the non-Brownian MWNT dispersions revealing a starting jammed state followed by shear-thinning and shear-thickened states. The present study further suggests that the shear-thickened state obtained as a function of shear stress is likely to be a generic feature of fractal clusters under flow, albeit under confinement. An understanding of the shear-thickening phenomena in confined geometries is pertinent for flow-controlled fabrication techniques in enhancing the mechanical strength and transport properties of thin films and wires of nanostructured composites as well as in lubrication issues.

Viscoelastic properties of nanocrystalline films of semiconducting chalcogenides at liquid/liquid interface.

The interfacial shear rheological properties of a continuous single-crystalline film of CuS and a 3D particulate gel of CdS nanoparticles (3-5 nm in diameter) formed at toluene-water interfaces have been studied. The ultrathin films (approximately 50 nm in thickness) are formed in situ in the shear cell through a reaction at the toluene-water interface between a metal-organic compound in the organic layer and an appropriate reagent for sulfidation in the aqueous layer. Linear viscoelastic spectra of the nanofilms reveal solid-like rheological behavior with the storage modulus higher than the loss modulus over the range of angular frequencies probed. Large strain amplitude sweep measurements on the CdS nanofilms formed at different reactant concentrations suggest that they form a weakly flocculated gel. Under steady shear, the films exhibit a yield stress, followed by a steady shear thinning at high shear rates. The viscoelastic and flow behavior of these films that are in common with those of many 3D "soft" materials like gels, foams, and concentrated colloidal suspensions can be described by the "soft" glassy rheology model.

Re-entrant phase behavior of a concentrated anionic surfactant system with strongly binding counterions.

The phase behavior of the anionic surfactant sodium dodecyl sulfate (SDS) in the presence of the strongly binding counterion p-toluidine hydrochloride (PTHC) has been examined using small-angle X-ray diffraction and polarizing microscopy. A hexagonal-to-lamellar transition on varying the PTHC to SDS molar ratio (alpha) occurs through a nematic phase of rodlike micelles (Nc) --> isotropic (I) --> nematic of disklike micelles (N(D)) at a fixed surfactant concentration (phi). The lamellar phase is found to coexist with an isotropic phase (I') over a large region of the phase diagram. Deuterium nuclear magnetic resonance investigations of the phase behavior at phi = 0.4 confirm the transition from N(C) to N(D) on varying alpha. The viscoelastic and flow behaviors of the different phases were examined. A decrease in the steady shear viscosity across the different phases with increasing alpha suggests a decrease in the aspect ratio of the micellar aggregates. From the transient shear stress response of the N() and N(D) nematic phases in step shear experiments, they were characterized to be tumbling and flow aligning, respectively. Our studies reveal that by tuning the morphology of the surfactant micelles strongly binding counterions modify the phase behavior and rheological properties of concentrated surfactant solutions.

Aggregation of a peptide antibiotic alamethicin at the air-water interface and its influence on the viscoelasticity of phospholipid monolayers.

The aggregation properties of an antibiotic membrane-active peptide alamethicin at the air-water interface have been studied using interfacial rheology and fluorescence microscopy techniques. Fluorescence microscopy of alamethicin monolayers revealed a coexistence of liquid expanded (LE) and solid phases at the surface concentrations studied. Interfacial oscillatory shear measurements on alamethicin monolayers indicate that its viscoelastic properties are determined by the area fraction of the solid domains. The role of zwitterionic phospholipids dioleoylphosphatidyl choline (DOPC) and dioleoylphosphatidyl ethanolamine (DOPE) on the peptide aggregation behavior was also investigated. Fluorescence microscopy of alamethicin/phospholipid monolayers revealed an intermediate phase (I) in addition to the solid and LE phase. In mixed monolayers of phospholipid (L)/alamethicin (P), with increase in L/P, the monolayer transforms from a viscoelastic to a viscous fluid with the increase in area fraction of the intermediate phase. Further, a homogeneous mixing of alamethicin/lipid molecules is observed at L/P > 4. Our studies also confirm that the viscoelasticity of alamethicin/phospholipid monolayers is closely related to the alamethicin/phospholipid interactions at the air-water interface.

Nonlinear viscoelasticity of sorbitan tristearate monolayers at liquid/gas interface.

The interfacial rheology of sorbitan tristearate monolayers formed at the liquid/air interface reveal a distinct nonlinear viscoelastic behavior under oscillatory shear usually observed in many 3D metastable complex fluids with large structural relaxation times. At large strain amplitudes (gamma), the storage modulus (G') decreases monotonically whereas the loss modulus (G'') exhibits a peak above a critical strain amplitude before it decreases at higher strain amplitudes. The power law decay exponents of G' and G'' are in the ratio 2:1. The peak in G'' is absent at high temperatures and low concentration of sorbitan tristearate. Strain-rate frequency sweep measurements on the monolayers do indicate a strain-rate dependence on the structural relaxation time. The present study on sorbitan tristearate monolayers clearly indicates that the nonlinear viscoelastic behavior in 2D Langmuir monolayers is more general and exhibits many of the features observed in 3D complex fluids.

Interfacial rheology of an ultrathin nanocrystalline film formed at the liquid/liquid interface.

We report the interfacial properties of monolayers of Ag nanoparticles 10-50 nm in diameter formed at the toluene-water interface under steady as well as oscillatory shear. Strain amplitude sweep measurements carried out on the film reveal a shear thickening peak in the loss moduli (G") at large amplitudes followed by a power law decay of the storage (G') and loss moduli with exponents in the ratio 2:1. In the frequency sweep measurements at low frequencies, the storage modulus remains nearly independent of the angular frequency, whereas G" reveals a power law dependence with a negative slope, a behavior reminiscent of soft glassy systems. Under steady shear, a finite yield stress is observed in the limit of shear rate .gamma going to zero. However, for .gamma > 1 s-1, the shear stress increases gradually. In addition, a significant deviation from the Cox-Merz rule confirms that the monolayer of Ag nanoparticles at the toluene-water interface forms a soft two-dimensional colloidal glass.

Synthesis of single-crystalline platinum nanorods within a soft crystalline surfactant-Pt(II) complex.

Single-crystalline platinum nanorods, monodisperse in diameter, are synthesized through a simple process at room temperature, in cetyltrimethyl ammonium bromide (CTAB) solution. The complexation of the CTA+ surfactant ion with tetrachloroplatinate in the presence of hexanol leads to the formation of a precipitate with a lamellar crystalline structure. The reduction of Pt(II) metal ions to Pt(0) is carried out using gamma radiolysis. Transmission electron microscopy (TEM) observations of the nanoparticles extracted from the solution, three weeks after radiolysis, revealed single-crystalline Pt nanorods, monodisperse in diameter (3-4 nm) and 20-60 nm long. By following the shape of the nanorods at various stages of the growth, it was found that the single-crystalline nanorods grow by coalescence of spherical seeds 3-4 nm in diameter. This suggests an aggregative mechanism similar to that recently observed for silver particles in solution.

Structure of DNA-CTAB-hexanol complexes.

We have probed structures of the complexes formed by DNA with the cationic surfactant cetyltrimethylammonium bromide in the presence of the cosurfactant hexanol, using small angle x-ray diffraction techniques. They are found to exhibit a hexagonal-->lamellar-->hexagonal transition with increasing hexanol content. Quantitative analysis of the diffraction data shows that the complexes formed at low hexanol concentrations have an intercalated hexagonal (HI) structure, whereas those formed at higher hexanol content have an inverted hexagonal (HII) structure.

Reentrant phase transitions of DNA-surfactant complexes.

Complexes of double-stranded DNA with the cationic surfactant cetyltrimethylammonium bromide have been studied using small angle x-ray diffraction at varying concentrations of DNA and the cosurfactant hexanol. At low DNA concentrations, an intercalated hexagonal (H(c)(I))-->lamellar (L(c)(alpha))-->inverted hexagonal (H(c)(II)) transformation is found on increasing hexanol content. The H(c)(II) structure is converted into L(c)(alpha) on adding more DNA. Further increase in hexanol content leads to a phase separation in the surfactant solution, and a reentrant L(c)(alpha)-->H(c)(II)-->L(c)(alpha) transition is observed as DNA concentration is increased. Such structural transformations of DNA-surfactant complexes, driven by DNA concentration, have not been reported until now.