Showing papers on "Particle published in 2010"

Surface modification, functionalization and bioconjugation of colloidal inorganic nanoparticles

Abstract: Inorganic colloidal nanoparticles are very small, nanoscale objects with inorganic cores that are dispersed in a solvent. Depending on the material they consist of, nanoparticles can possess a number of different properties such as high electron density and strong optical absorption (e.g. metal particles, in particular Au), photoluminescence in the form of fluorescence (semiconductor quantum dots, e.g. CdSe or CdTe) or phosphorescence (doped oxide materials, e.g. Y(2)O(3)), or magnetic moment (e.g. iron oxide or cobalt nanoparticles). Prerequisite for every possible application is the proper surface functionalization of such nanoparticles, which determines their interaction with the environment. These interactions ultimately affect the colloidal stability of the particles, and may yield to a controlled assembly or to the delivery of nanoparticles to a target, e.g. by appropriate functional molecules on the particle surface. This work aims to review different strategies of surface modification and functionalization of inorganic colloidal nanoparticles with a special focus on the material systems gold and semiconductor nanoparticles, such as CdSe/ZnS. However, the discussed strategies are often of general nature and apply in the same way to nanoparticles of other materials.

Food emulsions and foams: Stabilization by particles

Abstract: Recent advances in the stabilization of emulsions and foams by particles of nanoscale and microscopic dimensions are described. Ongoing research in this highly active field is providing insight into (i) the molecular factors controlling particle wettability and adsorption, (ii) the structural and mechanical properties of particle-laden liquid interfaces, and (ii) the stabilization mechanisms of particle-coated droplets and bubbles. There is much potential for exploiting the emerging knowledge in new food product applications. The preparation of cheap and effective colloidal particles based on food-grade ingredients, especially proteins, is the key technological challenge.

Active motion of a Janus particle by self-thermophoresis in a defocused laser beam

Abstract: We study self-propulsion of a half-metal coated colloidal particle under laser irradiation. The motion is caused by self-thermophoresis: i.e., absorption of a laser at the metal-coated side of the particle creates local temperature gradient which in turn drives the particle by thermophoresis. To clarify the mechanism, temperature distribution and a thermal slip flow field around a microscale Janus particle are measured for the first time. With measured temperature drop across the particle, the speed of self-propulsion is corroborated with the prediction based on accessible parameters. As an application for driving a micromachine, a microrotor is demonstrated.

The rheology of suspensions of solid particles

Abstract: We present data for the rheology of suspensions of monodisperse particles of varying aspect ratio, from oblate to prolate, and covering particle volume fractions from dilute to highly concentrated....

Ceria maintains smaller metal catalyst particles by strong metal-support bonding

Abstract: The energies of silver (Ag) atoms in Ag nanoparticles supported on different cerium and magnesium oxide surfaces, determined from previous calorimetric measurements of metal adsorption energies, were analyzed with respect to particle size. Their stability was found to increase with particle size below 5000 atoms per particle. Silver nanoparticles of any given size below 1000 atoms had much higher stability (30 to 70 kilojoules per mole of silver atoms) on reduced CeO2(111) than on MgO(100). This effect is the result of the very large adhesion energy (approximately 2.3 joules per square meter) of Ag nanoparticles to reduced CeO2(111), which we found to be a result of strong bonding to both defects and CeO2(111) terraces, apparently localized by lattice strain. These results explain the unusual sinter resistance of late transition metal catalysts when supported on ceria.

An amorphous solid state of biogenic secondary organic aerosol particles

Abstract: Secondary organic aerosol (SOA) particles are formed in the atmosphere from condensable oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs)(1-7). On a global scale, biogenic VOCs account for about 90% of VOC emissions(1,8) and of SOA formation (90 billion kilograms of carbon per year)(1-4). SOA particles can scatter radiation and act as cloud condensation or ice nuclei, and thereby influence the Earth's radiation balance and climate(1,2,5,9,10). They consist of a myriad of different compounds with varying physicochemical properties, and little information is available on the phase state of SOA particles. Gas-particle partitioning models usually assume that SOA particles are liquid(1,5,11), but here we present experimental evidence that they can be solid under ambient conditions. We investigated biogenic SOA particles formed from oxidation products of VOCs in plant chamber experiments and in boreal forests within a few hours after atmospheric nucleation events. On the basis of observed particle bouncing in an aerosol impactor and of electron microscopy we conclude that biogenic SOA particles can adopt an amorphous solid-most probably glassy-state. This amorphous solid state should provoke a rethinking of SOA processes because it may influence the partitioning of semi-volatile compounds, reduce the rate of heterogeneous chemical reactions, affect the particles' ability to accommodate water and act as cloud condensation or ice nuclei, and change the atmospheric lifetime of the particles(12-15). Thus, the results of this study challenge traditional views of the kinetics and thermodynamics of SOA formation and transformation in the atmosphere and their implications for air quality and climate.

The Role of Sulfuric Acid in Atmospheric Nucleation

Abstract: Nucleation is a fundamental step in atmospheric new-particle formation. However, laboratory experiments on nucleation have systematically failed to demonstrate sulfuric acid particle formation rates as high as those necessary to account for ambient atmospheric concentrations, and the role of sulfuric acid in atmospheric nucleation has remained a mystery. Here, we report measurements of new particles (with diameters of approximately 1.5 nanometers) observed immediately after their formation at atmospherically relevant sulfuric acid concentrations. Furthermore, we show that correlations between measured nucleation rates and sulfuric acid concentrations suggest that freshly formed particles contain one to two sulfuric acid molecules, a number consistent with assumptions that are based on atmospheric observations. Incorporation of these findings into global models should improve the understanding of the impact of secondary particle formation on climate.

Computer simulation of the translocation of nanoparticles with different shapes across a lipid bilayer

Abstract: Understanding how nanoparticles with different shapes interact with cell membranes is important in drug and gene delivery, but this interaction remains poorly studied. Using computer simulations, we investigate the physical translocation processes of nanoparticles with different shapes (for example, spheres, ellipsoids, rods, discs and pushpin-like particles) and volumes across a lipid bilayer. We find that the shape anisotropy and initial orientation of the particle are crucial to the nature of the interaction between the particle and lipid bilayer. The penetrating capability of a nanoparticle across a lipid bilayer is determined by the contact area between the particle and lipid bilayer, and the local curvature of the particle at the contact point. Particle volume affects translocation indirectly, and particle rotation can complicate the penetration process. Our results provide a practical guide to geometry considerations when designing nanoscale cargo carriers.

Deposition and biokinetics of inhaled nanoparticles

Abstract: Particle biokinetics is important in hazard identification and characterization of inhaled particles. Such studies intend to convert external to internal exposure or biologically effective dose, and may help to set limits in that way. Here we focus on the biokinetics of inhaled nanometer sized particles in comparison to micrometer sized ones.The presented approach ranges from inhaled particle deposition probability and retention in the respiratory tract to biokinetics and clearance of particles out of the respiratory tract. Particle transport into the blood circulation (translocation), towards secondary target organs and tissues (accumulation), and out of the body (clearance) is considered. The macroscopically assessed amount of particles in the respiratory tract and secondary target organs provides dose estimates for toxicological studies on the level of the whole organism. Complementary, microscopic analyses at the individual particle level provide detailed information about which cells and subcellular components are the target of inhaled particles. These studies contribute to shed light on mechanisms and modes of action eventually leading to adverse health effects by inhaled nanoparticles.We review current methods for macroscopic and microscopic analyses of particle deposition, retention and clearance. Existing macroscopic knowledge on particle biokinetics and microscopic views on particle organ interactions are discussed comparing nanometer and micrometer sized particles. We emphasize the importance for quantitative analyses and the use of particle doses derived from real world exposures.

Kinetic Theory of Granular Gases

Abstract: I MECHANICS OF PARTICLE COLLISIONS II GRANULAR GASES - VELOCITY DISTRIBUTION FUNCTION III SINGLE-PARTICLE TRANSPORT, SELF-DIFFUSION AND BROWNIAN MOTION IV TRANSPORT PROCESSES AND KINETIC COEFFICIENTS V STRUCTURE FORMATION

A physical end-to-end model for molecular communication in nanonetworks

Abstract: Molecular communication is a promising paradigm for nanoscale networks. The end-to-end (including the channel) models developed for classical wireless communication networks need to undergo a profound revision so that they can be applied for nanonetworks. Consequently, there is a need to develop new end-to-end (including the channel) models which can give new insights into the design of these nanoscale networks. The objective of this paper is to introduce a new physical end-to-end (including the channel) model for molecular communication. The new model is investigated by means of three modules, i.e., the transmitter, the signal propagation and the receiver. Each module is related to a specific process involving particle exchanges, namely, particle emission, particle diffusion and particle reception. The particle emission process involves the increase or decrease of the particle concentration rate in the environment according to a modulating input signal. The particle diffusion provides the propagation of particles from the transmitter to the receiver by means of the physics laws underlying particle diffusion in the space. The particle reception process is identified by the sensing of the particle concentration value at the receiver location. Numerical results are provided for three modules, as well as for the overall end-to-end model, in terms of normalized gain and delay as functions of the input frequency and of the transmission range.

Sedimentation and effective temperature of active colloidal suspensions.

Abstract: In this Letter, we investigate experimentally the nonequilibrium steady state of an active colloidal suspension under gravity field. The active particles are made of chemically powered colloids, showing self propulsion in the presence of an added fuel, here hydrogen peroxide. The active suspension is studied in a dedicated microfluidic device, made of permeable gel microstructures. Both the microdynamics of individual colloids and the global stationary state of the suspension under gravity are measured with optical microscopy. This yields a direct measurement of the effective temperature of the active system as a function of the particle activity, on the basis of the fluctuation-dissipation relationship. Our work is a first step in the experimental exploration of the out-of-equilibrium properties of active colloidal systems.

ISDD: A Computational Model of Particle Sedimentation, Diffusion and Target Cell Dosimetry for In Vitro Toxicity Studies

Abstract: Background: The difficulty of directly measuring cellular dose is a significant obstacle to application of target tissue dosimetry for nanoparticle and microparticle toxicity assessment, particularly for in vitro systems. As a consequence, the target tissue paradigm for dosimetry and hazard assessment of nanoparticles has largely been ignored in favor of using metrics of exposure (e.g. μg particle/mL culture medium, particle surface area/mL, particle number/mL). We have developed a computational model of solution particokinetics (sedimentation, diffusion) and dosimetry for non-interacting spherical particles and their agglomerates in monolayer cell culture systems. Particle transport to cells is calculated by simultaneous solution of Stokes Law (sedimentation) and the Stokes-Einstein equation (diffusion). Results: The In vitro Sedimentation, Diffusion and Dosimetry model (ISDD) was tested against measured transport rates or cellular doses for multiple sizes of polystyrene spheres (20-1100 nm), 35 nm amorphous silica, and large agglomerates of 30 nm iron oxide particles. Overall, without adjusting any parameters, model predicted cellular doses were in close agreement with the experimental data, differing from as little as 5% to as much as three-fold, but in most cases approximately two-fold, within the limits of the accuracy of the measurement systems. Applying the model, we generalize the effects of particle size, particle density, agglomeration state and agglomerate characteristics on target cell dosimetry in vitro. Conclusions: Our results confirm our hypothesis that for liquid-based in vitro systems, the dose-rates and target cell doses for all particles are not equal; they can vary significantly, in direct contrast to the assumption of doseequivalency implicit in the use of mass-based media concentrations as metrics of exposure for dose-response assessment. The difference between equivalent nominal media concentration exposures on a μg/mL basis and target cell doses on a particle surface area or number basis can be as high as three to six orders of magnitude. As a consequence, in vitro hazard assessments utilizing mass-based exposure metrics have inherently high errors where particle number or surface areas target cells doses are believed to drive response. The gold standard for particle dosimetry for in vitro nanotoxicology studies should be direct experimental measurement of the cellular content of the studied particle. However, where such measurements are impractical, unfeasible, and before such measurements become common, particle dosimetry models such as ISDD provide a valuable, immediately useful alternative, and eventually, an adjunct to such measurements.

Reversing the size-dependence of surface plasmon resonances

Abstract: The size-dependence of surface plasmon resonances (SPRs) is poorly understood in the small particle limit due to complex physical/chemical effects and uncertainties in experimental samples. In this article, we report an approach for synthesizing an ideal class of colloidal Ag nanoparticles with highly uniform morphologies and narrow size distributions. Optical measurements and theoretical analyses for particle diameters in the d ≈ 2–20 nm range are presented. The SPR absorption band exhibits an exceptional behavior: As size decreases from d ≈ 20 nm it blue-shifts but then turns over near d ≈ 12 nm and strongly red-shifts. A multilayer Mie theory model agrees well with the observations, indicating that lowered electron conductivity in the outermost atomic layer, due to chemical interactions, is the cause of the red-shift. We corroborate this picture by experimentally demonstrating precise chemical control of the SPR peak positions via ligand exchange.

Hydrothermal Synthesis of Metal Oxide Nanoparticles in Supercritical Water.

Abstract: This paper summarizes specific features of supercritical hydrothermal synthesis of metal oxide particles. Supercritical water allows control of the crystal phase, morphology, and particle size since the solvent's properties, such as density of water, can be varied with temperature and pressure, both of which can affect the supersaturation and nucleation. In this review, we describe the advantages of fine particle formation using supercritical water and describe which future tasks need to be solved.

Fracture of electrodes in lithium-ion batteries caused by fast charging

Abstract: During charging or discharging of a lithium-ion battery, lithium is extracted from one electrode and inserted into the other. This extraction-insertion reaction causes the electrodes to deform. An electrode is often composed of small active particles in a matrix. If the battery is charged at a rate faster than lithium can homogenize in an active particle by diffusion, the inhomogeneous distribution of lithium results in stresses that may cause the particle to fracture. The distributions of lithium and stress in a LiCoO2 particle are calculated. The energy release rates are then calculated for the particle containing preexisting cracks. These calculations predict the critical rate of charging and size of the particle, below which fracture is averted.

Evidence for the role of organics in aerosol particle formation under atmospheric conditions.

Abstract: New particle formation in the atmosphere is an important parameter in governing the radiative forcing of atmospheric aerosols. However, detailed nucleation mechanisms remain ambiguous, as laboratory data have so far not been successful in explaining atmospheric nucleation. We investigated the formation of new particles in a smog chamber simulating the photochemical formation of H2SO4 and organic condensable species. Nucleation occurs at H2SO4 concentrations similar to those found in the ambient atmosphere during nucleation events. The measured particle formation rates are proportional to the product of the concentrations of H2SO4 and an organic molecule. This suggests that only one H2SO4 molecule and one organic molecule are involved in the rate-limiting step of the observed nucleation process. Parameterizing this process in a global aerosol model results in substantially better agreement with ambient observations compared to control runs.

Dynamics of solids in the midplane of protoplanetary disks: implications for planetesimal formation

Abstract: We present local two-dimensional and three-dimensional hybrid numerical simulations of particles and gas in the midplane of protoplanetary disks (PPDs) using the Athena code. The particles are coupled to gas aerodynamically, with particle-to-gas feedback included. Magnetorotational turbulence is ignored as an approximation for the dead zone of PPDs, and we ignore particle self-gravity to study the precursor of planetesimal formation. Our simulations include a wide size distribution of particles, ranging from strongly coupled particles with dimensionless stopping time τ s ≡ Ωt stop = 10–4 (where Ω is the orbital frequency, t stop is the particle friction time) to marginally coupled ones with τ s = 1, and a wide range of solid abundances. Our main results are as follows. (1) Particles with τ s 10–2 actively participate in the streaming instability (SI), generate turbulence, and maintain the height of the particle layer before Kelvin-Helmholtz instability is triggered. (2) Strong particle clumping as a consequence of the SI occurs when a substantial fraction of the solids are large (τ s 10–2) and when height-integrated solid-to-gas mass ratio Z is super-solar. We construct a toy model to offer an explanation. (3) The radial drift velocity is reduced relative to the conventional Nakagawa-Sekiya-Hayashi (NSH) model, especially at high Z. Small particles may drift outward. We derive a generalized NSH equilibrium solution for multiple particle species which fits our results very well. (4) Collision velocity between particles with τ s 10–2 is dominated by differential radial drift, and is strongly reduced at larger Z. This is also captured by the multi-species NSH solution. Various implications for planetesimal formation are discussed. In particular, we show that there exist two positive feedback loops with respect to the enrichment of local disk solid abundance and grain growth. All these effects promote planetesimal formation.

Shapes of soot aerosol particles and implications for their effects on climate

Abstract: [1] Soot aerosol particles (also called light-absorbing, black, or elemental carbon) are major contributors to global warming through their absorption of solar radiation. When embedded in organic matter or sulfate, as is common in polluted areas such as over Mexico City (MC) and other megacities, their optical properties are affected by their shapes and positions within their host particles. However, large uncertainties remain regarding those variables and how they affect warming by soot. Using electron tomography with a transmission electron microscope, three-dimensional (3-D) images of individual soot particles embedded within host particles collected from MC and its surroundings were obtained. From those 3-D images, we calculated the optical properties using a discrete dipole approximation. Many soot particles have open, chainlike shapes even after being surrounded by organic matter and are located in off-center positions within their host materials. Such embedded soot absorbs sunlight less efficiently than if compact and located near the center of its host particle. In the case of our MC samples, their contribution to direct radiative forcing is ∼20% less than if they had a simple core-shell shape, which is the shape assumed in many climate models. This study shows that the shapes and positions of soot within its host particles have an important effect on particle optical properties and should be recognized as potentially important variables when evaluating global climate change.

The influence of particle characteristics on the behaviour of coarse grained soils

Abstract: This paper describes an experimental study examining the influence of the mechanical and geometrical properties of the constituent grains on the overall material response of cohesionless granular materials. Glass ballotini were used as an analogue soil; their relatively simple geometry allowed the influence of particle shape and inter-particle friction to be examined independently. Techniques were developed to control the surface roughness of the ballotini to facilitate a parametric study. The particle shape was also varied by crushing the ballotini. At the micro-scale, the particle characterisation included accurate measurements of inter-particle friction, contact stiffness, particle surface roughness and particle shape. At the macro-scale the sensitivity of overall material response to changes in surface roughness and geometry was characterised using triaxial tests and oedometer tests on smooth spherical ballotini, roughened ballotini and crushed angular ballotini. Compression tests indicated that the i...

Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

Abstract: . This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA) in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry for the same conditions (liquid water content, particle size). The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ∼5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend on aerosol loading or water content, which indicates a possibly catalytic role of aerosol water in SOA formation. However, the reversible nature of uptake under dark conditions is not captured by keffupt, and can be parameterized by an effective Henry's law constant including an equilibrium constant Kolig = 1000 (in ammonium sulfate solution). Such reversible glyoxal oligomerization contributes Sensitivity tests reveal five parameters that strongly affect the predicted SOA mass from glyoxal: (1) time scales to reach equilibrium states (as opposed to assuming instantaneous equilibrium), (2) particle pH, (3) chemical composition of the bulk aerosol, (4) particle surface composition, and (5) particle liquid water content that is mostly determined by the amount and hygroscopicity of aerosol mass and to a lesser extent by the ambient relative humidity. Glyoxal serves as an example molecule, and the conclusions about SOA formation in aqueous particles can serve for comparative studies of other molecules that form SOA as the result of multiphase chemical processing in aerosol water. This SOA source is currently underrepresented in atmospheric models; if included it is likely to bring SOA predictions (mass and O/C ratio) into better agreement with field observations.

Label-free imaging, detection, and mass measurement of single viruses by surface plasmon resonance.

Abstract: We report on label-free imaging, detection, and mass/size measurement of single viral particles in solution by high-resolution surface plasmon resonance microscopy. Diffraction of propagating plasmon waves along a metal surface by the viral particles creates images of the individual particles, which allow us to detect the binding of the viral particles to surfaces functionalized with and without antibodies. We show that the intensity of the particle image is related to the mass of the particle, from which we determine the mass and mass distribution of influenza viral particles with a mass detection limit of approximately 1 ag (or 0.2 fg/mm2). This work demonstrates a multiplexed method to measure the masses of individual viral particles and to study the binding activity of the viral particles.

Minimal Size of Coffee Ring Structure

Abstract: A macroscopic evaporating water droplet with suspended particles on a solid surface will form a ring-like structure at the pinned contact line due to induced capillary flow. As the droplet size shrinks, the competition between the time scales of the liquid evaporation and the particle movement may influence the resulting ring formation. When the liquid evaporates much faster than the particle movement, coffee ring formation may cease. Here, we experimentally show that there exists a lower limit of droplet size, Dc, for the successful formation of a coffee ring structure. When the particle concentration is above a threshold value, Dc can be estimated by considering the collective effects of the liquid evaporation and the particle diffusive motion within the droplet. For suspended particles of size ∼100 nm, the minimum diameter of the coffee ring structure is found to be ∼10 μm.

Fundamentals of Interface and Colloid Science

Abstract: Publisher Summary This chapter discusses Lyklema's definition of a colloid as “an entity, having at least in one direction a dimension between 1 nm and 1 μm—that is, between 10 –9 and 10 –6 m. The entities may be solid, liquid, or, in some cases, even gaseous. They are dispersed in the medium,” which may be also solid, liquid, or gaseous. All the colloids can be defined as “a collection of particles immersed in a liquid”; the particles can be solid (a suspension or dispersion), liquid (an emulsion), or gas (a foam). These three types of dispersed systems play an important role in all kinds of applications: paints, latices, food products, cements, minerals, ceramics, blood, and many others. All these disperse systems have one common feature; because of their small size, they all have a high surface area relative to their volume. It is the surface-related phenomena that primarily determines their behavior in various processes and justifies consideration of colloids as effectively a different state of matter. The chapter includes the combined terms and methods that have been created over the course of two centuries to characterize these very special systems. Real heterogeneous systems, by their very nature, are quite complex. Two of these complexities are the variation of the particle size and the shape within a particular dispersion. There are three groups of traditional particle sizing methods that can be applied to characterize the size of colloidal particles. These groups are: (1) counters, (2) fractionation techniques, and (3) macroscopic fitting techniques.