Silver-loaded nanoparticles affect ex-vivo mechanical behavior and mineralization of dentin.

BACKGROUND: The aim was to evaluate the effect of silver loaded nanoparticles (NPs) application on the triboscopic, crystallographic and viscoelastic properties of demineralized dentin. Polymethylmetacrylate-based NPs and Ag loaded NPs were applied on demineralized dentin. MATERIAL AND METHODS: Treated and untreated surfaces were probed by a nanoindenter to test viscoelasticity, and by atomic force microscopy to test nanoroughness and collagen fibril diameter. X-ray diffraction and transmission electron microscopy through selected area diffraction and bright-field imaging were also used. RESULTS: Dentin treated with Ag-NPs attained the lowest complex modulus, and the highest tan delta values after 7 days of storage. Dentin treated with undoped-NPs achieved the lowest nanoroughness and the greatest collagen bandwidths among groups. Crystals were identified as hydroxyapatite with the highest crystallographic maturity and crystallite size in dentin treated with undoped-NPs. Texture increased in all samples from 24 h to 7 d, except in dentin surfaces treated with Ag-NPs at 310 plane. Polyhedral, block-like, hexagonal or plate-like shaped apatite crystals constituted the bulk of minerals in dentin treated with Ag-NPs, after 7 d. Polyhedral or rounded/drop-like, and polymorphic in strata crystal apatite characterized the minerals when undoped-NPs were used, with more crystalline characteristics after 7 d than that found when Ag-NPs were applied. Ag-NPs application did not improve the mechanical performance of dentin and did not produce dentin remineralization. However, energy was dissipated through the dentin without showing stress concentration; contrary was occurring at dentin treated with undoped-NPs, that provoked bridge-like mineral deposits at the dentin surface. CONCLUSIONS: Ag-NPs application did not enhance the mechanical properties of cervical dentin, though the energy dissipation did not damage the dentin structure. Remineralization at dentin was not produced after Ag-NPs application, though improved crystallinity may lead to increase stability of the apatite that was generated at the dentin surface.

Ion-modified nanoparticles induce different apatite formation in cervical dentine.

AIM: To investigate if crystallinity and ultrastructure are modified when cervical dentine is treated with four different nanogels-based solutions for remineralizing purposes. METHODOLOGY: Experimental nanogels based on polymeric nanoparticles (NPs) and zinc, calcium or doxycycline-loaded NPs were applied to citric acid etched dentine to facilitate the occlusion of tubules and the mineralization of the dentine surface. Dentine surfaces were studied by X-ray diffraction and transmission electron microscopy through selected area diffraction and bright-field imaging. RESULTS: Crystals at the dentine surface were identified as hydroxyapatite with the highest crystallographic maturity and crystallite size in dentine treated with Zn-NPs-based gel. Texture increased in all samples from 24 h to 7 days, except in dentine surfaces treated with Zn-NPs gel. Polyhedral, plate-like and drop-like shaped apatite crystals constituted the bulk of minerals in dentine treated with Zn-NPs gel, after 7 days. Polymorphic, cubic and needle-like shaped crystals distinguished minerals, with more amorphous characteristics in dentine treated with Ca-NPs gel after 7 days than that found when Zn-NPs were applied. Doxycycline-NPs produced the smallest crystallites with poor crystallinity, maturity and chemical stability. CONCLUSIONS: Crystalline and amorphous phases of newly formed hydroxyapatite were described in both types of dentine treated with Zn-NPs as well as Ca-NPs gels with multiple shapes of crystallites. Crystal shapes ranged from rounded/drop-like or plate-like crystals to needle-like or polyhedral and cubic apatite appearance.

Effect of particle concentration on the microstructural and macromechanical properties of biocompatible magnetic hydrogels.

We analyze the effect of nanoparticle concentration on the physical properties of magnetic hydrogels consisting of polymer networks of the human fibrin biopolymer with embedded magnetic particles, swollen by a water-based solution. We prepared these magnetic hydrogels by polymerization of mixtures consisting mainly of human plasma and magnetic nanoparticles with OH- functionalization. Microscopic observations revealed that magnetic hydrogels presented some cluster-like knots that were connected by several fibrin threads. By contrast, nonmagnetic hydrogels presented a homogeneous net-like structure with only individual connections between pairs of fibers. The rheological analysis demonstrated that the rigidity modulus, as well as the viscoelastic moduli, increased quadratically with nanoparticle content following a square-like function. Furthermore, we found that time for gel point was shorter in the presence of magnetic nanoparticles. Thus, we can conclude that nanoparticles favor the cross-linking process, serving as nucleation sites for the attachment of the fibrin polymer. Attraction between the positive groups of the fibrinogen, from which the fibrin is polymerized, and the negative OH- groups of the magnetic particle surface qualitatively justifies the positive role of the nanoparticles in the enhancement of the mechanical properties of the magnetic hydrogels. Indeed, we developed a theoretical model that semiquantitatively explains the experimental results by assuming the indirect attraction of the fibrinogen through the attached nanoparticles. Due to this attraction the monomers condense into nuclei of the dense phase and by the end of the polymerization process the nuclei (knots) of the dense phase cross-link the fibrin threads, which enhances their mechanical properties.

Inverse magnetorheological fluids.

We report a new kind of field-responsive fluid consisting of suspensions of diamagnetic (DM) and ferromagnetic (FM) microparticles in ferrofluids. We designate them as inverse magnetorheological (IMR) fluids for analogy with inverse ferrofluids (IFFs). Observations on the particle self-assembly in IMR fluids upon magnetic field application showed that DM and FM microparticles were assembled into alternating chains oriented along the field direction. We explain such assembly on the basis of the dipolar interaction energy between particles. We also present results on the rheological properties of IMR fluids and, for comparison, those of IFFs and bidispersed magnetorheological (MR) fluids. Interestingly, we found that upon magnetic field application, the rheological properties of IMR fluids were enhanced with respect to bidispersed MR fluids with the same FM particle concentration, by an amount greater than the sum of the isolated contribution of DM particles. Furthermore, the field-induced yield stress was moderately increased when up to 30% of the total FM particle content was replaced with DM particles. Beyond this point, the dependence of the yield stress on the DM content was non-monotonic, as expected for FM concentrations decreasing to zero. We explain these synergistic results by two separate phenomena: the formation of exclusion areas for FM particles due to the perturbation of the magnetic field by DM particles and the dipole-dipole interaction between DM and FM particles, which enhances the field-induced structures. Based on the second phenomenon, we present a theoretical model for the yield stress that semi-quantitatively predicts the experimental results.

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.

Shear elasticity of isotropic magnetic gels.

The paper deals with a theoretical study of the effective shear modulus of a magnetic gel, consisting of magnetizable particles randomly and isotropically distributed in an elastic matrix. The effect of an external magnetic field on the composite modulus is the focus of our consideration. We take into account that magnetic interaction between the particles can induce their spatial rearrangement and lead to internal anisotropy of the system. Our results show that, if this magnetically induced anisotropy is insignificant, the applied field reduces the total shear modulus of the composite. Strong anisotropy can qualitatively change the magnetomechanic effect and induce an increase of this modulus with the field.

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.

Stability and magnetic characterization of oleate-covered magnetite ferrofluids in different nonpolar carriers.

This work describes the preparation and stability evaluation of suspensions consisting of hydrophobic magnetite nanoparticles dispersed in different organic solvents. The ferrite particles are covered by a shell of chemisorbed oleate ions following a procedure that is described in detail. The oleate-covered particles were dispersed in different organic solvents with dielectric constants, epsilon(r), ranging between 1.8 and 9, and the centrifugal field strength needed to remove particle aggregates formed during the synthesis was determined for the different liquid carriers used. A thermodynamic analysis demonstrated that the observed stability of the suspensions in liquids with epsilon(r) < 5 is well correlated with the very low lyophobic attraction between the particles. This can easily be surmounted by thermal agitation, since the van der Waals attraction is negligible. In contrast, for liquids with epsilon(r) > 9, the suspensions become unstable because of the combined action of the van der Waals and lyophobic attractions, the latter being dominant for very polar solvents. Finally, a complete magnetic characterization of the oleate-magnetite powder, as well as of several stable ferrofluids prepared with it, was carried out. From this characterization, the magnetic diameters and magnetic moments of the particles immersed in the different liquid carriers were estimated and compared to those corresponding to the dry magnetic particles. This made it possible to estimate the thickness of the nonmagnetic layer on the particles.

A slender-body micromechanical model for viscoelasticity of magnetic colloids: comparison with preliminary experimental data.

The storage modulus, G', together with the yield stress, is an essential quantity characterizing the rheological properties of magnetic field-responsive suspensions (magnetorheological fluids or MRF). In this work, we present both experimental and theoretical results on the viscoelastic properties of MRFs. Two MRFs are used: In one the solid phase consists of cobalt ferrite particles + silica gel, with silicone oil as liquid phase. The second system is formed by carbonyl iron + silica gel also dispersed in silicone oil. The cobalt ferrite particles are synthesized as monodisperse colloidal spheres with an average diameter of 850 nm. We describe a new model based on the slender-body approach for hydrodynamic interactions. The predictions of the model are compared to preliminary experimental G' data obtained in a controlled stress plate-plate rheometer. It is found that the model gives the correct order of magnitude for the highest fields in iron suspensions, but underestimates the experimental results obtained in ferrite ones. In the case of high permeability materials such as carbonyl iron, by the inclusion of high-order multipolar interactions and saturation effects we also predict the order of magnitude of the experimental results. When dealing with low permeability cobalt ferrite based MRFs, other effects, such as remanence (at low fields) and saturation (at high fields), must be considered.

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.

Dynamic characterization of extremely bidisperse magnetorheological fluids.

In this work, we investigate the stability and redispersibility of magnetorheological fluids (MRFs). These are disperse systems where the solid is constituted by ferro- or ferri-magnetic microparticles. Upon the application of external magnetic field, they experience rapid and reversible increases in yield stress and viscosity. The problem considered here is first of all the determination of their stability against sedimentation, an essential issue in their practical application. Although this problem is typically faced through the addition of thixotropic agents to the liquid medium, in this work, we propose the investigation of the effect of magnetic nanoparticles addition, so that the dispersion medium is in reality a ferrofluid. It is found that a volume fraction of nanoparticles not higher than 3% is enough to provide a long-lasting stabilization to MRFs containing above 30% iron microparticles. In the, in fact unavoidable, event of settling, the important point is the ease of redispersion of the sediment. This is indirectly evaluated in the present investigation by measuring the penetration force in the suspension, using a standard hardness needle. Again, it is found that the nanoparticles addition produces soft sediments by avoiding short-range attractions between the large iron particles. Finally, the performance of the designed MRFs is evaluated by obtaining their steady-state rheograms for different volume fractions of magnetite and different magnetic field strengths. The yield stress is found to be strongly field-dependent, and it can achieve the high values expected in standard magnetorheological fluids but with improved stability and redispersibility.

Rheological characterization of human fibrin and fibrin-agarose oral mucosa substitutes generated by tissue engineering.

In regenerative medicine, the generation of biocompatible substitutes of tissues by in vitro tissue engineering must fulfil certain requirements. In the case of human oral mucosa, the rheological properties of tissues deserve special attention because of their influence in the acoustics and biomechanics of voice production. This work is devoted to the rheological characterization of substitutes of the connective tissue of the human oral mucosa. Two substitutes, composed of fibrin and fibrin-agarose, were prepared in cell culture for periods in the range 1-21 days. The time evolution of the rheological properties of both substitutes was studied by two different experimental procedures: steady-state and oscillatory measurements. The former allows the plastic behaviour of the substitutes to be characterized by estimating their yield stress; the latter is employed to quantify their viscoelastic responses by obtaining the elastic (G') and viscous (G'') moduli. The results demonstrate that both substitutes are characterized by a predominant elastic response, in which G' (order 100 Pa) is roughly one order of magnitude larger than G'' (order 10 Pa). But the most relevant insight is the stability, throughout the 21 days of culture time, of the rheological quantities in the case of fibrin-agarose, whereas the fibrin substitute shows a significant hardening. This result provides evidence that the addition to fibrin of a small amount of agarose allows the rheological stability of the oral mucosa substitute to be maintained. This feature, together with its viscoelastic similitude with native tissues, makes this biomaterial appropriate for potential use as a scaffold in regenerative therapies of human oral mucosa.

Description and performance of a fully automatic device for the study of the sedimentation of magnetic suspensions.

In this paper we describe an experimental setup for the automatic determination of the sedimentation behavior of magnetic suspensions (i.e., disperse systems consisting on ferro- or ferri-magnetic particles in a suitable fluid) of arbitrary volume fraction of solids. The device is based on the evaluation of the inductance of a thin coil surrounding the test tube containing the sample. The inductance L is evaluated from the measurement of the resonant frequency of a parallel LC circuit constructed with the coil and a capacitor of known capacitance. The coil can be moved vertically along the tube at specified steps and time intervals, and from the knowledge of L as a function of the vertical position and time, one can get an image of the particle concentration profiles at given instants of time. The performance of the device is tested against suspensions of spherical iron particles in the micrometer size range dispersed in silicone oil, with various initial concentrations of solids. The sedimentation profiles are then compared with the predictions of existing models for the settling of disperse systems of non-interacting particles.

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.

Preparation and sedimentation behavior in magnetic fields of magnetite-covered clay particles.

This work is devoted to the preparation of magnetite-covered clay particles in aqueous medium. For this purpose, magnetite nanoparticles were synthesized by a coprecipitation method. These magnetic particles are adhered to sodium montmorillonite (NaMt) particles in aqueous suspensions of both materials, by appropriate control of the electrolyte concentrations. The best condition to produce such heteroaggregation corresponds to acid pH and approximately 1 mol/L ionic strength, when the electrokinetic potentials (zeta-potential) of both NaMt and Fe3O4 particles have high enough and opposite sign, as demonstrated from electrophoresis measurements. When a layer of magnetite re-covers the clay particles, the application of an external magnetic field induces a magnetic moment in clay-magnetite particles parallel to the external magnetic flux density. The sedimentation behavior of such magnetic particles is studied in the absence or presence of an external magnetic field in a vertical direction. The whole sedimentation behavior is also strongly affected by the formation of big flocculi in the suspensions under the action of internal colloidal interactions. van der Waals and dipole-dipole magnetic attractions between magnetite-covered clay particles dominate the flocculation processes. The different relative orientation of the clay-magnetite particles (edge-to-edge, face-to-edge, and face-to-face) are discussed in order to predict the most favored flocculi configuration.