Nanoconfinement of water layers in lamellar structures prepared in the presence and absence of organic solvent.

An attempt is made to draw a line of comparison between the extent of rigidity of the hydration layers bound to the interfacial region of lamellar structures of Aerosol OT (AOT, sodium bis(2-ethylhexyl) sulfosuccinate) in water, in the presence and absence of an organic solvent using POM, SAXS, cryo-TEM, and time-resolved fluorescence spectroscopy. These systems are ternary mixtures of AOT, water, and n-heptane containing lamellar structures in an aqueous layer at higher w(0) values (w(0) = 300 and 150) and a binary solution of 20 and 50% AOT in neat water (w/w). The solvation shells residing at the vicinity of these lamellar structures are monitored using two different coumarin probes (C153 and C500). It is intended to envisage a comparative solvation dynamics study of the restricted aqueous region confined in lamellar structures formed in ternary mixture and binary solution. Though steady state measurements show a similar microenvironment probed by the fluorophores in lamellar structures formed in the two different aqueous phases, temporal evolution of the solvent correlation function C(t) unveils the existence of lamellar structures with different degrees of confinement of water layers in these two systems. A slower relaxation of the restricted aqueous region in lamellar structures of binary solution signifies the presence of more rigid interfacially bound water layers at the lamellar interface than in the ternary mixture having a similar weight percentage of AOT in water. The present investigation concludes that the lamellar structures formed under two different conditions provide a similar hydrophobic environment with different extents of localized water populations at the lamellar interface as manifested by the solvent relaxation time in agreement with SAXS and cryo-TEM images.

Helix--rod transition in a nanospring.

A model of helical spring is described whose effective pitch and length are decided by the balance of the attractive van der Waals and repulsive hydration and electrical double layer forces. Also the electric contribution to the curvature free energy is taken into account. The stability of the nanospring is investigated and it is shown that the spring becomes unstable and jumps to its extended state on increase of electrostatic repulsion beyond a limit implying a jump in viscosity of suspension of springs in the solution. The magnitude of the jump and threshold potential are investigated.

An analysis of FtsZ assembly using small angle X-ray scattering and electron microscopy.

Small angle X-ray scattering (SAXS) was used for the first time to study the self-assembly of the bacterial cell division protein, FtsZ, with three different additives: calcium chloride, monosodium glutamate and DEAE-dextran hydrochloride in solution. The SAXS data were analyzed assuming a model form factor and also by a model-independent analysis using the pair distance distribution function. Transmission electron microscopy (TEM) was used for direct observation of the FtsZ filaments. By sectioning and negative staining with glow discharged grids, very high bundling as well as low bundling polymers were observed under different assembly conditions. FtsZ polymers formed different structures in the presence of different additives and these additives were found to increase the bundling of FtsZ protofilaments by different mechanisms. The combined use of SAXS and TEM provided us a significant insight of the assembly of FtsZ and microstructures of the assembled FtsZ polymers.

Catanionic surfactants as nanospring suspensions: a model.

A model for a dilute suspension of nanosprings, whose equilibrium configuration and extension are controlled by electrical double layer forces, is presented along with a model for changing packing parameter. The dependence of viscosity on surface charge is calculated. The possibility of shear-thickening is demonstrated. It is argued that mixtures of cationic and anionic surfactants which show two peaks in viscosity and a minimum along with shear-thickening are likely candidates for this model.

A small-angle X-ray scattering study of the structure of lysozyme-sodium dodecyl sulfate complexes.

The structure of lysozyme-sodium dodecyl sulfate (SDS) complexes in solution is studied using small-angle X-ray scattering (SAXS). The SAXS data cannot be explained by the necklace and bead model for unfolded polypeptide chain interspersed with surfactant micelles. For the protein and surfactant concentrations used in the study, there is only marginal growth of SDS micelles as they complex with the protein. Being a small and rather rigid protein, lysozyme can penetrate the micellar core which is occupied by flexible and disordered paraffin chains and also the shell occupied by the hydrated head groups. A partially embedded swollen micellar model seems appropriate and describes well the scattering data. The SAXS intensity profiles are analyzed by considering the change in the electron scattering length density of the micellar core and shell due to complexation with protein and treating the intermicellar interaction using rescaled mean spherical approximation (RMSA) for charged spheres.

Architecture of fiber network: from understanding to engineering of molecular gels.

A new approach of engineering of molecular gels was established on the basis of a nucleation-initiated network formation mechanism. A variety of gel network structures can be obtained by regulating the starting temperature of the sol-gel transition. This enables us to tune the network from the spherulitic domains pattern to the extensively interconnected fibrillar network. As the consequence of fibrous network structure turning, desirable rheological and other in-use properties of the materials can be obtained accordingly. This approach of micro-/nanostructural fabrication may open up a new route for micro-/nanofunctional materials engineering in general.

Design of superior spider silk: from nanostructure to mechanical properties.

Spider dragline silk is of practical interest because of its excellent mechanical properties. However, the structure of this material is still largely unknown. In this article, we report what we believe is a new model of the hierarchical structure of silk based on scanning electron microscope and atomic force microscope images. This hierarchical structure includes beta-sheet, polypeptide chain network, and silk fibril. It turns out that an exceptionally high strength of the spider dragline silk can be obtained by decreasing the size of the crystalline nodes in the polypeptide chain network while increasing the degree of orientation of the crystalline nodes. Based on this understanding, how the reeling speed affects mechanical properties of spider dragline silk can be understood properly. Hopefully, the understanding obtained in this study will shed light on the formation of spider silk, and consequently, on the principles for the design of ultrastrong silk.

Colloidal phase transition driven by alternating electric field.

The transverse two-dimensional assembly of colloidal particles near an electrode surface subjected to ac polarization is studied by varying the frequency and field strength in the absence and presence of an added electrolyte. The variation of the translational and bond-orientational correlation functions with frequency suggests the existence of a hexatic phase in which the particles retain the remnants of the crystalline long-range orientational order, but has a liquidlike translational order. The electrohydrodynamic (EHD) flow is analyzed in the light of the existing theoretical models. The equilibrium distribution of particles is considered to be the resultant of the two opposing forces--Stoke's force due to EHD flow and the screened Coulomb interaction between the colloidal particles. Several features of the experimental results are discussed, such as the role played by the EHD flow in the particle aggregation, the dependence of the equilibrium interparticle separation on ionic strength, zeta potential, and particle size.

Investigation on the mechanism of crystallization of soluble protein in the presence of nonionic surfactant.

The mechanism of crystallization of soluble, globular protein (lysozyme) in the presence of nonionic surfactant C8E4 (tetraoxyethylene glycol monooctyl ether) was examined using both static and dynamic light scattering. The interprotein interaction was found to be attractive in solution conditions that yielded crystals and repulsive in the noncrystallizing solution conditions. The validity of the second virial coefficient as a criterion for predicting protein crystallization could be established even in the presence of nonionic surfactants. Our experiments indicate that the origin of the change in interactions can be attributed to the adsorption of nonionic surfactant monomers on soluble proteins, which is generally assumed to be the case with only membrane proteins. This adsorption screens the hydrophobic attractive force and enhances the hydration and electrostatic repulsive forces between protein molecules. Thus at low surfactant concentration, the effective protein-protein interaction remains repulsive. Large surfactant concentrations promote protein crystallization, possibly due to the attractive depletion force caused by the intervening free surfactant micelles.

Topology evolution and gelation mechanism of agarose gel.

Kinetics as well as the evolution of the agarose gel topology is discussed, and the agarose gelation mechanism is identified. Aqueous high melting (HM) agarose solution (0.5% w/v) is used as the model system. It is found that the gelation process can be clearly divided into three stages: induction stage, gelation stage, and pseudoequilibrium stage. The induction stage of the gelation mechanism is identified using an advanced rheological expansion system (ARES, Rheometric Scientific). When a quench rate as large as 30 deg C/min is applied, gelation seems to occur through a nucleation and growth mechanism with a well-defined induction time (time required for the formation of the critical nuclei which enable further growth). The relationship between the induction time and the driving force which is determined by the final setting temperature follows the 3D nucleation model. A schematic representation of the three stages of the gelation mechanism is given based on turbidity and rheological measurements. Aggregation of agarose chains is promoted in the polymer-rich phase and this effect is evident from the increasing mass/length ratio of the fiber bundles upon gelation. Continuously increasing pore size during gelation may be attributed to the coagulation of the local polymer-rich phase in order to achieve the global minimum of the free energy of the gelling system. The gel pore size determined using turbidity measurements has been verified by electrophoretic mobility measurements.

Formation of ordered arrays of oriented polyaniline nanoparticle nanorods.

We report the preparation of ordered polyaniline (PANI) nanorod arrays in an aqueous medium. The oriented PANI nanorods (80-400 nm in diameter and 8-15 mum in length) were synthesized in the presence of hydrophilic Allura Red AC (ARAC) as the structure-directing agent and ammonium persulfate as an oxidant in HCl solution. The morphologies of the oriented PANI nanoparticle nanorods were confirmed by scanning electron microscopy (SEM) and transmission electron microscopy images, and the effect of reaction conditions on the morphology of PANI nanostructures was also studied. On the basis of the result obtained from small-angle X-ray scattering, we propose that rodlike micelle arrays of ARAC-aniline are responsible for directing the formation of oriented PANI nanoparticle nanorods. SEM images and the data analysis of static and dynamic light scattering give supportive evidence to the formation of the PANI nanoparticle nanorods by an elongation process. The chemical and electronic structures of the PANI nanorods were also studied by Fourier transform IR and UV-vis spectrometries, respectively.

Protein interactions in undersaturated and supersaturated solutions: a study using light and x-ray scattering.

Protein interactions in undersaturated and supersaturated solutions were investigated using static and dynamic light scattering and small angle x-ray scattering. A morphodrom of lysozyme crystals determined at 35 degrees C and pH = 4.6 was used as a guideline in selecting the protein and precipitant concentrations. The osmotic second virial coefficient, B(22), was determined by static and dynamic light scattering. At low ionic strengths for which no crystals were formed, B(22) was positive indicating repulsive interactions between the protein molecules. Negative B(22) at higher ionic strengths corresponds to attractive interactions where crystallization becomes possible. At two extreme salt concentrations, small angle x-ray scattering data were collected and fitted with a statistical mechanical model based on Derjaguin-Landau-Verwey-Overbeek potential using Random Phase Approximation. This model accounted well for the small angle x-ray scattering data at undersaturated condition with constant potential parameters. At very high salt concentration corresponding to supersaturated solution this model seems to fail, possibly due to the presence of non-Derjaguin-Landau-Verwey-Overbeek hydration repulsion between the molecules.

Gelation of aqueous pectin solutions: a dynamic light scattering study.

We report the dynamic light scattering study of the gelation of aqueous solutions of the biopolymer, pectin, induced by the addition of calcium chloride. The time correlation function data are analyzed under the framework of the coupling model. As the solution enters the semidilute regime where gelation sets in, the relaxation process shows a stretched exponential behavior. The stretching exponent decreases and the characteristic time of the stretched exponential diverges as the system evolves to a gel. Aqueous pectin solutions in the presence of 0.1 M NaCl show similar behavior. Thus, the molecular relaxation modes of pectin solutions can be well described by the coupling model.