Guruswamy Kumaraswamy

Novel flow apparatus for investigating shear-enhanced crystallization and structure development in semicrystalline polymers

An instrument to study the effects of shearing on the crystallization process in semicrystalline polymers is described. It can impose transient stresses similar to those encountered in polymer processing and provides in situ monitoring of microstructure development during and after cessation of flow. Box-like wall shear stress profiles (rise and fall times under 50 ms with maximum wall shear stress on the order of 0.1 MPa) can be applied for controlled durations. A unique feature of our device is that it accommodates a wide variety of real-time probes of structure such as visible and infrared polarimetry and light and x-ray scattering measurements. The design also allows us to retrieve the sample for ex situ optical and electron microscopy. Data are acquired with millisecond resolution enabling us to record the extent of shear deformation of the polymer melt during the pressure pulse. Our device works with small sample quantities (as little as 5 g; each experiment takes ~ 500 mg) as opposed to the kilogram quantities required by previous instruments capable of imposing comparable deformations. This orders-of-magnitude reduction in the sample size allows us to study model polymers and new developmental resins, both of which are typically available only in gram-scale quantities. The compact design of the shear cell makes it possible to transport it to synchrotron light sources for in situ x-ray scattering studies of the evolution of the crystalline structure. Thus, our device is a valuable new tool that can be used to evaluate the crystallization characteristics of resins with experimental compositions or molecular architectures when subjected to processing-like flow conditions. We demonstrate some of the features of this device by presenting selected results on isotactic polypropylenes.

Self-assembly of silica particles in a nonionic surfactant hexagonal mesophase.

We investigate the process of self-assembly, and the resultant structures in composites of silica particles with a hexagonal mesophase of a nonionic surfactant and water. We report a systematic transition in behavior when the particle size is increased relative to the characteristic mesophase spacing. Water dispersible cage-like silsesquioxanes that are molecular analogues of silica particles and are smaller than the mesophase spacing swell the space between the surfactant cylinders. Silica particles comparable to the characteristic hexagonal spacing partition into the hexagonal phase and into strandlike particulate aggregates. Even larger particles phase separate from the hexagonal phase to form particulate strands that organize with a mesh size comparable to the wavelength of visible light. This self-assembly is reversible and the particles disperse by breaking up the aggregates on heating the composite into the isotropic phase. On cooling from the isotropic phase into the hexagonal, the particles are expelled from the growing hexagonal domains and finally impinge to form strandlike aggregates. Unusually, the isotropization temperature is increased in the composites as the particles nucleate the formation of the hexagonal phase.

Enhancing Cubosome Functionality by Coating with a Single Layer of Poly-ε-lysine

We report the preparation and characterization of monoolein cubosomes that can be easily surface modified through adsorption of a single layer of cationic poly-ε-lysine. Poly-ε-lysine coated cubosomes show remarkable stability in serum solution, are nontoxic and, are readily internalized by HeLa cells. The poly-ε-lysine coating provides chemical handles for further bioconjugation of the cubosome surface. We also demonstrate that the initial release rate of a hydrophilic drug, Naproxen sodium, from the cubosomes is retarded with just a single layer of polymer. Interestingly, cubosomes loaded with Naproxen sodium, recently shown to have anticancer properties, cause more apoptosis in HeLa cells when compared to free unencapsulated drug.

Assembly of polyethyleneimine in the hexagonal mesophase of nonionic surfactant: effect of pH and temperature.

We investigate the dispersion of a pH responsive polymer, polyethyleneimine, PEI, in a hexagonal (H(1)) mesophase of a nonionic surfactant, C(12)E(9), and water, at pH ranging from basic (pH = 12.8) to acidic (pH = 1). While the C(12)E(9)/H(2)O phase behavior is independent of pH, we demonstrate that, in the PEI/C(12)E(9)/H(2)O system, changing the pH influences PEI-C(12)E(9) interactions, and thus, influences the isotropic-H(1) phase transition. With decrease in pH, there is increasing protonation of the PEI chain, and consequently, the chain extends. We show, using a combination of SAXs, optical microscopy and visual experiments, that the inclusion of PEI in a 1:1 surfactant-water mixture, lowers the hexagonal-isotropic transition temperature, T(HI). At higher pH = 12.8, T(HI) shows a pronounced decrease from 50 to 13 °C on addition of PEI, and the PEI/C(12)E(9)/H(2)O system forms a transparent gel. At pH = 1, we observe qualitatively different behavior and an opaque gel forms below T(HI) = 25 °C. The isotropic-H(1) transition, in turn, influences the phase separation of PEI chains from the C(12)E(9)/H(2)O system. 2D NMR ROESY data provides evidence that there are strong surfactant-PEI interactions at high pH that significantly reduce at lower pH. The NMR data is in accord with molecular dynamics simulations that show that surfactants strongly aggregate with unprotonated PEI chains, but not with fully protonated chains; thus, in this system, the pH controls a cascade of microstructural organization: increasing pH decreases chain protonation and increases polymer-surfactant interactions, resulting in suppression of the isotropic-H(1) transition to lower temperatures, thus, influencing the phase separation of PEI from the surfactant/water system.

Synthesis of poly-L-glutamic acid grafted silica nanoparticles and their assembly into macroporous structures.

Polypeptide-coated silica nanoparticles represent an interesting class of organic-inorganic hybrids since the ordered secondary structure of the polypeptide grafts imparts functional properties to these nanoparticles. The synthesis of a poly-l-glutamic acid (PLGA) silica nanoparticle hybrid by employing N-carboxyanhydride (NCA) polymerization to synthesize the polypeptide chains and Cu catalyzed azide alkyne cycloaddition reaction to graft these chains onto the silica surface is reported. This methodology enables the synthesis of well-defined polypeptide chains that are attached onto the silica surface at high surface densities. The PLGA-silica conjugate particles are well dispersed in water, and have been thoroughly characterized using multinuclear ((13)C, (29)Si) solid state NMR, thermogravimetric analysis, Fourier transform infrared, dynamic light scattering, and transmission electron microscopy. The pH-dependent reversible aggregation of the PLGA-silica particles, driven by the change in PLGA structure, has also been studied. Preliminary results on the use of aqueous dispersions of silica-PLGA for the preparation of three-dimensional macroporous structures with oriented pores by ice templating methodology are also demonstrated. These macroporous materials, comprising a biocompatible polymer shell covalently attached to rigid inorganic cores, adopts an interesting lamellar structure with fishbone-type architecture.

Gelation of covalently edge-modified laponites in aqueous media. 1. rheology and nuclear magnetic resonance.

We describe the covalent modification of the edges of laponite with organic groups and the influence of this modification on gelation behavior. We compare three materials: an unmodified laponite, a laponite edge modified with a trimethyl moiety (MLap), and an octyldimethyl moiety (OLap). Gelation is investigated using rheology and NMR T1 relaxation measurements and nuclear Overhauser enhancement spectroscopy (NOESY). MLap and OLap show qualitatively different gelation. Gelation of MLap is very similar to laponite: MLap gels over the same time scale as laponite and has about the same solid modulus, and the MLap gel is almost as transparent as laponite. In contrast, OLap gels rapidly relative to laponite and forms a weak, turbid gel. We believe that gelation in laponite and MLap results from the formation of a network of well-dispersed platelets (or a few platelets), while in OLap, gelation results from a network of stacks of several platelets. NMR relaxation measurements indicate that gelation does not affect the average relaxation of water protons. However, T1 increases marginally for the protons in the organic moieties in MLap and decreases for protons in the organic moieties in OLap. Relaxation measurements, analyses of line width, and NOESY taken together suggest that, in OLap, gelation is a consequence of association of the organic moieties on the laponite edges, and that this association strengthens with time. Thus, the time-dependent changes in NMR suggest a structural origin for the time-dependent changes in the rheological behavior.

Polymer and Colloidal Inclusions in Lyotropic Lamellar and Hexagonal Surfactant Mesophases

Abstract Introduction of colloidal particles or polymers as inclusions into lyotropic surfactant mesophases influences mesophase stability and structure. Such mesophase/inclusion composites have relevance for areas as diverse as nanomedicine, consumer care products, catalyst supports, and photonic metamaterials. Localization of the inclusions in the mesophase depends on specific interactions between inclusion and surfactant and on the nature of the mesophase. This chapter focuses on inclusions in lamellar and hexagonal mesophases. We review the experimental literature on the influence of particles and polymers on the interaction between surfactant structures in the mesophase and the theoretical explanations for the observed behavior.

Preparation of macroporous scaffolds with holes in pore walls and pressure driven flows through them

Controlling the pore architecture in macroporous scaffolds has important implications for their use as reactor packings and as catalyst supports. We report the preparation of a macroporous structure, where the pore walls are perforated by holes. These materials are prepared by modification of the ice-templating protocol developed in our group. We freeze a dispersion of colloidal silica, polymer and cross-linker in a water/acetonitrile medium and allow crosslinking to proceed in the frozen state. The presence of a small fraction of acetonitrile (varying between 1.6% to 6.4%) results in the formation of holes in the pore walls. Increasing the acetonitrile concentration changes the pore size distribution, and produces smaller pores on average. This also results in an increasing fraction of the wall area being covered by small pores, of the order of a few microns in size. Perforation of the walls by pores does not change the overall porosity or modulus of the scaffolds. However, the introduction of pores leads to a drastic reduction in the pressure drop required to pump liquid through the scaffolds. The observed residence time distribution (RTD) in the scaffolds is represented by two plug flow reactors (PFRs) in parallel. The RTD results indicate that increasing the hole fraction in the pore walls results in increased channelling which explains the aforementioned decreased pressure drop during pressure driven flow.

Single-Particle Tracking To Probe the Local Environment in Ice-Templated Crosslinked Colloidal Assemblies

We use single-particle tracking to investigate colloidal dynamics in hybrid assemblies comprising colloids enmeshed in a crosslinked polymer network. These assemblies are prepared using ice templating and are macroporous monolithic structures. We investigate microstructure-property relations in assemblies that appear chemically identical but show qualitatively different mechanical response. Specifically, we contrast elastic assemblies that can recover from large compressive deformations with plastic assemblies that fail on being compressed. Particle tracking provides insights into the microstructural differences that underlie the different mechanical response of elastic and plastic assemblies. Since colloidal motions in these assemblies are sluggish, particle tracking is especially sensitive to imaging artifacts such as stage drift. We demonstrate that the use of wavelet transforms applied to trajectories of probe particles from fluorescence microscopy eliminates stage drift, allowing a spatial resolution of about 2 nm. In elastic and plastic scaffolds, probe particles are surrounded by other particles-thus, their motion is caged. We present mean square displacement and van Hove distributions for particle motions and demonstrate that plastic assemblies are characterized by significantly larger spatial heterogeneity when compared with the elastic sponges. In elastic assemblies, particle diffusivities are peaked around a mean value, whereas in plastic assemblies, there is a wide distribution of diffusivities with no clear peak. Both elastic and plastic assemblies show a frequency independent solid modulus from particle tracking microrheology. Here too, there is a much wider distribution of modulus values for plastic scaffolds as compared to elastic, in contrast to bulk rheological measurements where both assemblies exhibit a similar response. We interpret our results in terms of the spatial distribution of crosslinks in the polymer mesh in the colloidal assemblies.

Large PAMAM Dendron Induces Formation of Unusual P4332 Mesophase in Monoolein/Water Systems

Compact macromolecular dendrons have previously been shown to induce the formation of discontinuous inverse micellar assemblies with Fd3 m symmetry in monoolein/water systems. Here, we demonstrate that a large PAMAM dendron (G5: fifth generation) induces the formation of a very unusual mesophase with P4332 symmetry. This mesophase had previously been observed in monoolein/water systems only on addition of cytochrome c. The P4332 mesophase can be considered an intermediate phase between the bicontinuous Ia3 d and discontinuous micellar mesophases. We present a detailed investigation of the phase behavior of monoolein/water as a function of G5 concentration and temperature. Addition of 1% G5 in 85/15 monoolein/water system induces a transition from the Lα to Ia3 d phase. Further increase in G5 concentration to above 2% induces the formation of the P4332 phase. In contrast to this, incorporation of lower generation PAMAM dendrons (G2-G4) in monoolein/water yields a qualitatively different phase diagram with the formation of the reverse micellar Fd3 m phase. PAMAM dendrons of all generations, G2-G5, bear terminal amine groups that interact with the monoolein headgroup. The compact molecular architecture of the dendrons and these attractive interactions induce bending of the monoolein bilayer structure. For smaller dendrons, G2-G4, this results in the formation of the Fd3 m phase. However, the large size of the G5 dendron precludes this and a rare intermediate phase between the Ia3 d and discontinuous micellar phase, and the P4332 mesophase forms instead.