Active colloids on fluid interfaces

We review recent work on active colloids at interfaces, including self-propelled colloids that move by generating a propulsive force, and driven colloids that move under external fields. Features unique to fluid interfaces alter the flows generated at interfaces by active colloid motion, and hydrodynamic interactions with these layers. We emphasize recent observations of natural swimmers, like bacteria, and bio-mimetic colloids including self-propelled phoretic and Marangoni swimmers, and magnetically driven colloids. We discuss active colloid interaction with boundaries and with each other. We conclude with a discussion of open issues and opportunities to design active colloids as active surface agents that manipulate interfacial properties and the transport in the vicinity of interfaces.     

壳聚糖-硫酸葡聚糖聚电解质复合物纳米胶体粒膨胀性能研究

制备了壳聚糖-硫酸葡聚糖聚电解质复合物纳米胶体粒子,探讨了胶体粒形成的作用机理,并对其在不同条件下的膨胀行为进行了研究。结果表明,复合物胶体粒子带负电荷,形成过程中所加组分CS的量可以控制胶体所带的负电荷量;复合物胶体有良好的膨胀性,膨胀率最大可达380%,且随组分分子量、含量及pH值的变化呈现一定的规律性。     

Model analysis of the colloid and radionuclide retardation experiment at the Grimsel Test Site

The colloid and radionuclide retardation experiments performed at NAGRA's Grimsel Test Site in Switzerland are part of an international collaboration program designed to collect in situ data on the impacts of colloids on radionuclide transport. In this work, breakthrough behaviors of trivalent americium (i.e., 241Am and 243Am) both in the absence and presence of bentonite colloids are analyzed with COLFRAC--a code that models colloid-facilitated solute transport in discretely-fractured, porous media. Model fits to the experimental results indicate that Am sorbed onto mobile colloids, which enhance Am transport relative to a non-sorbing tracer, 131I. Modelling results suggest that Am is kinetically sorbed onto both naturally occurring and exogenous bentonite colloids. Results also indicate that desorption of Am from colloids is slow with respect to the duration of the experiment. In addition, early colloid breakthrough compared to a conservative tracer suggests the effects of hydrodynamic chromatography. Overall, Am breakthrough curves suggest enhanced mobility due to co-transport with both naturally occurring and bentonite colloids.     

Silica-supported chromium oxide: colloids as building blocks

In this contribution, the formation and immobilisation of chromium(iii) hydroxyoxide colloids is investigated. Nano-sized Cr(iii) colloids are generated in situ upon reduction of Cr(vi), dosed to a stirred reactor. The growth of the elementary colloids by the consumption of solved Cr is kinetically unfavorable compared to their aggregation to larger secondary particles, the size of which depends on the concentration of the building block colloids. This aggregation process can be steered by simple process parameters such as dosing rate and concentration of the Cr(vi). The Cr(iii) colloids are immobilised in situ on a support material via precipitation chromatography. Upon drying, the initially amorphose hydroxyoxides are gradually transformed into crystalline Cr(2)O(3) nanoparticles, mainly located at the external surface of the support. This approach opens new opportunities for the synthesis of supported metal oxide catalysts.     

Active colloids: Progress and challenges towards realising autonomous applications

Active colloids are small scale materials capable of producing enhanced motion within fluid environments. The field of active colloids has grown rapidly over the last ten years and is approaching maturity where viable applications are within reach. In this review, recent advances are surveyed with a strong emphasis on developments that can enable autonomous applications, where colloids execute useful tasks without external interventions. These applications are likely to prove transformative as the resulting technologies will be significantly less complex than current methods. A survey of the requirements to achieve autonomous applications is provided, considering guidance, solution compatibilities, manufacture and function; with reference to recent developments in these capacities. Following on from this, progress towards applications in environmental remediation, lab-on-a-chip microfluidics and in vivo drug delivery is highlighted.     

Self-assembly and field-responsive optical diffractions of superparamagnetic colloids

Superparamagnetic Fe(3)O(4) colloids with highly charged surfaces have been assembled into ordered structures in water in response to external magnetic fields. The colloids form chainlike structures with regular interparticle spacings of a few hundred nanometers along the direction of the external field so that the system strongly diffracts visible light. The balance between attractive (in this case, magnetic) and repulsive (electrostatic) forces dictates interparticle spacing and therefore optical properties. By changing the relative strength of these two forces, one can tune the peak diffraction wavelength over the entire visible spectrum. We were able to optimize the diffraction intensity and the tuning range through studying their dependence on variables such as the size distribution and concentration of the Fe(3)O(4) colloids or ionic strength of the solutions. The fast, reversible response and the feasibility for miniaturization impart these photonic materials great potential in applications such as optoelectronic devices, sensors, and color displays.     

One-step synthesis of silver nanoparticles by sonication or heating using amphiphilic block copolymer as templates

Block copolymer-supported Ag Nps (nanoparticles) have either a "cherry"-like or "raspberry"-like morphology [Antonietti, et al., Adv. Mater. 7 (1995) 1000-1005] depending on the amount of silver nitrate loading and the external conditions. Sonication favors silver nitrate and polyethyleneimine diffusion; the nucleation sites are well distributed in the micellar cores, so it is easy to form the cherry-like Ag NP colloids. However, when the amount of silver nitrate is decreased, it is heating that induces the formation of raspberry-like Ag NP colloids. The Ag NP colloids were investigated by transmission electron microscopy to demonstrate the nanosize dimensions and the location of the Ag NPs in the micelles. X-ray diffraction was employed to determine the crystal structure of the Ag NPs. UV-vis spectroscopy was employed for further qualitative characterization of the optical properties of Ag NPs.     

Studies about the influence of self-organization of colloidal magnetic nanoparticles on the magnetic Néel relaxation time

The monodomain magnetic nanoparticle-based colloids are mainly used in biomedical applications. In this type of colloids, there is a tendency of agglomeration even in the absence of external magnetic field. So, the Néel magnetic relaxation time of the system is affected by that tendency. In this paper, we propose a model to study how the nanoparticle tendency to agglomerate in the nanofluid affects the Néel relaxation time of the system. For simulating the self-organization of colloidal nanoparticles, we apply a Monte Carlo method, and the Néel magnetic relaxation time is assessed through the adaptation and solution of Coffey equations in oblique magnetic field, adapted to the local magnetic field on a nanoparticle.     

Magnetic click colloidal assembly

We introduce a new class of spherical colloids that reversibly self-assemble into well-defined nonlinear structures by virtue of "magnetic patches". This assembly is driven by tunable magnetostatic binding forces that originate from microscopic permanent magnets embedded underneath the surface of the particles. The resulting clusters form spontaneously in the absence of external magnetizing fields, and their geometry is determined by an interplay between magnetic, steric, and electrostatic interactions. Imposing an external magnetic field enables the clusters to unbind or change their geometry allowing, in principle, the creation of materials with a reconfigurable structural arrangement.     

Role of anisotropy in electrodynamically induced colloidal aggregates

We investigate the assembly of spherical and anisotropic colloidal particles with the shape of peanuts when subjected to an external alternating electric field. By varying the strength and frequency of the applied field, we observe that both types of particles form clusters at low frequencies due to attractive electrohydrodynamic interactions or disperse into a liquidlike phase at high frequencies due to repulsive dipolar interactions. We characterize the observed structures via pair correlation functions and radius of gyration, and observe a clear difference in the ordering process between the isotropic and anisotropic colloids. Further on, we interpret the cluster formation kinetics in terms of dynamic scaling theory, and observe a faster aggregation of the anisotropic colloids with respect to the isotropic ones.     

Colloid filtration theory and the Happel sphere-in-cell model revisited with direct numerical simulation of colloids

The transport of colloids and bacterial cells through saturated porous media is a complex phenomenon involving many interrelated processes that are often treated via application of classical colloid filtration theory (CFT). This paper presents a numerical investigation of CFT from the Lagrangian perspective, to evaluate the role of some of the classical assumptions underlying the theory and to demonstrate a means to include processes relevant to bacterial transport that were inadequately characterized or neglected in the original formulation, including Brownian diffusion and potentially hysteretic potential functions. The methodology is based on conducting a Lagrangian trajectory analysis within Happel's sphere-in-cell porous media model to obtain the collection efficiency (eta), the frequency at which colloids or bacteria make contact with the solid phase of the porous medium. The Lagrangian framework of our model lends itself to mechanistic modeling of the biological processes that may be important in subsurface bacterial transport. The numerical study presented here focuses on the size range of bacterial colloids and smaller (down to 10 nm). Results of our model runs are in good agreement with the deterministic trajectory analysis of Rajagopalan and Tien (when diffusion is neglected) and in excellent agreement with the analytical solution to the Smoluchowski-Levich approximation of the convective-diffusion equation (when external forces and interception are neglected). Simple addition of our result for the deterministic eta to our result for the Smoluchowski-Levich eta matches the overall Rajagopalan and Tien eta to within 5% error or less for all cases studied. When we simulate diffusion and the deterministic forces together, our results diverge from the Rajagopalan and Tien eta as the particle size decreases, with discrepancies as large as 73%. These results suggest that accurate prediction of eta values for bacteria-sized (and all submicrometer) colloids requires simultaneous consideration of the primary transport mechanisms.     

Field induced formation of mesoscopic polymer chains from functional ferromagnetic colloids

The assembly and direct imaging of ferromagnetic nanoparticles into one-dimensional mesostructures (1-D) are reported. Polymer-coated ferromagnetic colloids (19 nm, 24 nm) were assembled at a crosslinkable oil-water interface under both magnetic field induced and zero-field conditions and permanently fixed into 1-D mesoscopic polymer chains (1-9 mum) in a process referred to as Fossilized Liquid Assembly (FLA). In the FLA process, nanoparticle chains were fixed at the oil interface through photopolymerization, enabling direct visualization of organized mesostructures using atomic force microscopy. Using the FLA methodology, we systematically investigated different conditions and demonstrated that dispersed ferromagnetic colloids possess sufficient dipolar interactions to organize into mesoscopic assemblies. Application of an external magnetic field during assembly enabled the formation of micron-sized chains which were aligned in the direction of the applied field. This universal methodology is an attractive alternative technique to cryogenic transmission electron microscopy (cryo-TEM) for the visualization of nanoparticle assembly in dispersed organic media.     

Ultrasonic attenuation by nanoporous particles. Part II: experimental

In Part I of this paper O'Brien presented a new theory that describes the dissipation of ultrasonic energy by porous colloidal particles in suspension. In this paper we present experimental measurements on several such suspensions and compare the resulting ultrasonic attenuation spectra with O'Brien's theory. We find that microporous colloids (e.g. zeolites) and mesoporous colloids (e.g. porous silicas) both show greater attenuation of ultrasound than would solid particles of the same size and effective density, as predicted by O'Brien. Fitting theoretical spectra to the experimental data provides information about the porosity and pore diameters in the particles. This makes the technique potentially suitable as a convenient method of characterizing nanoporous materials, especially those already in suspension.     

Inverse patchy colloids: Synthesis,modeling and self-organization

Inverse patchy colloids are nano- to micro-scale particles with a surface divided into differently charged regions. This class of colloids combines directional, selective bonding with a relatively simple particle design: owing to the competitive interplay between the orientation-dependent attraction and repulsion — induced by the interactions between like/oppositely charged areas — experimentally accessible surface patterns are complex enough to favor the stabilization of specific structures of interest. Most important, the behavior of heterogeneously charged units can be ideally controlled by means of external parameters, such as the pH and the salt concentration. We present a concise review about this class of systems, spanning the range from the synthesis of model inverse patchy particles to their self-assembly, covering their coarse-grained modeling and the related numerical/analytical treatments.     

On the heterometric titration of small amounts of sulfates

We found that a mixture of 2 parts water, I part ethanol, and I part n-butanol is the most suitable medium for the heterometric titration of small amounts of sulfate (2–20 mg). The addition of protective colloids is not necessary if the solution is stirred vigorously during the course of the titration. The disturbing effect of some other ions was investigated. Calcium, aluminium, and ferric iron can be precipitated beforehand in the cuvette without seriously hindering the sulfate titration.     

Cooperative magnetophoresis of superparamagnetic colloids: theoretical aspects

Superparamagnetic colloids have a great practical interest for their applications to processes ranging from biomedicine to environmental waste and pollutants removal. A fast and efficient separation of these particles from the solvent constitutes a key step in the practical implementation of this technology. Recent experiments show fast magnetophoretic separation using relatively small magnetic gradients and high magnetic fields. The mechanism underlying this fast separation was shown to be the reversible aggregation of the magnetic beads induced by the external field. In this paper, we analyze theoretically the physicochemical conditions under which reversible aggregation can be typically achieved, the timescale at which aggregates form, and their shape. In the case of colloids stabilized electrostatically, for reasonable surface potentials (approximately −70 mV), we find that the interaction potential between two superparamagnetic particles displays a barrier with a minimum so that reversible aggregates can form. We also show that the aggregation of particles is quite fast (typically less than a second for usual concentrations) and that lateral aggregation is more energetically stable than tip-to-tip aggregation for long chains (larger than 14 microspheres). This is consistent with experimental observations and very relevant for a fast magnetophoresis since thick aggregates move faster than thin ones.     

Dense colloid transport in a bifurcating fracture

In this work, the transport of dense colloids through a water-saturated, bifurcating fracture is investigated using a constant spatial step particle tracking technique. The size of the constituents of a colloid plume is an important factor affecting the partitioning of dense colloids at the bifurcation. While neutrally buoyant colloids partition between daughter fractures in proportion to flow rates, dense colloids will preferentially exit fractures that are gravitationally downgradient, notwithstanding that the majority of the interstitial fluid may flow through the upper fracture. Comparison of the partitioning ratio between daughter fractures with the ratios of characteristic settling, diffusion, and advection time reveal that these parameters control how colloids behave at fracture bifurcations.     

Clustering versus percolation in the assembly of colloids coated with long DNA

We report an experimental study in which we compare the self-assembly of 1 mum colloids bridged through hybridization of complementary single-stranded DNA (ssDNA) strands (12 bp) attached to variable-length double-stranded DNA spacers that are grafted to the colloids. We considered three different spacer lengths: long spacers (48 500 bp), intermediate length spacers (7500 bp), and no spacers (in which case the ssDNA strands were directly grafted to the colloids). In all three cases, the same ssDNA pairs were used. However, confocal microscopy revealed that the aggregation behavior is very different. Upon cooling, the colloids coated with short and intermediate length DNAs undergo a phase transition to a dense amorphous phase that undergoes structural arrest shortly after percolation. In contrast, the colloids coated with the longest DNA systematically form finite-sized clusters. We speculate that the difference is due to the fact that very long DNA can easily be stretched by the amount needed to make only intracluster bonds, and in contrast, colloids coated with shorter DNA always contain free binding sites on the outside of a cluster. The grafting density of the DNA decreases strongly with increasing spacer length. This is reflected in a difference in the temperature dependence of the aggregates: for the two systems coated with long DNA, the resulting aggregates were stable against heating, whereas the colloids coated with ssDNA alone would dissociate upon heating.     

Colloidal crystallization and transport in stripes and mazes

We study guided crystallization and transport of paramagnetic spheres on top of a magnetic film that arranges its domains into stripes or mazes. In the absence of liquid flow, the paramagnetic spheres are confined within the magnetic domains, and it is shown how the particles self-assemble into several interesting phases depending on the complexity of the domain patterns. We also find that colloids guided through a complex maze exhibit structured patterns that can be controlled by an external magnetic field. The results presented here could help us understand both static and dynamic properties of pattern formation in confined geometries of tunable complexity.     

Synthesis of anionic core-shell poly(styrene-<Emphasis Type="Italic">co-N</Emphasis>-isopropylacrylamide) colloids by a two-step surfactant-free emulsion polymerization

The aim of the performed work is to produce anionic core-shell poly(styrene-co-N-isopropylacrylamide) colloids with an N-isopropylacrylamide (NIPAM) content in the range from 5 to 30 mol %. Different batches of poly(styrene-co-NIPAM) colloids (poly(ST-co-NIPAM) colloids) are produced with varying NIPAM mol %, and the produced poly(ST-co-NIPAM) colloids are characterized by dynamic light scattering and scanning electron microscopy. Results show that the produced colloids have a core-shell morphology with a poly(styrene) core and a poly(NIPAM) shell. The swelling ratio of the produced poly(ST-co-NIPAM) colloids is similar to the swelling ratio found for similar poly(ST-co-NIPAM) colloids produced by the two-step seeded polymerization process. The text was submitted by the author in English.