Patrick Davidson

Swollen liquid-crystalline lamellar phase based on extended solid-like sheets

Ordering particles at the nanometre length scale is a challenging and active research area in materials science. Several approaches have so far been developed, ranging from the manipulation of individual particles to the exploitation of self-assembly in colloids. Nanometre-scale ordering is well known to appear spontaneously when anisotropic organic moieties form liquid-crystalline phases; this behaviour is also observed for anisotropic mineral nanoparticles resulting in the formation of nematic, smectic and hexagonal mesophases. Here we describe a lyotropic liquid-crystalline lamellar phase comprising an aqueous dispersion of planar solid-like sheets in which all the atoms involved in a layer are covalently bonded. The spacing of these phosphatoantimonate single layers can be increased 100-fold, resulting in one-dimensional structures whose periodicity can be tuned from 1.5 to 225 nanometres. These highly organized materials can be mechanically or magnetically aligned over large pH and temperature ranges, and this property can be used to measure residual dipolar couplings for the structure determination of biomolecules by liquid-state NMR. We also expect that our approach will result in the discovery of other classes of mineral lyotropic lamellar phases.

Liquid–crystalline aqueous clay suspensions

This article demonstrates the occurrence of a true isotropic/nematic transition in colloidal Brownian aqueous suspensions of natural nontronite clay. The liquid–crystalline character is further evidenced by polarized light microscopy and small-angle x-ray scattering experiments in the presence and absence of modest external magnetic fields. The complete phase diagram ionic strength/volume fraction then exhibits a clear biphasic domain in the sol region just before the gel transition in contrast with the situation observed for other swelling clays in which the sol/gel transition hinders the isotropic/nematic transition. Small-angle x-ray scattering measurements of gel samples reveal strong positional and orientational orders of the particles, proving unambiguously the nematic character of the gel and, thus, clearly refuting the still prevalent “house of cards” model, which explains the gel structure by means of attractive interactions between clay platelets. Such order also is observed in various other swelling clay minerals; therefore, this very general behavior must be taken into account to reach a better understanding of the rheological properties and phase behavior of these systems.

Lamellar Biogels: Fluid-Membrane-Based Hydrogels Containing Polymer Lipids

A class of lamellar biological hydrogels comprised of fluid membranes of lipids and surfactants with small amounts of low molecular weight poly(ethylene glycol)-derived polymer lipids (PEG-lipids) were studied by x-ray diffraction, polarized light microscopy, and rheometry. In contrast to isotropic hydrogels of polymer networks, these membrane-based birefringent liquid crystalline biogels, labeled Lα,g, form the gel phase when water is added to the liquid-like lamellar Lα phase, which reenters a liquid-like mixed phase upon further dilution. Furthermore, gels with larger water content require less PEG-lipid to remain stable. Although concentrated (∼50 weight percent) mixtures of free PEG (molecular weight, 5000) and water do not gel, gelation does occur in mixtures containing as little as 0.5 weight percent PEG-lipid. A defining signature of the Lα,g regime as it sets in from the fluid lamellar Lα phase is the proliferation of layer-dislocation-type defects, which are stabilized by the segregation of PEG-lipids to the defect regions of high membrane curvature that connect the membranes.

Fibrillogenesis in Dense Collagen Solutions: A Physicochemical Study

Fibrillogenesis, the formation of collagen fibrils, is a key factor in connective tissue morphogenesis. To understand to what extent cells influence this process, we systematically studied the physicochemistry of the self-assembly of type I collagen molecules into fibrils in vitro. We report that fibrillogenesis in solutions of type I collagen, in a high concentration range close to that of living tissues (40-300 mg/ml), yields strong gels over wide pH and ionic strength ranges. Structures of gels were described by combining microscopic observations (transmission electron microscopy) with small- and wide-angle X-ray scattering analysis, and the influence of concentration, pH, and ionic strength on the fibril size and organization was evaluated. The typical cross-striated pattern and the corresponding small-angle X-ray scattering 67-nm diffraction peaks were visible in all conditions in the pH 6 to pH 12 range. In reference conditions (pH 7.4, ionic strength=150 mM, 20 degrees C), collagen concentration greatly influences the overall macroscopic structure of the resultant fibrillar gels, as well as the morphology and structure of the fibrils themselves. At a given collagen concentration, increasing the ionic strength from 24 to 261 mM produces larger fibrils until the system becomes biphasic. We also show that fibrils can form in acidic medium (pH approximately 2.5) at very high collagen concentrations, beyond 150 mg/ml, which suggests a possible cholesteric-to-smectic phase transition. This set of data demonstrates how simple physicochemical parameters determine the molecular organization of collagen. Such an in vitro model allows us to study the intricate process of fibrillogenesis in conditions of molecular packing close to that which occurs in biological tissue morphogenesis.

Invited Article. X-ray diffraction by mesomorphic comb-like polymers

Abstract This article presents a survey of the literature on X-ray diffraction by mesomorphic comb-like polymers. Special emphasis is placed upon two points: it is often possible to study the localization of the backbone in the smectic phases by considering the intensities of the Bragg reflections from the layers. It is also possible to observe different kinds of short range order and localized defects through their contribution to the X-ray diffuse scattering. For instance, the average SA structure may be affected by layer undulations or disturbed by edge dislocations. By examining the many X-ray diffraction studies already published, it can be shown that the backbones have an ambiguous influence upon the molecular organization. They sometimes tend, for entropic reasons, to lessen the positional long range order or to create defects, whereas they sometimes promote short range order because they induce correlations among the mesogenic cores chemically linked to them.

Liquid-crystalline nematic phase in aqueous suspensions of a disk-shaped natural beidellite clay.

After size-selection and osmotic pressure measurements at fixed ionic strength, the behavior of aqueous colloidal suspensions of anisotropic disklike beidellite clay particles has been investigated by combining optical observations under polarized light, rheological, and small angle X-ray scattering (SAXS) experiments. The obtained phase diagrams (volume fraction/ionic strength) reveal, for ionic strength below 10(-3) M/L, a first-order isotropic/nematic (I/N) phase transition before gel formation at low volume fractions, typically around 0.5%. This I/N transition line displays a positive slope for increasing ionic strength and shifts toward lower volume fraction with increasing particle size, confirming that the system is controlled by repulsive interactions. The swelling laws, derived from the interparticle distances obtained by SAXS, display a transition from isotropic swelling at low volume fractions to lamellar swelling at higher volume fractions. The liquid-crystal properties have then been investigated in detail. Highly aligned nematic samples can be obtained in three different ways, by applying a magnetic field, an ac electric field, and by spontaneous homeotropic anchoring on surfaces. The birefringence of the fluid nematic phase is negative with typical values around 5 x 10(-4) at a volume fraction of about 0.6%. High nematic order parameters have been obtained as expected for well-aligned samples. The nematic director is aligned parallel to the magnetic field and perpendicular to the electric field.

Self-Assembly of CdSe Nanoplatelets into Giant Micrometer-Scale Needles Emitting Polarized Light

We report on the self-assembly of colloidal CdSe nanoplatelets into micrometers long anisotropic needle-like superparticles (SPs), which are formed in solution upon addition of an antisolvent to a stable colloidal dispersion. Optical fluorescence microscopy, transmission electron microscopy, and small-angle X-ray scattering provide detailed structural characterization and show that each particle is composed of 10(6) nanoplatelets organized in highly aligned columns. Within the SPs, the nanoplatelets are stacked on each other to maximize the contact surface between the ligands. When deposited on a substrate, the planes of the platelets are oriented perpendicularly to its surface and the SPs exhibit polarized emission properties.

Aqueous suspensions of natural swelling clay minerals. 1. Structure and electrostatic interactions.

In this article, we present a general overview of the organization of colloidal charged clay particles in aqueous suspension by studying different natural samples with different structural charges and charge locations. Small-angle X-ray scattering experiments (SAXS) are first used to derive swelling laws that demonstrate the almost perfect exfoliation of clay sheets in suspension. Using a simple approach based on geometrical constraints, we show that these swelling laws can be fully modeled on the basis of morphological parameters only. The validity of this approach was further extended to other clay data from the literature, in particular, synthetic Laponite. For all of the investigated samples, experimental osmotic pressures can be properly described by a Poisson-Boltzmann approach for ionic strength up to 10(-3) M, which reveals that these systems are dominated by repulsive electrostatic interactions. However, a detailed analysis of the Poisson-Boltzmann treatment shows differences in the repulsive potential strength that are not directly linked to the structural charge of the minerals but rather to the charge location in the structure for tetrahedrally charged clays (beidellite and nontronites) undergoing stronger electrostatic repulsions than octahedrally charged samples (montmorillonites, laponite). Only minerals subjected to the strongest electrostatic repulsions present a true isotropic to nematic phase transition in their phase diagrams. The influence of ionic repulsions on the local order of clay platelets was then analyzed through a detailed investigation of the structure factors of the various clay samples. It appears that stronger electrostatic repulsions improve the liquidlike positional local order.

Sol−Gel and Isotropic/Nematic Transitions in Aqueous Suspensions of Natural Nontronite Clay. Influence of Particle Anisotropy. 2. Gel Structure and Mechanical Properties

After size-selection, the phase behavior of aqueous suspensions of nontronite clay was analyzed by osmotic pressure measurements, rheological experiments, and small-angle X-ray scattering. All the measurements confirm that for ionic strength < or =10(-3) M/L, the system is purely repulsive. By combining results from osmotic pressure measurements and X-ray scattering, it appears that the pressure of the system can be well-described using a simple Poisson-Boltzmann treatment based on the interaction between charged infinite parallel planes. In terms of rheological properties, even if the status of the sol/gel transition remains partially unclear as the number density of particles at the sol-gel transition exhibits a -2 power dependence with average particle size, the yield stress and elasticity of the gels can be easily renormalized for all particle sizes on the basis of the volume of the particles. Furthermore, rheological modeling of the flow curves shows that for all the particles, an approach based on excluded volume effects captures most features of nontronite suspensions. Still, the high shear flow properties of the suspensions that reveal a strong orientation of particles in the flow are affected by electrostatic interactions. This study then shows that the rich phase behavior of clay minerals, notably the fact that some clay minerals display an isotropic/nematic transition while others exhibit a sol-gel transition, requires a full understanding of all the interactions in the system that can only be achieved by working on well-characterized size-selected samples.

Sol/gel and isotropic/nematic transitions in aqueous suspensions of natural nontronite clay. Influence of particle anisotropy. 1. Features of the i/n transition.

The phase behavior of a natural nontronite clay was studied for size-selected particles by combining osmotic pressure measurements, visual observations under polarized light, and rheological experiments. In parallel, the positional and orientational correlations of the particles were analyzed by small-angle X-ray scattering. Aqueous suspensions of nontronite exhibit a true isotropic/nematic (I/N) transition that occurs before the sol/gel transition, for ionic strengths below 10(-3) M/L. In this region of the phase diagrams, the system appears to be purely repulsive. The I/N transition shifts toward lower volume fractions for increasing particle anisotropy, and its position in the phase diagram agrees well with the theoretical predictions for platelets. SAXS measurements reveal the presence of characteristic interparticular distances in the isotropic, nematic, and gel phases. The swelling law (separation distance vs swelling law) exhibits two regimes. For high volume fractions, the swelling law is one-dimensional as in layered systems and reveals the presence of isolated platelets. At lower volume fraction, distances scale as phi(-1/3), indicating isotropic volumic swelling. Finally, the experimental osmotic pressure curves can be satisfactorily reproduced by considering the interparticle distances between two charged planes whose effective charge is around 10% of the structural charge.