Improved Magneto-Microfluidic Separation of Nanoparticles through Formation of the ß-Cyclodextrin-Curcumin Inclusion Complex.

Molecular adsorption to the nanoparticle surface may switch the colloidal interactions from repulsive to attractive and promote nanoparticle agglomeration. If the nanoparticles are magnetic, then their agglomerates exhibit a much stronger response to external magnetic fields than individual nanoparticles. Coupling between adsorption, agglomeration, and magnetism allows a synergy between the high specific area of nanoparticles (∼100 m2/g) and their easy guidance or separation by magnetic fields. This yet poorly explored concept is believed to overcome severe restrictions for several biomedical applications of magnetic nanoparticles related to their poor magnetic remote control. In this paper, we test this concept using curcumin (CUR) binding (adsorption) to ß-cyclodextrin (ßCD)-coated iron oxide nanoparticles (IONP). CUR adsorption is governed by host-guest hydrophobic interactions with ßCD through the formation of 1:1 and, possibly, 2:1 ßCD:CUR inclusion complexes on the IONP surface. A 2:1 stoichiometry is supposed to promote IONP primary agglomeration, facilitating the formation of the secondary needle-like agglomerates under external magnetic fields and their magneto-microfluidic separation. The efficiency of these field-induced processes increases with CUR concentration and ßCD surface density, while their relatively short timescale (<5 min) is compatible with magnetic drug delivery application.

Adsorption of Organic Dyes on Magnetic Iron Oxide Nanoparticles. Part II: Field-Induced Nanoparticle Agglomeration and Magnetic Separation.

This paper (part II) is devoted to the effect of molecular adsorption on the surface of magnetic iron oxide nanoparticles (IONP) on the enhancement of their (secondary) field-induced agglomeration and magnetic separation. Experimentally, we use Methylene Blue (MB) cationic dye adsorption on citrate-coated maghemite nanoparticles to provoke primary agglomeration of IONP in the absence of the field. The secondary agglomeration is manifested through the appearance of needlelike micron-sized agglomerates in the presence of an applied magnetic field. With the increasing amount of adsorbed MB molecules, the size of the field-induced agglomerates increases and the magnetic separation on a magnetized micropillar becomes more efficient. These effects are mainly governed by the ratio of magnetic-to-thermal energy α, suspension supersaturation Δ0, and Brownian diffusivity Deff of primary agglomerates. The three parameters (α, Δ0, and Deff) are implicitly related to the surface coverage θ of IONP by MB molecules through the hydrodynamic size of primary agglomerates exponentially increasing with θ. Experiments and developed theoretical models allow quantitative evaluation of the θ effect on the efficiency of the secondary agglomeration and magnetic separation.

Single-walled carbon nanotubes as a photo-thermo-acoustic cancer theranostic agent: theory and proof of the concept experiment.

Theranostics is the emerging field of medicine that uniquely combines diagnostic techniques and active agents to diagnose and treat medical conditions simultaneously or sequentially. Finding a theranostic agent capable to cure the affected cells and being safe for the healthy ones is the key for successful treatment. Here, we demonstrate that agglomerated single-walled carbon nanotubes (SWCNTs) are promising theranostic agent that enables photo-activated 'cold' destruction of the cancer cells keeping their environment alive. The absorption of picosecond pulses by SWCNT agglomerates results in the mechanical (due to photoacoustic effect) rather than photothermal cancer cell destruction, which was visualized by micro-Raman and ultrafast near-infrared CARS. The developed theoretical model allows us to distinguish photothermal, photoacoustic, and photothermoacoustic regimes of the cancer cell destruction, and also to optimize SWCNT-based theranostics recipe.

Kinetics of field-induced phase separation of a magnetic colloid under rotating magnetic fields.

This paper is focused on the experimental and theoretical study of the phase separation of a magnetic nanoparticle suspension under rotating magnetic fields in a frequency range, 5 Hz ≤ ν ≤ 25 Hz, relevant for several biomedical applications. The phase separation is manifested through the appearance of needle-like dense particle aggregates synchronously rotating with the field. Their size progressively increases with time due to the absorption of individual nanoparticles (aggregate growth) and coalescence with neighboring aggregates. The aggregate growth is enhanced by the convection of nanoparticles toward rotating aggregates. The maximal aggregate length, Lmax ∝ ν-2, is limited by fragmentation arising as a result of their collisions. Experimentally, the aggregate growth and coalescence occur at a similar timescale, ∼1 min, weakly dependent on the field frequency. The proposed theoretical model provides a semi-quantitative agreement with the experiments on the average aggregate size, aggregation timescale, and size distribution function without any adjustable parameter.

Creation of metasurface from vertically aligned carbon nanotubes as versatile platform for ultra-light THz components.

Here a simple and reproducible method for obtaining terahertz metasurfaces formed from multiwall carbon nanotubes (MWCNTs) is presented. The metasurfaces were obtained from a vertically aligned array of MWCNTs using a laser engraving technique followed by polymer covering. The structures under study demonstrate frequency-selective reflection in terahertz range following the Huygens-Fresnel formalism. For a normal incidence of the electromagnetic wave, the model for numerical calculation of backscattering from the metasurfaces was proposed. Lightweight and compact MWCNT-based metasurfaces are capable to replace conventional pyramidal absorbers and could serve as a versatile platform for scalable cost-efficient production of ultra-light electromagnetic components for THz applications.

Carbon nanotube sponges as tunable materials for electromagnetic applications.

The microwave conductivity and permittivity of both single-walled and multi-walled carbon nanotube (SWCNT and MWCNT) sponges were measured while compressing the samples. Compression leads to a huge variation of the absorptance, reflectance, and transmittance of the samples. The dependence of the microwave conductivity on the sponge density follows a power-law relation with exponents 1.7 ± 0.1 and 2.0 ± 0.2 for MWCNT and SWCNT sponges, respectively. These exponents can be decreased slightly by the addition of a non-conducting component which partly electrically separates adjacent tubes within the samples. The conductivity of MWCNT sponge was measured in the terahertz range while heating in air from 300 to 513 K and it increased due to an increase of a number of conducting channels in MWCNTs.

Two-stage kinetics of field-induced aggregation of medium-sized magnetic nanoparticles.

The present paper is focused on the theoretical and experimental study of the kinetics of field-induced aggregation of magnetic nanoparticles of a size range of 20-100 nm. Our results demonstrate that (a) in polydisperse suspensions, the largest particles could play a role of the centers of nucleation for smaller particles during the earliest heterogeneous nucleation stage; (b) an intermediate stage of the aggregate growth (due to diffusion and migration of individual nanoparticles towards the aggregates) is weakly influenced by the magnetic field strength, at least at high supersaturation;

Kinetics of doublet formation in bicomponent magnetic suspensions: The role of the magnetic permeability anisotropy.

Micron-sized particles (microbeads) dispersed in a suspension of magnetic nanoparticles, i.e., ferrofluids, can be assembled into different types of structures upon application of an external magnetic field. This paper is devoted to theoretical modeling of a relative motion of a pair of microbeads (either soft ferromagnetic or diamagnetic) in the ferrofluid under the action of applied uniform magnetic field which induces magnetic moments in the microbeads making them attracting to each other. The model is based on a point-dipole approximation for the magnetic interactions between microbeads mediated by the ferrofluid; however, the ferrofluid is considered to possess an anisotropic magnetic permeability thanks to field-induced structuring of its nanoparticles. The model is tested against experimental results and shows generally better agreement with experiments than the model considering isotropic magnetic permeability of ferrofluids. The results could be useful for understanding kinetics of aggregation of microbeads suspended in a ferrofluid. From a broader perspective, the present study is believed to contribute to a general understanding of particle behaviors in anisotropic media.

Microfluidic separation of magnetic nanoparticles on an ordered array of magnetized micropillars.

Microfluidic separation of magnetic particles is based on their capture by magnetized microcollectors while the suspending fluid flows past the microcollectors inside a microchannel. Separation of nanoparticles is often challenging because of strong Brownian motion. Low capture efficiency of nanoparticles limits their applications in bioanalysis. However, at some conditions, magnetic nanoparticles may undergo field-induced aggregation that amplifies the magnetic attractive force proportionally to the aggregate volume and considerably increases nanoparticle capture efficiency. In this paper, we have demonstrated the role of such aggregation on an efficient capture of magnetic nanoparticles (about 80 nm in diameter) in a microfluidic channel equipped with a nickel micropillar array. This array was magnetized by an external uniform magnetic field, of intensity as low as 6-10 kA/m, and experiments were carried out at flow rates ranging between 0.3 and 30 µL/min. Nanoparticle capture is shown to be mostly governed by the Mason number Ma, while the dipolar coupling parameter α does not exhibit a clear effect in the studied range, 1.4 < α < 4.5. The capture efficiency Λ shows a strongly decreasing Mason number behavior, Λ∝Ma^{-1.78} within the range 32 ≤ Ma ≤ 3250. We have proposed a simple theoretical model which considers destructible nanoparticle chains and gives the scaling behavior, Λ∝Ma^{-1.7}, close to the experimental findings.

Flexible transparent graphene/polymer multilayers for efficient electromagnetic field absorption.

Thanks to its high electrical conductivity, a graphene plane presents a good shielding efficiency against GHz electromagnetic radiations. Several graphene planes separated by thin polymer spacers add their conductivities arithmetically, because each of them conserves the intrinsic properties of isolated graphene. Maximum absorption of radiations for frequency around 30 GHz is achieved with six separated graphene planes, which is the optimum number. This remarkable result is demonstrated experimentally from electromagnetic measurements performed in the Ka band on a series of multilayers obtained by piling 1, 2, 3... graphene/PMMA units on a silica substrate. Theoretical calculations convincingly explain the observed absorption and transmission data in the GHz domain. It is concluded that graphene/PMMA multilayers can be used as an efficient optically transparent and flexible shielding media.

How nonmagnetic particles intensify rotational diffusion in magnetorheological fluids.

In this work we propose a mechanism to explain the enhancement of the magnetic-field-induced yield stress when nonmagnetic particles are added to magnetic particulate suspensions, i.e., two-component suspensions. Our main hypothesis is that the nonmagnetic particles collide with the field-induced magnetic aggregates under shear flow. Consequently, supplementary fluctuations of the orientations of the magnetic aggregates occur, resulting in an effective rotary diffusion process, which increases the dynamic yield stress of the suspension. Furthermore, the collision rate and the rotary diffusivity of the aggregates should increase with the concentration of nonmagnetic particles. Rheological measurements in plate-plate and cylindrical Couette geometries confirm the increase of the yield stress with the volume fraction of nonmagnetic particles. In addition, such an effect appears to be more important in Couette geometry, for which orientation fluctuations of the magnetic aggregates play a more significant role. Finally, a theoretical model based on this rotary diffusion mechanism is developed, providing a quantitative explanation of the experimentally observed trends.

Behavior of nanoparticle clouds around a magnetized microsphere under magnetic and flow fields.

When a micron-sized magnetizable particle is introduced into a suspension of nanosized magnetic particles, the nanoparticles accumulate around the microparticle and form thick anisotropic clouds extended in the direction of the applied magnetic field. This phenomenon promotes colloidal stabilization of bimodal magnetic suspensions and allows efficient magnetic separation of nanoparticles used in bioanalysis and water purification. In the present work, the size and shape of nanoparticle clouds under the simultaneous action of an external uniform magnetic field and the flow have been studied in detail. In experiments, a dilute suspension of iron oxide nanoclusters (of a mean diameter of 60 nm) was pushed through a thin slit channel with the nickel microspheres (of a mean diameter of 50 µm) attached to the channel wall. The behavior of nanocluster clouds was observed in the steady state using an optical microscope. In the presence of strong enough flow, the size of the clouds monotonically decreases with increasing flow speed in both longitudinal and transverse magnetic fields. This is qualitatively explained by enhancement of hydrodynamic forces washing the nanoclusters away from the clouds. In the longitudinal field, the flow induces asymmetry of the front and the back clouds. To explain the flow and the field effects on the clouds, we have developed a simple model based on the balance of the stresses and particle fluxes on the cloud surface. This model, applied to the case of the magnetic field parallel to the flow, captures reasonably well the flow effect on the size and shape of the cloud and reveals that the only dimensionless parameter governing the cloud size is the ratio of hydrodynamic-to-magnetic forces-the Mason number. At strong magnetic interactions considered in the present work (dipolar coupling parameter α≥2), the Brownian motion seems not to affect the cloud behavior.

Epoxy resin/carbon black composites below the percolation threshold.

A set of epoxy resin composites filled with 0.25-2.0 wt.% of commercially available ENSACO carbon black (CB) of high and low surface area (CBH and CBL respectively) has been produced. The results of broadband dielectric spectroscopy of manufactured CB/epoxy below the percolation threshold in broad temperature (200 K to 450 K) and frequency (20 Hz to 1 MHz) ranges are reported. The dielectric properties of composites below the percolation threshold are mostly determined by alpha relaxation in pure polymer matrix. The glass transition temperature for CB/epoxy decreases in comparison with neat epoxy resin due to the extra free volume at the polymer-filler interface. At room temperature, the dielectric permittivity is higher for epoxy loaded with CBH additives. In contrast, at high temperature, the electrical conductivity was found to be higher for composites with CBL embedded. The established influence of the CB surface area on the broadband dielectric characteristics can be exploited for the production of effective low-cost antistatic paints and coatings working at different temperatures.

Multilayered graphene in K(a)-band: nanoscale coating for aerospace applications.

We report on the experimental study of electromagnetic (EM) properties of multilayered graphene in K(a)-band synthesized by catalytic chemical vapor deposition (CVD) process in between nanometrically thin Cu catalyst film and dielectric (SiO2) substrate. The quality of the produced multilayered graphene samples was monitored by Raman spectroscopy. The thickness of graphene films was controlled by atomic force microscopy (AFM) and was found to be a few nanometers (up to 5 nm). We discovered, that the fabricated graphene, being only some thousandth of skin depth, provided remarkably high EM shielding efficiency caused by absorption losses at the level of 35-43% of incident power. Being highly conductive at room temperature, multilayer graphene emerges as a promising material for manufacturing ultrathin microwave coatings to be used in aerospace applications.

Soft cutting of single-wall carbon nanotubes by low temperature ultrasonication in a mixture of sulfuric and nitric acids.

To decrease single-wall carbon nanotube (SWCNT) lengths to a value of 100-200 nm, aggressive cutting methods, accompanied by a high loss of starting material, are frequently used. We propose a cutting approach based on low temperature intensive ultrasonication in a mixture of sulfuric and nitric acids. The method is nondestructive with a yield close to 100%. It was applied to cut nanotubes produced in three different ways: gas-phase catalysis, chemical vapor deposition, and electric-arc-discharge methods. Raman and Fourier transform infrared spectroscopy were used to demonstrate that the cut carbon nanotubes have a low extent of sidewall degradation and their electronic properties are close to those of the untreated tubes. It was proposed to use the spectral position of the far-infrared absorption peak as a simple criterion for the estimation of SWCNT length distribution in the samples.

Haloing in bimodal magnetic colloids: the role of field-induced phase separation.

If a suspension of magnetic micrometer-sized and nanosized particles is subjected to a homogeneous magnetic field, the nanoparticles are attracted to the microparticles and form thick anisotropic halos (clouds) around them. Such clouds can hinder the approach of microparticles and result in effective repulsion between them [M. T. López-López, A. Yu. Zubarev, and G. Bossis, Soft Matter 6, 4346 (2010)]. In this paper, we present detailed experimental and theoretical studies of nanoparticle concentration profiles and of the equilibrium shapes of nanoparticle clouds around a single magnetized microsphere, taking into account interactions between nanoparticles. We show that at a strong enough magnetic field, the ensemble of nanoparticles experiences a gas-liquid phase transition such that a dense liquid phase is condensed around the magnetic poles of a microsphere while a dilute gas phase occupies the rest of the suspension volume. Nanoparticle accumulation around a microsphere is governed by two dimensionless parameters--the initial nanoparticle concentration (φ(0)) and the magnetic-to-thermal energy ratio (α)--and the three accumulation regimes are mapped onto a α-φ(0) phase diagram. Our local thermodynamic equilibrium approach gives a semiquantitative agreement with the experiments on the equilibrium shapes of nanoparticle clouds. The results of this work could be useful for the development of the bimodal magnetorheological fluids and of the magnetic separation technologies used in bioanalysis and water purification systems.

Synthesis and magnetorheology of suspensions of submicron-sized cobalt particles with tunable particle size.

Different samples of cobalt powder were synthesized. Particle size and shape were characterized using electron microscopy and light scattering. These measurements showed that the synthesized powders consisted of monodisperse spheres with average diameters ranging between 63 and 760 nm. These powders were used for the preparation of magnetorheological (MR) fluids by dispersing them in silicone oil. The MR properties of these MR fluids were investigated. It was found that particle size did not have much influence on the MR response of MR fluids, for average particle diameters larger than 100 nm. On the other hand, the MR response decreased appreciably when the average particle diameter was diminished below 100 nm; a theory based on the change of the shape of the aggregates with the size of the particles could explain these observations.

Oscillatory squeeze flow of suspensions of magnetic polymerized chains.

We report a rheological study of suspensions of non-Brownian chain-like magnetic particles in the presence of magnetic fields. These particles have been synthesized using spherical iron particles by linking them with a polymer and are called polymerized chains. We have shown that, in oscillatory squeeze mode, the suspensions of such chain-like particles develop yield stress several times higher than that of conventional magnetorheological fluids based on spherical iron particles. This is explained in terms of solid friction between polymerized chains, which form entangled aggregates in the presence of a magnetic field. For the suspension of spherical particles, the squeezing force increases with the magnetic field intensity at low magnetic fields, but decreases dramatically at higher fields because of cavitation or air entrainment. Such a decrease in transmitted force does not take place in suspensions of polymerized chains, at least for fields smaller than 30 kA m(-1), which could make these suspensions preferable for application in squeeze-film dampers.

Dipole polarizability of onion-like carbons and electromagnetic properties of their composites.

Onion-like carbons (OLC) obtained by thermal transformation of nanodiamonds are agglomerates of multi-shell fullerenes, often covered by an external graphitic mantle. For the present work, elemental OLC units were constructed on the computer by coalescence of several two-layer fullerenes, in a structure similar to carbon peapods with a corrugated external wall. The electrical polarizability of such pod-of-peas fullerenes has been computed by a classical monopole-dipole atomistic theory. The description of pod-of-peas fullerenes was further simplified by representing them as linear arrays of point-like objects, whose polarizability matches that of the starting molecules. Calculations demonstrated that the static polarizability of spherically shaped assemblies of these arrays, modeling real OLC materials, is weakly dependent on the geometry of its constituent molecules and is chiefly proportional to the volume of the whole cluster. It increases with increasing filling fraction of the pod-of-peas fullerenes in the OLC aggregate. The polarizability so obtained can be used in Maxwell-Garnett theory to predict the permittivity of OLC-based composites, at least for static excitations. Experimental results obtained at GHz frequencies reveal a weak attenuation for OLC- and nanodiamond-based polydimethylsiloxane composites. In these silicone composites, we did not find long chains of coupled OLCs. Quite separated clusters were found instead, which contribute little to the polarizability and to the dielectric properties, in good agreement with our theoretical predictions.