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At least 379 records · Page 21

Hopping and crawling DNA-coated colloids

Understanding the motion of particles with multivalent ligand-receptors is important for biomedical applications and material design. Yet, even among a single design, the prototypical DNA-coated colloids, seemingly similar micrometric particles hop or roll, depending on the study. We shed light on this problem by observing DNA-coated colloids diffusing near surfaces coated with complementary strands for a wide array of coating designs. We find colloids rapidly switch between 2 modes: They hop—with long and fast steps—and crawl—with short and slow steps. Both modes occur at all temperatures around the melting point and over various designs. The particles become increasingly subdiffusive as temperature decreases, in line with subsequent velocity steps becoming increasingly anticorrelated, corresponding to switchbacks in the trajectories. Overall, crawling (or hopping) phases are more predominant at low (or high) temperatures; crawling is also more efficient at low temperatures than hopping to cover large distances. We rationalize this behavior within a simple model: At lower temperatures, the number of bound strands increases, and detachment of all bonds is unlikely, hence, hopping is prevented and crawling favored. We thus reveal the mechanism behind a common design rule relying on increased strand density for long-range self-assembly: Dense strands on surfaces are required to enable crawling, possibly facilitating particle rearrangements.

Science & Technology - Other Topics↗

Advanced Colloids Experiment (ACE) Science Overview

The Advanced Colloids Experiment is being conducted on the International Space Station (ISS) using the Light Microscopy Module (LMM) in the Fluids Integrated Rack (FIR). Work to date will be discussed and future plans and opportunities will be highlighted. The LMM is a microscope facility designed to allow scientists to process, manipulate, and characterize colloidal samples in micro-gravity where the absence of gravitational settling and particle jamming enables scientists to study such things as:a.The role that disordered and ordered-packing of spheres play in the phase diagram and equation of state of hard sphere systems,b.crystal nucleation and growth, growth instabilities, and the glass transition, c.gelation and phase separation of colloid polymer mixtures,d.crystallization of colloidal binary alloys,e.competition between crystallization and phase separation,f.effects of anisotropy and specific interactions on packing, aggregation, frustration and crystallization,g.effects of specific reversible and irreversible interactions mediated in the first case by hybridization of complementary DNA strands attached to separate colloidal particles,h.Lock and key interactions between colloids with dimples and spheres which match the size and shape of the dimples,i.finding the phase diagrams of isotropic and interacting particles,j.new techniques for complex self-assembly including scenarios for self-replication, k.critical Casimir forces,l.biology (real and model systems) in microgravity,m.etc. By adding additional microscopy capabilities to the existing LMM, NASA will increase the tools available for scientists that fly experiments on the ISS enabling scientists to observe directly what is happening at the particle level. Presently, theories are needed to bridge the gap between what is being observed (at a macroscopic level when photographing samples) with what is happening at a particle (or microscopic) level. What is happening at a microscopic level will be directly accessible with the availability of the Light Microscopy Module (LMM) on ISS. To meet these goals, the ACE experiment is being built-up in stages, with the availability of confocal microscopy being the ultimate objective. Supported by NASAs Physical Sciences Research Program, ESAESTEC, and the authors respective governments.

Microgravity Biology Research↗

Cholesterics of colloidal helices: Predicting the macroscopic pitch from the particle shape and thermodynamic state

Building a general theoretical framework to describe the microscopic origin of macroscopic chirality in (colloidal) liquid crystals is a long-standing challenge. Here, we combine classical density functional theory with Monte Carlo calculations of virial-type coefficients to obtain the equilibrium cholesteric pitch as a function of thermodynamic state and microscopic details. Applying the theory to hard helices, we observe both right- and left-handed cholesteric phases that depend on a subtle combination of particle geometry and system density. In particular, we find that entropy alone can even lead to a (double) inversion in the cholesteric sense of twist upon changing the packing fraction. We show how the competition between single-particle properties (shape) and thermodynamics (local alignment) dictates the macroscopic chiral behavior. Moreover, by expanding our free-energy functional, we are able to assess, quantitatively, Straley’s theory of weak chirality, which is used in several earlier studies. Furthermore, by extending our theory to different lyotropic and thermotropic liquid-crystal models, we analyze the effect of an additional soft interaction on the chiral behavior of the helices. Finally, we provide some guidelines for the description of more complex chiral phases, like twist-bend nematics. Our results provide new insights into the role of entropy in the microscopic origin of this state of matter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colloidal Disorder-Order Transition Experiment Probes Particle Interactions in Microgravity

Everything in the universe is made up of the same basic building blocks - atoms. All physical properties of matter such as weight, hardness, and color are determined by the kind of atoms present and the way they interact with each other. The Colloidal Disorder-Order Transition (CDOT) shuttle flight experiment tested fundamental theories that model atomic interactions. The experiment was part of the Second United States Microgravity Laboratory (USML-2) aboard the Space Shuttle Columbia, which flew from October 20 to November 5, 1995.

Source record↗

A new class of tunable hypersonic phononic crystals based on polymer-tethered colloids

The design and engineering of hybrid materials exhibiting tailored phononic band gaps are fundamentally relevant to innovative material technologies in areas ranging from acoustics to thermo-optic devices. Phononic hybridization gaps, originating from the anti-crossing between local resonant and propagating modes, have attracted particular interest because of their relative robustness to structural disorder and the associated benefit to ‘manufacturability’. Although hybridization gap materials are well known, their economic fabrication and efficient control of the gap frequency have remained elusive because of the limited property variability and expensive fabrication methodologies. Here we report a new strategy to realize hybridization gap materials by harnessing the ‘anisotropic elasticity’ across the particle–polymer interface in densely polymer-tethered colloidal particles. Theoretical and Brillouin scattering analysis confirm both the robustness to disorder and the tunability of the resulting hybridization gap and provide guidelines for the economic synthesis of new materials with deliberately controlled gap position and width frequencies.

36 MATERIALS SCIENCE↗

Induced phase transformation in ionizable colloidal nanoparticles

Abstract Acid–base equilibria directly influence the functionality and behavior of particles in a system. Due to the ionizing effects of acid–base functional groups, particles will undergo charge exchange. The degree of ionization and their intermolecular and electrostatic interactions are controlled by varying the pH and salt concentration of the solution in a system. Although the pH can be tuned in experiments, it is hard to model this effect using simulations or theoretical approaches. This is due to the difficulty in treating charge regulation and capturing the cooperative effects in a colloidal suspension with Coulombic interaction. In this work, we analyze a suspension of ionizable colloidal particles via molecular dynamics (MD) simulations, along with Monte Carlo simulations for charge regulation (MC-CR) and derive a phase diagram of the system as a function of pH. It is observed that as pH increases, particles functionalized with acid groups change their arrangement from face-centered cubic (FCC) packing to a disordered state. We attribute these transitions to an increase in the degree of charge polydispersity arising from an increase in pH. Our work shows that charge regulation leads to amorphous solids in colloids when the mean nanoparticle charge is sufficiently high. Graphical abstract

36 MATERIALS SCIENCE↗

Dynamical Threshold of Diluteness of Soft Colloids

The dynamics of soft colloids in solutions is characterized by internal collective motion as well as center-of-mass diffusion. Using neutron scattering we demonstrate that the competition between the relaxation processes associated with these two degrees of freedom results in strong dependence of dynamics and structure on colloid concentration, c, well below the overlap concentration c*. Triggered by the increasing inter-particle collisions, substantial structural dehydration and slowing-down of internal dynamics occurs before geometrically defined colloidal overlap develops. This observation is surprising since it is generally believed that the internal dynamics and conformation of soft colloidal particles essentially remain invariant below c*. The competition between these two relaxation processes gives rise to a new dynamically-defined dilute threshold concentration well below c*.

Chen, Wei-Ren↗

Shape-Directed Microspinners Powered by Ultrasound

The propulsion of micro- and nanoparticles using ultrasound is an attractive strategy for the remote manipulation of colloidal matter using biocompatible energy inputs. However, the physical mechanisms underlying acoustic propulsion are poorly understood, and our ability to transduce acoustic energy into different types of particle motions remains limited. Here in this paper, we show that the three-dimensional shape of a colloidal particle can be rationally engineered to direct desired particle motions powered by ultrasound. We investigate the dynamics of gold microplates with twisted star shape (C nh symmetry) moving within the nodal plane of a uniform acoustic field at megahertz frequencies. By systematically perturbing the parametric shape of these “spinners”, we quantify the relationship between the particle shape and its rotational motion. The experimental observations are reproduced and explained by hydrodynamic simulations that describe the steady streaming flows and particle motions induced by ultrasonic actuation. Our results suggest how particle shape can be used to design colloids capable of increasingly complex motions powered by ultrasound.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Physics of Colloids in Space: Flight Hardware Operations on ISS

The Physics of Colloids in Space (PCS) experiment was launched on Space Shuttle STS-100 in April 2001 and integrated into EXpedite the PRocess of Experiments to Space Station Rack 2 on the International Space Station (ISS). This microgravity fluid physics investigation is being conducted in the ISS U.S. Lab 'Destiny' Module over a period of approximately thirteen months during the ISS assembly period from flight 6A through flight 9A. PCS is gathering data on the basic physical properties of simple colloidal suspensions by studying the structures that form. A colloid is a micron or submicron particle, be it solid, liquid, or gas. A colloidal suspension consists of these fine particles suspended in another medium. Common colloidal suspensions include paints, milk, salad dressings, cosmetics, and aerosols. Though these products are routinely produced and used, we still have much to learn about their behavior as well as the underlying properties of colloids in general. The long-term goal of the PCS investigation is to learn how to steer the growth of colloidal structures to create new materials. This experiment is the first part of a two-stage investigation conceived by Professor David Weitz of Harvard University (the Principal Investigator) along with Professor Peter Pusey of the University of Edinburgh (the Co-Investigator). This paper describes the flight hardware, experiment operations, and initial science findings of the first fluid physics payload to be conducted on ISS: The Physics of Colloids in Space.

Doherty, Michael P.↗

A protected annealing strategy to enhanced light emission and photostability of YAG:Ce nanoparticle-based films

A significant obstacle in the development of YAG:Ce nanoparticles as light converters in white LEDs and as biological labels is associated with the difficulty of finding preparative conditions that allow simultaneous control of structure, particle size and size distribution, while maintaining the optical properties of bulk samples. Preparation conditions frequently involve high-temperature treatments of precursors (up to 1400 C), which result in increased particle size and aggregation, and lead to oxidation of Ce(III) to Ce(IV). We report here a process that we term protected annealing, that allows the thermal treatment of preformed precursor particles at temperatures up to 1000 C while preserving their small size and state of dispersion. In a first step, pristine nanoparticles are prepared by a glycothermal reaction, leading to a mixture of YAG and boehmite crystalline phases. The preformed nanoparticles are then dispersed in a porous silica. Annealing of the composite material at 1000 C is followed by dissolution of the amorphous silica by hydrofluoric acid to recover the annealed particles as a colloidal dispersion. This simple process allows completion of YAG crystallization while preserving their small size. The redox state of Ce ions can be controlled through the annealing atmosphere. The obtained particles of YAG:Ce (60 {+-} 10 nm in size) can be dispersed as nearly transparent aqueous suspensions, with a luminescence quantum yield of 60%. Transparent YAG:Ce nanoparticle-based films of micron thickness can be deposited on glass substrates using aerosol spraying. Films formed from particles prepared by the protected annealing strategy display significantly improved photostability over particles that have not been subject to such annealing.

36 MATERIALS SCIENCE↗

Advanced Colloids Experiment (Temperature Controlled) - (ACE-T11)

Increment 59-60 Science Symposium presentation of Advanced Colloids Experiment (ACE-T11, Khusid - NJIT (New Jersey Inst. of Technology)) to RPO (Research Program Office). The purpose of this event is for Principal Investigators to present their science objectives, testing approach, and measurement methods to agency scientists, managers, and other investigators. It is often assumed that time-average weightlessness simulated in a clinostat can reduce the effect of gravity on samples. Why not use it for colloids? Low-gravity parabolic flight tests on a non-buoyancy matched suspension demonstrated that time-average weightlessness in a clinostat does not eliminate gravity effect on patterns in colloids formed by an electric field. The long-term microgravity ISS (International Space Station) experiment provides a unique opportunity to reveal the relationship between external forces on the scale of individual particles and the colloid dynamics on the macroscopic scale.

ISS↗

On the Faraday Effect in Magnetic Colloids

The propagation of plane-polarized microwave radiation in magnetic colloids with magnetite particles and magnetosensitive emulsions based on such particles is experimentally studied. A magnetic field exerted along the propagation direction leads to the rotation of the polarization plane (Faraday effect) provided that the magnetite concentration is higher than a certain critical level. Specific features of the effect in structured magnetic colloids and magnetic emulsions related to structural changes in the presence of magnetic field are revealed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Linking deposit morphology and clogging in subsurface remediation: Final Technical Report

Groundwater is a crucial resource for water supply, especially in arid and semiarid areas of the United States west of the 100th meridian. Accordingly, remediation of contaminated groundwater is an important application of science and technology, particularly for the U.S. Department of Energy (DOE), which oversees a number of groundwater remediation sites from Cold War era mining. Groundwater remediation is complex, because it depends on identifying, locating, and treating contaminants in the subsurface, where remediation reactions depend on interacting geological, hydrological, geochemical, and microbiological factors. Within this context, permeability is a fundamental concept, because it controls the rates and pathways of groundwater flow. Colloid science is intimately related to permeability, because when colloids are present (particles with equivalent diameters between 1 nanometer and 10 micrometers), changes in hydrological or geochemical conditions can trigger a detrimental reduction in permeability called clogging. Accordingly, clogging is a major concern in groundwater remediation. Several lines of evidence suggest that clogging by colloids depends on (1) colloid deposition, and (2) deposit morphology, that is, the structure of colloid deposits, which can be quantified as a fractal dimension. This report describes research, performed under a 2-year, exploratory grant from the DOE’s Subsurface Biogeochemical Research (SBR) program. This research employed a novel laboratory technique to simultaneously measure flow, colloid deposition, deposit morphology, and permeability in a flow cell, and also collected field samples from wells at the DOE’s Old Rifle remediation site. Field results indicate that suspended solids at the Old Rifle site have fractal structures. Laboratory results indicate that clogging is associated with colloid deposits with smaller fractal dimensions, in accordance with previous studies on initially clean granular media. Preliminary modeling has identified the deposit radius of gyration as a candidate variable to account for clogging as a function of (1) colloid accumulation and (2) deposit morphology.

54 ENVIRONMENTAL SCIENCES↗

Raspberry colloid-templated approach for the synthesis of palladium-based oxidation catalysts with enhanced hydrothermal stability and low-temperature activity

It is becoming increasingly urgent to develop and utilize novel, more efficient and stable materials for mobile and stationary emission control applications as the deleterious consequences of anthropogenic air pollution are becoming more evident and pressing. Tightening regulations, particularly related to automotive exhaust treatment, together with continued improvements in engine design, that result in lowering the engine operating temperatures and inadvertently lead to the release of an overwhelming proportion of pollutants during the cold start, present new challenges for materials design, specifically for oxidation catalysts. In particular, improvements in the low-temperature activity while maintaining catalyst stability at high temperatures are required from the next-generation catalyst. Typical catalysts for removal of pollutants from automotive exhaust streams incorporate platinum group metals (PGMs). They tend to be inefficient at low temperatures (below 250 °C), thus accounting for the cold start problem, yet sinter and lose their activity at high temperatures that are frequently encountered during catalyst operation. High PGM loadings are often employed to compensate for catalyst inefficiencies and fast degradation, ultimately resulting in high-cost catalytic converters. Here, we have developed a new approach for the design and formation of catalytic materials that allows for both significantly more efficient PGM incorporation and improved overall catalyst performance at reduced PGM loadings. The method provides control over the composition and geometry of the support through self-assembly of sacrificial composite template — “raspberry” polymeric colloids decorated with catalytic particles — accompanied by infiltration with metal-oxide precursor and subsequent removal of the colloids. This method simultaneously structures the porous network and organizes the catalytic particles within it. Uniquely, the resulting catalytic particles are partially embedded in the support matrix and partially exposed to the pore interior, producing catalytic sites that are both stable and accessible. Herein, the feasibility of this novel and versatile approach for automotive catalytic conversion is demonstrated: the studies include testing alumina-based raspberry-colloid-templated (RCT) catalysts containing Pd nanoparticles (RCT Pd/Al2O3) for oxidation of propane and carbon monoxide under simulated diesel exhaust conditions and hydrothermal aging at 800 °C for 50 h in the simulated stream. The RCT Pd/Al2O3 catalysts exhibit exceptional activity toward CO oxidation, reduced reaction onset temperature, and high stability to elevated temperatures (demonstrated through prolonged exposure to temperatures up to 950 °C) and reactive gas streams, without migration, sintering or loss of the precious metal NPs. Notably, the novel catalyst shows the same or slightly better performance than the commercial catalysts even when the PGM load is reduced by ~80 % compared to the commercial counterparts. These results provide confidence for the utilization of the RCT approach for the fabrication of robust nanostructured catalysts for next-generation, energy-efficient catalytic converters with improved performance at low and high temperatures and reduced costs. The RCT methodology is, in addition, highly generalizable, and can thus be applied for the design of a wide range of catalytic systems in the automotive sector and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Method to separate lignin-rich solid phase from acidic biomass suspension at an acidic pH

A method of separating a lignin-rich solid phase from a solution suspension, by pretreating a lignocellulosic biomass with a pretreatment fluid having remove soluble components, colloidal material and primarily lignin containing particles; separating the pretreated lignocellulosic biomass from the pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles; flocculating the separated pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles using polyethylene oxide (i.e., PEO) or cationic Poly acrylamide (i.e., CPAM) as a flocculating agent; and filtering the flocculated separated pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles to remove agglomerates.

09 BIOMASS FUELS↗

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.↗

Silica Supported Ceria Nanoparticles: A Hybrid Nanostructure To Increase Stability And Surface Reactivity Of Nano-crystalline Ceria

The mixed oxidation state (3+/4+) of ceria nanoparticles of smaller sizes make them attractive materials for their catalytic antioxidant biological properties. However the unmodified smaller ceria nanoparticles are limited in their use due to particles agglomeration and reduced surface chemical reactivity in the solutions used to disperse the nanoparticles. This work describes an effort to stabilize small ceria nanoparticles, retaining their desired activity, on a larger stable silica support. The ceria nanoparticles attached to silica was synthesized by a solution synthesis technique in which the surface functional groups of silica nanoparticles were found to be essential for the formation of smaller ceria nanoparticles. The surface chemical and vibrational spectroscopy analysis revealed cerium–silicate (Ce-O-Si) covalent bond linkage between silica and cerium oxide nanoparticles. The colloidal properties (agglomerate particle size and suspension stability) of ceria attached to silica was significantly improved due to inherent physico-chemical characteristics of silica against random collision and gravitation settling as opposed to unmodified ceria nanoparticles in solution. The bio-catalytic activity of ceria nanoparticles in the 3+ oxidation state was not found to be limited by attachment to the silica support as measured by free radical scavenging activity in different biological media conditions.

Environmental Molecular Sciences Laboratory↗