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At least 19 records

Glass/Jamming Transition in Colloidal Aggregation

We have studied colloidal aggregation in a model colloid plus polymer system with short-range attractive interactions. By varying the colloid concentration and the strength of the attraction, we explored regions where the equilibrium phase is expected to consist of colloidal crystallites in coexistance with colloidal gas (i.e. monomers). This occurs for moderate values of the potential depth, U approximately equal to 2-5 kT. Crystallization was not always observed. Rather, over an extended sub-region two new metastable phases appear, one fluid-like and one solid-like. These were examined in detail with light scattering and microscopy techniques. Both phases consist of a near uniform distribution of small irregular shaped clusters of colloidal particles. The dynamical and structural characteristics of the ergodic-nonergodic transition between the two phases share much in common with the colloidal hard sphere glass transition.

Segre, Philip N.↗

Laser light scattering as a probe of fractal colloid aggregates

The extensive use of laser light scattering is reviewed, both static and dynamic, in the study of colloid aggregation. Static light scattering enables the study of the fractal structure of the aggregates, while dynamic light scattering enables the study of aggregation kinetics. In addition, both techniques can be combined to demonstrate the universality of the aggregation process. Colloidal aggregates are now well understood and therefore represent an excellent experimental system to use in the study of the physical properties of fractal objects. However, the ultimate size of fractal aggregates is fundamentally limited by gravitational acceleration which will destroy the fractal structure as the size of the aggregates increases. This represents a great opportunity for spaceborne experimentation, where the reduced g will enable the growth of fractal structures of sufficient size for many interesting studies of their physical properties.

Weitz, David A.↗

Binodal Colloidal Aggregation Test - 4: Polydispersion

Binodal Colloidal Aggregation Test - 4: Polydispersion (BCAT-4-Poly) will use model hard-spheres to explore seeded colloidal crystal nucleation and the effects of polydispersity, providing insight into how nature brings order out of disorder. Crewmembers photograph samples of polymer and colloidal particles (tiny nanoscale spheres suspended in liquid) that model liquid/gas phase changes. Results will help scientists develop fundamental physics concepts previously cloaked by the effects of gravity.

Chaikin, Paul M.↗

A coarse-grained model of clay colloidal aggregation and consolidation with explicit representation of the electrical double layer

The aggregation of clay minerals in liquid water exemplifies colloidal self-assembly in nature. These negatively charged aluminosilicate platelets interact through multiple mechanisms with different sensitivities to particle shape, surface charge, aqueous chemistry, and interparticle distance and exhibit complex aggregation structures. Experiments have difficulty resolving the associated colloidal assemblages at the scale of individual particles. Conversely, all-atom molecular dynamics (MD) simulations provide detailed insight on clay colloidal interaction mechanisms, but they are limited to systems containing a few particles. We develop a new coarse-grained (CG) model capable of representing assemblages of hundreds of clay particles with accuracy approaching that of MD simulations, at a fraction of the computational cost. Our CG model is parameterized based on MD simulations of a pair of smectite clay particles in liquid water. A distinctive feature of our model is that it explicitly represents the electrical double layer (EDL), i.e., the cloud of charge-compensating cations that surrounds the clay particles. Our model captures the simultaneous importance of long-range colloidal interactions (i.e., interactions consistent with simplified analytical models, already included in extant clay CG models) and short-range interactions such as ion correlation and surface and ion hydration effects. The resulting simulations correctly predict, at low solid-water ratios, the existence of ordered arrangements of parallel particles separated by water films with a thickness up to ~10 nm and, at high solid-water ratios, the coexistence of crystalline and osmotic swelling states, in agreement with experimental observations.

54 ENVIRONMENTAL SCIENCES↗

Assembly of Colloidal Aggregates by Electrohydrodynamic Flow: Kinetic Experiments and Scaling Analysis

Electric fields generate transverse flows near electrodes that sweep colloidal particles into densely packed assemblies. We interpret this behavior in terms of electrohydrodynamic motion stemming from distortions of the field by the particles that alter the body force distribution in the electrode charge polarization layer. A scaling analysis shows how the action of the applied electric field generates fluid motion that carries particles toward one another. The resulting fluid velocity is proportional to the square of the applied field and decreases inversely with frequency. Experimental measurements of the particle aggregation rate accord with the electrohydrodynamic theory over a wide range of voltages and frequencies.

Ristenpart, W. D.↗

Unconventional colloidal aggregation in chiral bacterial baths

Abstract When in equilibrium, thermal forces agitate molecules, which then diffuse, collide and bind to form materials. However, the space of accessible structures in which micron-scale particles can be organized by thermal forces is limited, owing to the slow dynamics and metastable states. Active agents in a passive fluid generate forces and flows, forming a bath with active fluctuations. Two unanswered questions are whether those active agents can drive the assembly of passive components into unconventional states and which material properties they will exhibit. Here we show that passive, sticky beads immersed in a bath of swimmingEscherichia colibacteria aggregate into unconventional clusters and gels that are controlled by the activity of the bath. We observe a slow but persistent rotation of the aggregates that originates in the chirality of theE. coliflagella and directs aggregation into structures that are not accessible thermally. We elucidate the aggregation mechanism with a numerical model of spinning, sticky beads and reproduce quantitatively the experimental results. We show that internal activity controls the phase diagram and the structure of the aggregates. Overall, our results highlight the promising role of active baths in designing the structural and mechanical properties of materials with unconventional phases.

Physics↗

Quantifying electron transport in aggregated colloidal suspensions in the strong flow regime

Electron transport in complex fluids, biology, and soft matter is a valuable characteristic in processes ranging from redox reactions to electrochemical energy storage. These processes often employ conductor–insulator composites in which electron transport properties are fundamentally linked to the microstructure and dynamics of the conductive phase. While microstructure and dynamics are well recognized as key determinants of the electrical properties, a unified description of their effect has yet to be determined, especially under flowing conditions. In this work, the conductivity and shear viscosity are measured for conductive colloidal suspensions to build a unified description by exploiting both recent quantification of the effect of flow-induced dynamics on electron transport and well-established relationships between electrical properties, microstructure, and flow. These model suspensions consist of conductive carbon black (CB) particles dispersed in fluids of varying viscosities and dielectric constants. In a stable, well-characterized shear rate regime where all suspensions undergo self-similar agglomerate breakup, competing relationships between conductivity and shear rate were observed. To account for the role of variable agglomerate size, equivalent microstructural states were identified using a dimensionless fluid Mason number, Mn f , which allowed for isolation of the role of dynamics on the flow-induced electron transport rate. At equivalent microstructural states, shear-enhanced particle–particle collisions are found to dominate the electron transport rate. This work rationalizes seemingly contradictory experimental observations in literature concerning the shear-dependent electrical properties of CB suspensions and can be extended to other flowing composite systems.

Science & Technology - Other Topics↗

Protein Colloidal Aggregation Project

To investigate the pathways and kinetics of protein aggregation to allow accurate predictive modeling of the process and evaluation of potential inhibitors to prevalent diseases including cataract formation, chronic traumatic encephalopathy, Alzheimer's Disease, Parkinson's Disease and others.

Technology Portfolio System↗

"Smart" Magnetic Fluids Experiment Operated on the International Space Station

InSPACE is a microgravity fluid physics experiment that was operated on the International Space Station (ISS) in the Microgravity Science Glovebox from late March 2003 through early July 2003. (InSPACE is an acronym for Investigating the Structure of Paramagnetic Aggregates From Colloidal Emulsions.) The purpose of the experiment is to obtain fundamental data of the complex properties of an exciting class of smart materials termed magnetorheological (MR) fluids. MR fluids are suspensions, or colloids, comprised of small (micrometer-sized) superparamagnetic particles in a nonmagnetic medium. Colloids are suspensions of very small particles suspended in a liquid. (Examples of other colloids are blood, milk, and paint.) These controllable fluids can quickly transition into a nearly solid state when exposed to a magnetic field and return to their original liquid state when the magnetic field is removed. Controlling the strength of the magnetic field can control the relative stiffness of these fluids. MR fluids can be used to improve or develop new seat suspensions, robotics, clutches, airplane landing gear, and vibration damping systems. The principal investigator for InSPACE is Professor Alice P. Gast of the Massachusetts Institute of Technology (MIT). The InSPACE hardware was developed at the NASA Glenn Research Center. The InSPACE samples were delivered to the ISS in November 2002, on the Space Shuttle Endeavour, on Space Station Utilization Flight UF-2/STS113. Operations began on March 31, 2003, with the processing of three different particle size samples at multiple test parameters. This investigation focused on determining the structural organization of MR colloidal aggregates when exposed to a pulsing magnetic field. On Earth, the aggregates take the shape of footballs with spiky tips. This characteristic shape may be influenced by the pull of gravity, which causes most particles initially suspended in the fluid to sediment, (i.e., settle and collect at the bottom of the cell). In the absence of sedimentation effects on the ISS, the behavior and shape of these MR aggregate structures are dominated exclusively by magnetic and surface tension forces. The microscopic detail of these structures was imaged under two orthogonal camera views. The video was downlinked to the InSPACE team at Glenn's Telescience Support Center and to MIT and also recorded onboard the ISS on videotapes that will be brought back to the ground by the space shuttles. The study examined the effect on the structure formation by varying the magnetic field strength and pulse frequency, and particle size. Fundamental data that characterized the structure formation were obtained. InSPACE completed its last planned test run on July 2, 2003. Operations occurred on 21 days over approximately a 3-month period. Forty-one test points were completed during 26 test runs. During the initial testing, the procedures followed by the crew were modified to maximize the observation of some unexpected and interesting aggregate behavior. As a result Dr. Gast has reported on the formation of aggregate shapes that are more extended and diverse than those observed on the ground. Sheets of magnetic material folded over in a labyrinth pattern and large columnar aggregates with complex interfaces with the surrounding fluid are examples of the interesting structures that have been observed on the ISS. In light of these early findings, the understanding of the fundamental properties of MR fluids on the basis of ground-based observations may need to be reconsidered.The experiments on the ISS have provided a vast amount of video data for analysis. While this analysis is ongoing, plans are being made for additional experimental runs. For this purpose, additional hardware and cells containing samples of different magnetic particles and sizes are being fabricated for a future launch to the ISS. The InSPACE hardware will remain on orbit until this testing is completed.

Agui, Juan H.↗

Interaction and Aggregation of Colloidal Biological Particles and Droplets in Electrically-Driven Flows

The primary objective of this research was to develop a fundamental understanding of aggregation and coalescence processes during electrically-driven migration of cells, particles and droplets. The process by which charged cells, particles, molecules, or drops migrate in a weak electric field is known as electrophoresis. If the migrating species have different charges or surface potentials, they will migrate at different speeds and thus may collide and aggregate or coalesce. Aggregation and coalescence are undesirable, if the goal is to separate the different species on the basis of their different electrophoretic mobilities.

Davis, Robert H.↗

Electrophoretic interactions and aggregation of colloidal biological particles

The separation of cells or particles from solution has traditionally been accomplished with centrifuges or by sedimentation; however, many particles have specific densities close to unity, making buoyancy-driven motion slow or negligible, but most cells and particles carry surface charges, making them ideal for electrophoretic separation. Both buoyancy-driven and electrophoretic separation may be influenced by hydrodynamic interactions and aggregation of neighboring particles. Aggregation by electrophoresis was analyzed for two non-Brownian particles with different zeta potentials and thin double layers migrating through a viscous fluid. The results indicate that the initial rate of electrophoretically-driven aggregation may exceed that of buoyancy-driven aggregation, even under conditions in which buoyancy-driven relative motion of noninteracting particles is dominant.

Davis, Robert H.↗

Ink-substrate interactions during 3D printing revealed by time-resolved coherent X-ray scattering

Additive printing techniques are regarded as revolutionary and versatile methods of advanced device manufacturing, stemming from the possibility to pattern materials on a custom-based approach and the potential to create novel microstructures and achieve new functionalities. Despite these advantages, the inherent anisotropy of the printing process is a source of property gradients within the printed materials, often associated with variable and/or poor performance. Up to date, the evolutionary pathways associated with printing have largely remained unaddressed, mainly owing to the difficulty to study the transformations induced in the material during processing. Time-resolved coherent X-ray scattering techniques, such as X-ray photon correlation spectroscopy, enable the in situ study of transient nanoscale and mesoscale states in a large variety of materials, including amorphous ones, by directly accessing the most relevant timescales and length scales of their nanoscale and mesoscale dynamics, self-assembly, and mesostructure evolution. In this work, we conduct in operando studies of continuous-flow direct writing with colloidal inks, focusing on how the ink formulation and ink-substrate interactions affect the processes that determine the macroscopic properties of the printed materials. We find fundamental differences in the ink structural relaxations emerging from the primary colloid properties (monodisperse versus aggregated colloids) and the substrates surface energy and mechanical properties. Our work helps to reveal and quantify the basic science governing the evolution of 3D-printed materials during processing, ultimately improving engineering criteria for the design of printable materials.

36 MATERIALS SCIENCE↗

Simultaneous Insight into Dissolution and Aggregation of Metal Sulfide Nanoparticles through Single-Particle Inductively Coupled Plasma Mass Spectrometry

Nanoparticles (NPs) and their colloidal aggregates are ubiquitous and play important roles in the transport and release of metals. Knowledge of their dissolution rates and aggregation behavior in solution are crucial for better prediction of their fate in biogeochemical cycling, ecotoxicity, and environmental remediation. There are however significant technical challenges to accurately obtain such information as a result of the heterogeneity and highly dynamic transformation exhibited by NPs, particularly at relatively low particle concentrations in aqueous systems. Here, we quantitatively examine the simultaneous dissolution and aggregation behavior of metal sulfide NPs using single-particle inductively coupled plasma mass spectrometry (spICP–MS). We focus on nickel sulfide (NiS), with additional data presented for copper sulfide (CuS) and cobalt sulfide (CoS). The kinetics of metal release (dissolution and disaggregation) of NiS was fastest under strongly oxidizing conditions (from 0.04 to >3 min –1 with H 2 O 2 ) and were slower under near-neutral (HEPES buffer/H 2 O) and acidic (1 mM HNO 3 ) conditions (≤0.006 min –1 ). Metal release kinetics in HNO 3 was not faster than in H 2 O or HEPES, suggesting that the solution pH has an influence over both the dissolution kinetics of individual particles and the NP aggregation states, which in combination affect metal release rates over time. Between different metal sulfides, the measured metal release rates were largely consistent with predictions based on the crystallinity, solubility products, and specific surface areas of the NPs, following an order of CoS > NiS > CuS. Here, the spICP–MS approach described here can be easily applied to the characterization of metal release and aggregation of other NPs at low concentrations (~10 5 particles/mL) typically found in natural environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bulk Anion Recognition Kinetically Holds Back Interfacial Adsorption

The competition between bulk and interfacial phenomena underlies many key processes in complex chemical phenomena and transport. While competitive processes are often framed in a thermodynamic context, opportunities to leverage transient species found away from equilibrium can provide a kinetic handle to achieve unconventional reaction outcomes. In this work, we outfit an iminoguanidinium headgroup capable of selective SO 4 2– complexation with alkyl tails of varying complexity to probe competitive bulk and interfacial reaction pathways and tune kinetic pathways for selective chemical separations. Using sum frequency generation (SFG) vibrational spectroscopy we unexpectedly find that adsorption of ligands to the air–aqueous interface was dramatically slowed down for species with increasingly hydrophobic tails. Underlying this phenomenon, we show that the formation of bulk colloidal species with differing propensities for SO 4 2– inhibited surface adsorption via a kinetic bottleneck in the exchange of molecular extractants with colloidal aggregates. This kinetic effect could open up avenues to access unconventional selectivity via complexation of strongly coordinating species in the bulk phase, allowing for more weakly coordinating species to transport via interfacial mechanisms. Furthermore, this work broadly probes nonequilibrium phenomena in chemical separations that arise through unexpected interfacial events that are neglected in traditional equilibrium descriptions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterizing inhibitors of human AP endonuclease 1

AP endonuclease 1 (APE1) processes DNA lesions including apurinic/apyrimidinic sites and 3´-blocking groups, mediating base excision repair and single strand break repair. Much effort has focused on developing specific inhibitors of APE1, which could have important applications in basic research and potentially lead to clinical anticancer agents. We used structural, biophysical, and biochemical methods to characterize several reported inhibitors, including 7-nitroindole-2-carboxylic acid (CRT0044876), given its small size, reported potency, and widespread use for studying APE1. Intriguingly, NMR chemical shift perturbation (CSP) experiments show that CRT0044876 and three similar indole-2-carboxylic acids bind a pocket distal from the APE1 active site. A crystal structure confirms these findings and defines the pose for 5-nitroindole-2-carboxylic acid. However, dynamic light scattering experiments show the indole compounds form colloidal aggregates that could bind (sequester) APE1, causing nonspecific inhibition. Endonuclease assays show the compounds lack significant APE1 inhibition under conditions (detergent) that disrupt aggregation. Thus, binding of the indole-2-carboxylic acids at the remote pocket does not inhibit APE1 repair activity. Myricetin also forms aggregates and lacks APE1 inhibition under aggregate-disrupting conditions. Two other reported compounds (MLS000552981, MLS000419194) inhibit APE1 in vitro with low micromolar IC50 and do not appear to aggregate in this concentration range. However, NMR CSP experiments indicate the compounds do not bind specifically to apo- or Mg 2+ -bound APE1, pointing to a non-specific mode of inhibition, possibly DNA binding. Our results highlight methods for rigorous interrogation of putative APE1 inhibitors and should facilitate future efforts to discover compounds that specifically inhibit this important repair enzyme.

59 BASIC BIOLOGICAL SCIENCES↗

Phase Diagrams of Electric-Fduced Aggregation in Conducting Colloids

Under the application of a sufficiently strong electric field, a suspension may undergo reversible phase transitions from a homogeneous random arrangement of particles into a variety of ordered aggregation patterns. The surprising fact about electric-field driven phase transitions is that the aggregation patterns, that are observed in very diverse systems of colloids, display a number of common structural features and modes of evolution thereby implying that a universal mechanism may exist to account for these phenomena. It is now generally believed that this mechanism emanates from the presence of the long-range anisotropic interactions between colloidal particles due to their polarization in an applied field. But, in spite of numerous applications of the electric-field-driven phenomena in biotechnology, separation, materials engineering, chemical analysis, etc. our understanding of these phenomena is far from complete. Thus, it is the purpose of the proposed research to develop a theory and then test experimentally, under normal- and low-gravity conditions, the accuracy of the theoretical predictions regarding the effect of the synergism of the interparticle electric and hydrodynamic interactions on the phase diagram of a suspension. The main results from our theoretical studies performed to-date enable one to trace how the variations of the electrical properties of the constituent materials influence the topology of the suspension phase diagram and then, by using an appropriate phase diagram, to evaluate how the electric-field-induced transformations will depend on the frequency and the strength of the applied field.

Khusid, B.↗