Dynamics of anisotropic colloidal systems: What to choose, DLS, DDM or XPCS?

Investigation of the dynamics of colloids in bulk can be hindered by issues such as multiple scattering and sample opacity. These challenges are exacerbated when dealing with inorganic materials. In this study, we employed a model system of Akaganeite colloidal rods to assess three leading dynamics measurement techniques: 3D-(depolarized) dynamic light scattering (3D-(D)DLS), polarized-differential dynamic microscopy (P-DDM), and x-ray photon correlation spectroscopy (XPCS). Our analysis revealed that the translational and rotational diffusion coefficients captured by these methods show a remarkable alignment. Additionally, by examining the q-ranges and maximum volume fractions for each approach, we offer insights into the best technique for investigating the dynamics of anisotropic systems at the colloidal scale.

Probing Cage Relaxation in Concentrated Protein Solutions by X-Ray Photon Correlation Spectroscopy.

Diffusion of proteins on length scales of their size is crucial for understanding the machinery of living cells. X-ray photon correlation spectroscopy (XPCS) is currently the only way to access long-time collective diffusion on these length scales, but radiation damage so far limits the use in biological systems. We apply a new approach to use XPCS to measure cage relaxation in crowded α-crystallin solutions. This allows us to correct for radiation effects, obtain missing information on long time diffusion, and support the fundamental analogy between protein and colloid dynamical arrest.

Extending depolarized DLS measurements to turbid samples.

The application of dynamic light scattering to soft matter systems has strongly profited from advanced approaches such as the so-called modulated 3D cross correlation technique (Mod3D-DLS) that suppress contributions from multiple scattering, and can therefore be used for the characterization of turbid samples. Here we now extend the possibilities of this technique to allow for depolarized light scattering (Mod3D-DDLS) and thus obtain information on both translational and rotational diffusion, which is important for the characterization of anisotropic particles. We describe the required optical design and test the performance of the approach for increasingly turbid samples using well defined anisotropic colloidal models systems. Our measurements demonstrate that 3D-DDLS experiments can be performed successfully for samples with a reduced transmission due to multiple scattering as low as 1%. We compare the results from this approach with those obtained by standard DDLS experiments, and point out the importance of using an appropriate optical design when performing depolarized dynamic light scattering experiments with turbid systems.

Structure and anisotropic dynamics of stimuli responsive colloidal ellipsoids at the nearest neighbor length scale.

Stimuli-responsive self-assembly of (an) isotropic colloids has resulted in a plethora of self-assembled structures with potential applications in fabricating smart materials. A lack of detailed understanding of the interplay between these self-assembled structures and the resulting dynamics has often impeded the exploitation of their full potential. Herein, we have unveiled the relationship between the field-driven self-assembled structures and the corresponding collective dynamics at the nearest neighbor length scale using X-ray photon correlation spectroscopy and magnetic colloidal ellipsoids. We demonstrate that the effective long-time collective diffusion coefficient, Deff(q), scales with the inverse of the scattered intensity for various stimuli-responsive self-assembled phases. At high-volume fraction, the system approaches a kinetically arrested state. The anisotropic slowdown of Deff(q) hints towards the formation of an oriented glass. Our approach opens new avenues for exploring the stimuli-responsive dynamics of strongly interacting colloidal systems with diverse shapes and properties.

Shape Matters in Magnetic-Field-Assisted Assembly of Prolate Colloids.

An anisotropic colloidal shape in combination with an externally tunable interaction potential results in a plethora of self-assembled structures with potential applications toward the fabrication of smart materials. Here we present our investigation on the influence of an external magnetic field on the self-assembly of hematite-silica core-shell prolate colloids for two aspect ratios ρ = 2.9 and 3.69. Our study shows a rather counterintuitive but interesting phenomenon, where prolate colloids self-assemble into oblate liquid crystalline (LC) phases. With increasing concentration, particles with smaller ρ reveal a sequence of LC phases involving para-nematic, nematic, smectic, and oriented glass phases. The occurrence of a smectic phase for colloidal ellipsoids has been neither predicted nor reported before. Quantitative shape analysis of the particles together with extensive computer simulations indicate that in addition to ρ, a subtle deviation from the ideal ellipsoidal shape dictates the formation of this unusual sequence of field-induced structures. Particles with ρ = 2.9 exhibit a hybrid shape containing features from both spherocylinders and ellipsoids, which make their self-assembly behavior richer than that observed for either of the "pure" shapes. The shape of the particles with higher ρ matches closely with the ideal ellipsoids, as a result their phase behavior follows the one expected for a "pure" ellipsoidal shape. Using anisotropic building blocks and external fields, our study demonstrates the ramifications of the subtle changes in the particle shape on the field-directed self-assembled structures with externally tunable properties.

Probing roto-translational diffusion of small anisotropic colloidal particles with a bright-field microscope.

Soft and biological materials are often composed of elementary constituents exhibiting an incessant roto-translational motion at the microscopic scale. Tracking this motion with a bright-field microscope becomes increasingly challenging when the particle size becomes smaller than the microscope resolution, a case which is frequently encountered. Here we demonstrate squared-gradient differential dynamic microscopy (SG-DDM) as a tool to successfully use bright-field microscopy to extract the roto-translational dynamics of small anisotropic colloidal particles, whose rotational motion cannot be tracked accurately in direct space. We provide analytical justification and experimental demonstration of the method by successful application to an aqueous suspension of peanut-shaped particles.

Manipulating Extracellular Matrix Organizations and Parameters to Control Local Cancer Invasion.

Metastasis contributes to over 90 percent of cancer mortalities and may be influenced by the extracellular matrix (ECM). ECM microenvironments differ in matrix organization, cell-matrix adhesions, and fiber rigidity, which may affect cancer migration and, thus, should be investigated. To understand the interactions between cancer cells and the ECM, we simulate local invasion through ECM organizations of varying determinants. Randomly curved organizations of normal ovarian stroma exhibit minimal local invasion. In contrast, wave-like and parallel linear structures in reorganized ECM organizations provide contact guidance, which increases cancer invasiveness. ECM organizations with strong cell-matrix attachments generate cell pseudopodia, which aid in increasing invasion rate, while weaker attachments prevent the cells from attaching to the fibers and forming pseudopodia, limiting local invasion. ECM organizations with rigid fibers elongate the cell body, allowing them to form cell protrusions and spread rapidly. Conversely, soft fibers stimulate cell rounding and limit migration. Optimizing cell-matrix adhesions and fiber rigidity results in below 10 percent local invasion and reinforces the importance of using computational modeling to discover novel approaches to restricting cancer movement.

Path-Dependent Self-Assembly of Magnetic Anisotropic Colloidal Peanuts.

Here we present the field induced self-assembly of anisotropic colloidal particles whose shape resembles peanuts. Being made up of hematite core and silica shell, these particles align in a direction perpendicular to the applied external magnetic field. Using small-angle X-ray scattering with microradian resolution (µrad-SAXS) in sedimented samples, we have found that one can tune the self-assembled structures by changing the time of application of the external field. If the field is applied after the sedimentation, the self-assembled structure is a nematic one, while dipolar chains are formed if the field is applied during the sedimentation process. Interestingly, within each chain particles form a smectic phase with defects. Further, these aforementioned nematic and smectic phases are of oblate type in spite of the prolate shape of the individual particles. For dipolar chains, an unusual diffraction peak shape has been observed with highly anisotropic tails in the transverse direction (perpendicular to the external field). The peak shape can be rationalized by considering the fact that the dipolar chains can act as a building block aligned along the field direction to form a para-nematic phase.

Anisotropic dynamics and kinetic arrest of dense colloidal ellipsoids in the presence of an external field studied by differential dynamic microscopy.

Anisotropic dynamics on the colloidal length scale is ubiquitous in nature. Of particular interest is the dynamics of systems approaching a kinetically arrested state. The failure of classical techniques for investigating the dynamics of highly turbid suspensions has contributed toward the limited experimental information available up until now. Exploiting the recent developments in the technique of differential dynamic microscopy (DDM), we report the first experimental study of the anisotropic collective dynamics of colloidal ellipsoids with a magnetic hematite core over a wide concentration range approaching kinetic arrest. In addition, we have investigated the effect of an external magnetic field on the resulting anisotropic collective diffusion. We combine DDM with small-angle x-ray scattering and rheological measurements to locate the glass transition and to relate the collective short- and long-time diffusion coefficients to the structural correlations and the evolution of the zero shear viscosity as the system approaches an arrested state.

Anomalous Dynamics of Magnetic Anisotropic Colloids Studied by XPCS.

The influence of an applied magnetic field on the collective dynamics of novel anisotropic colloidal particles whose shape resembles peanuts is reported. Being made up of hematite cores and silica shells, these micrometer-sized particles align in a direction perpendicular to the applied external magnetic field, and assemble into chains along the field direction. The anisotropic dynamics of these particles is investigated using multispeckle ultrasmall-angle X-ray photon correlation spectroscopy (USA-XPCS). The results indicate that along the direction of the magnetic field, the particle dynamics strongly depends on the length scale probed. Here, the relaxation of the intermediate scattering function follows a compressed exponential behavior at large distances, while it appears diffusive at distances comparable or smaller than the particle size. Perpendicular to the applied field (and along the direction of gravity), the experimental data can be quantitatively reproduced by a combination of an advective term originating from sedimentation and a purely diffusive one that describes the thermal diffusion of the assembled chains and individual particles.

Hybrid magnetic iron oxide nanoparticles with tunable field-directed self-assembly.

We describe the synthesis of hybrid magnetic ellipsoidal nanoparticles that consist of a mixture of two different iron oxide phases, hematite (α-Fe2O3) and maghemite (γ-Fe2O3), and characterize their magnetic field-driven self-assembly. We demonstrate that the relative amount of the two phases can be adjusted in a continuous way by varying the reaction time during the synthesis, leading to strongly varying magnetic properties of the particles. Not only does the saturation magnetization increase dramatically as the composition of the spindles changes from hematite to maghemite, but also the direction of the induced magnetic moment changes from being parallel to the short axis of the spindle to being perpendicular to it. The magnetic dipolar interaction between the particles can be further tuned by adding a screening silica shell. Small-angle X-ray scattering (SAXS) experiments reveal that at high magnetic field, magnetic dipole-dipole interaction forces the silica coated particles to self-assemble into a distorted hexagonal crystal structure at high maghemite content. However, in the case of uncoated maghemite particles, the crystal structure is not very prominent. We interpret this as a consequence of the strong dipolar interaction between uncoated spindles that then become arrested during field-induced self-assembly into a structure riddled with defects.

Observation of solid-solid transitions in 3D crystals of colloidal superballs.

Self-organization in anisotropic colloidal suspensions leads to a fascinating range of crystal and liquid crystal phases induced by shape alone. Simulations predict the phase behaviour of a plethora of shapes while experimental realization often lags behind. Here, we present the experimental phase behaviour of superball particles with a shape in between that of a sphere and a cube. In particular, we observe the formation of a plastic crystal phase with translational order and orientational disorder, and the subsequent transformation into rhombohedral crystals. Moreover, we uncover that the phase behaviour is richer than predicted, as we find two distinct rhombohedral crystals with different stacking variants, namely hollow-site and bridge-site stacking. In addition, for slightly softer interactions we observe a solid-solid transition between the two. Our investigation brings us one step closer to ultimately controlling the experimental self-assembly of superballs into functional materials, such as photonic crystals.

Observation of the Chiral and Achiral Hexatic Phases of Self-assembled Micellar polymers.

We report the discovery of a thermodynamically stable line hexatic (N + 6) phase in a three-dimensional (3D) system made up of self-assembled polymer-like micelles of amphiphilic molecules. The experimentally observed phase transition sequence nematic (N) N + 6 two-dimensional hexagonal (2D-H) is in good agreement with the theoretical predictions. Further, the present study also brings to light the effect of chirality on the N + 6 phase. In the chiral N + 6 phase the bond-orientational order within each "polymer" bundle is found to be twisted about an axis parallel to the average polymer direction. This structure is consistent with the theoretically envisaged Moiré state, thereby providing the first experimental demonstration of the Moiré structure. In addition to confirming the predictions of fundamental theories of two-dimensional melting, these results are relevant in a variety of situations in chemistry, physics and biology, where parallel packing of polymer-like objects are encountered.

Swelling enhanced remanent magnetization of hydrogels cross-linked with magnetic nanoparticles.

Hydrogels that are pH-sensitive and partially cross-linked by cobalt ferrite nanoparticles exhibit remarkable remanent magnetization behavior. The magnetic fields measured outside our thin disks of ferrogel are weak, but in the steady state, the field dependence on the magnetic content of the gels and the measurement geometry is as expected from theory. In contrast, the time-dependent behavior is surprisingly complicated. During swelling, the remanent field first rapidly increases and then slowly decreases. We ascribe the swelling-induced field enhancement to a change in the average orientation of magnetic dipolar structures, while the subsequent field drop is due to the decreasing concentration of nanoparticles. During shrinking, the field exhibits a much weaker time dependence that does not mirror the values found during swelling. These observations provide original new evidence for the markedly different spatial profiles of the pH during swelling and shrinking of hydrogels.

Tuning the colloidal crystal structure of magnetic particles by external field.

Manipulation of the self-assembly of magnetic colloidal particles by an externally applied magnetic field paves a way toward developing novel stimuli responsive photonic structures. Using microradian X-ray scattering technique we have investigated the different crystal structures exhibited by self-assembly of core-shell magnetite/silica nanoparticles. An external magnetic field was employed to tune the colloidal crystallization. We find that the equilibrium structure in absence of the field is random hexagonal close-packed (RHCP) one. External field drives the self-assembly toward a body-centered tetragonal (BCT) structure. Our findings are in good agreement with simulation results on the assembly of these particles.

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.

Thermal unbinding and ordering of amphiphile bilayers in the presence of salt.

We have studied the effect of KBr on the electrostatically stabilized fluid lamellar phase of the ionic surfactant, C12-alkenylsuccinic acid (ASA). Three distinct regimes are found in the temperature - salt phase diagram of this system at a fixed ASA concentration of 20 wt.%. A collapsed lamellar phase is formed in the low-salt regime, which exhibits an unbinding transition into uncorrelated bilayers on heating. In the intermediate salt regime the opposite trend is observed, with the uncorrelated bilayers present at low temperatures ordering into a lamellar phase at higher temperatures. As far as we are aware, this is the first report of such an ordering transition of uncorrelated bilayers. In the high salt regime, the topology of the bilayer changes, resulting in a lamellar-sponge transition. All the three transitions are reversible and the corresponding transition temperatures decrease with increasing salt concentration. The occurrence of these transitions in a single amphiphile system demonstrates the strong influence of salt on the bilayer elastic moduli as well as on the inter-bilayer interactions in the present system.

Phase behavior of two-component lipid membranes: theory and experiments.

The structure of the ripple phase of phospholipid membranes remains poorly understood in spite of a large number of theoretical studies, with many experimentally established structural features of this phase unaccounted for. In this article we present a phenomenological theory of phase transitions in single- and two-component achiral lipid membranes in terms of two coupled order parameters: a scalar order parameter describing lipid chain melting, and a vector order parameter describing the tilt of the hydrocarbon chains below the chain-melting transition. This model reproduces all the salient structural features of the ripple phase, providing a unified description of the phase diagram and microstructure. In addition, it predicts a variant of this phase that does not seem to have been experimentally observed. Using this model we have calculated generic phase diagrams of two-component membranes. We have also determined the phase diagram of a two-component lipid membrane from x-ray diffraction studies on aligned multilayers. This phase diagram is found to be in good agreement with that calculated from the model.