The role of thermal diffusion, particle clusters, hydrodynamic and magnetic forces on the flow behaviour of magneto-polymer composites.

In this paper, we study the shear-induced flow of magneto-polymer composites, consisting of dispersions of magnetic particles in solutions of polymers, as a competition between the colloidal forces amid particles and their bulk transport induced by the hydrodynamic forces. For this aim, we analyse the role of different experimental parameters. Firstly, by using only solutions of a well-known anionic polymer (sodium alginate), we provoke a moderate hindering of particle movement, but keeping the liquid-like state of the samples. On the contrary, a gel-like behaviour is conferred to the samples when a cationic polymer (chitosan) is additionally added, which further reduces the particle movement. We analyse the effect of an applied magnetic field, which is opposed to particle transport by hydrodynamic forces, by inducing magnetic attraction between the particles. We perform the analysis under both stationary and oscillatory shear. We show that by using dimensionless numbers the differences between samples and experimental conditions are emphasized. In all cases, as expected, the transport of particles driven by bulk hydrodynamic forces dominates at high values of the shear rate. This article is part of the theme issue 'Transport phenomena in complex systems (part 1)'.

In vivo time-course biocompatibility assessment of biomagnetic nanoparticles-based biomaterials for tissue engineering applications.

Novel artificial tissues with potential usefulness in local-based therapies have been generated by tissue engineering using magnetic-responsive nanoparticles (MNPs). In this study, we performed a comprehensive in vivo characterization of bioengineered magnetic fibrin-agarose tissue-like biomaterials. First, in vitro analyses were performed and the cytocompatibility of MNPs was demonstrated. Then, bioartificial tissues were generated and subcutaneously implanted in Wistar rats and their biodistribution, biocompatibility and functionality were analysed at the morphological, histological, haematological and biochemical levels as compared to injected MNPs. Magnetic Resonance Image (MRI), histology and magnetometry confirmed the presence of MNPs restricted to the grafting area after 12 weeks. Histologically, we found a local initial inflammatory response that decreased with time. Structural, ultrastructural, haematological and biochemical analyses of vital organs showed absence of damage or failure. This study demonstrated that the novel magnetic tissue-like biomaterials with improved biomechanical properties fulfil the biosafety and biocompatibility requirements for future clinical use and support the use of these biomaterials as an alternative delivery route for magnetic nanoparticles.

Role of particle clusters on the rheology of magneto-polymer fluids and gels.

Even in the absence of cross-linking, at large enough concentration, long polymer strands have a strong influence on the rheology of aqueous systems. In this work, we show that solutions of medium molecular weight (120 000-190 000 g mol-1) alginate polymer retained a liquid-like behaviour even for concentrations as large as 20% w/v. On the contrary, solutions of alginate polymer of larger (and also polydisperse) molecular weight (up to 600 000 g mol-1) presented a gel-like behaviour already at concentrations of 7% w/v. We dispersed micrometre-sized iron particles at a concentration of 5% v/v in these solutions, which resulted in either stable magnetic fluids or gels, depending on the type of alginate polymer employed (medium or large molecular weight, respectively). These magneto-polymer composites presented a shear-thinning behaviour that allowed injection through a syringe and recovery of the original properties afterwards. More interestingly, application of a magnetic field resulted in the formation of particle clusters elongated along the field direction. The presence of these clusters intensely affected the rheology of the systems, allowing a reversible control of their stiffness. We finally developed theoretical modelling for the prediction of the magnetic-sensitive rheological properties of these magneto-polymer colloids. This article is part of the theme issue 'Patterns in soft and biological matters'.

Rheology of magnetic colloids containing clusters of particle platelets and polymer nanofibres.

Magnetic hydrogels (ferrogels) are soft materials with a wide range of applications, especially in biomedicine because (i) they can be provided with the required biocompatibility; (ii) their heterogeneous structure allows their use as scaffolds for tissue engineering; (iii) their mechanical properties can be modified by changing different design parameters or by the action of magnetic fields. These characteristics confer them unique properties for acting as patterns that mimic the architecture of biological systems. In addition, and (iv) given their high porosity and aqueous content, ferrogels can be loaded with drugs and guided towards specific targets for local (non-systemic) pharmaceutical treatments. The ferrogels prepared in this work contain magnetic particles obtained by precipitation of magnetite nanoparticles onto the porous surface of bentonite platelets. Then, the particles were functionalized by adsorption of alginate molecules and dispersed in an aqueous solution of sodium alginate. Finally, the gelation was promoted by cross-linking the alginate molecules with Ca2+ ions. The viscoelastic properties of the ferrogels were measured in the absence/presence of external magnetic fields, showing that these ferrogels exhibited a strong enough magnetorheological effect. This behaviour is explained considering the field-induced strengthening of the heterogeneous (particle-polymer) network generated inside the ferrogel. This article is part of the theme issue 'Patterns in soft and biological matters'.

In vitro characterization of a novel magnetic fibrin-agarose hydrogel for cartilage tissue engineering.

The encapsulation of cells into biopolymer matrices enables the preparation of engineered substitute tissues. Here we report the generation of novel 3D magnetic biomaterials by encapsulation of magnetic nanoparticles and human hyaline chondrocytes within fibrin-agarose hydrogels, with potential use as articular hyaline cartilage-like tissues. By rheological measurements we observed that, (i) the incorporation of magnetic nanoparticles resulted in increased values of the storage and loss moduli for the different times of cell culture; and (ii) the incorporation of human hyaline chondrocytes into nonmagnetic and magnetic fibrin-agarose biomaterials produced a control of their swelling capacity in comparison with acellular nonmagnetic and magnetic fibrin-agarose biomaterials. Interestingly, the in vitro viability and proliferation results showed that the inclusion of magnetic nanoparticles did not affect the cytocompatibility of the biomaterials. What is more, immunohistochemistry showed that the inclusion of magnetic nanoparticles did not negatively affect the expression of type II collagen of the human hyaline chondrocytes. Summarizing, our results suggest that the generation of engineered hyaline cartilage-like tissues by using magnetic fibrin-agarose hydrogels is feasible. The resulting artificial tissues combine a stronger and stable mechanical response, with promising in vitro cytocompatibility. Further research would be required to elucidate if for longer culture times additional features typical of the extracellular matrix of cartilage could be expressed by human hyaline chondrocytes within magnetic fibrin-agarose hydrogels.

Mechanical properties of magnetic gels containing rod-like composite particles.

Magnetic gels (ferrogels) are heterogeneous systems structured at the nanoscale that contains magnetic particles dispersed in three-dimensional networks of polymer chains. In the present work, the magnetic particles were synthesized with a core-shell structure, consisting of sepiolite particles covered by magnetite nanoparticles. These composite particles had a rod-like shape with a high aspect ratio. The obtained sepiolite-magnetite particles showed a high enough susceptibility and saturation magnetization. The magneto-rheological (MR) properties, and the intensity of the MR effect, of aqueous suspensions of the synthesized particles were studied. The particles, functionalized by adsorption of alginate molecules, were imbedded in alginate hydrogels to get homogeneous soft materials. The particles were linked to the polymer chains as the knots in a network and dominated in a great extent the mechanical properties of the materials. After determining the optimal compositions of the ferrogels, their viscoelastic properties were measured in the absence/presence of magnetic fields. The results pointed out that the MR effect provided by the clay-magnetite particles was considerably more intense than those achieved in ferrogels that contain spherical magnetic microparticles. Therefore, the imbedding of rod-shaped magnetic particles in hydrogels allows controlling the mechanical properties in a wider range than in conventional ferrogels. This article is part of the theme issue 'Heterogeneous materials: metastable and non-ergodic internal structures'.

Anisotropic magnetic hydrogels: design, structure and mechanical properties.

Anisotropy is an intrinsic feature of most of the human tissues (e.g. muscle, skin or cartilage). Because of this, there has been an intense effort in the search of methods for the induction of permanent anisotropy in hydrogels intended for biomedical applications. The dispersion of magnetic particles or beads in the hydrogel precursor solution prior to cross-linking, in combination with applied magnetic fields, which gives rise to columnar structures, is one of the most recently proposed approaches for this goal. We have gone even further and, in this paper, we show that it is possible to use magnetic particles as actuators for the alignment of the polymer chains in order to obtain anisotropic hydrogels. Furthermore, we characterize the microstructural arrangement and mechanical properties of the resulting hydrogels. This article is part of a theme issue 'Heterogeneous materials: metastable and non-ergodic internal structures'.

Ex vivo characterization of a novel tissue-like cross-linked fibrin-agarose hydrogel for tissue engineering applications.

The generation of biomaterials with adequate biomechanical and structural properties remains a challenge in tissue engineering and regenerative medicine. Earlier research has shown that nanostructuration and cross-linking techniques improved the biomechanical and structural properties of different biomaterials. Currently, uncompressed and nanostructured fibrin-agarose hydrogels (FAH and NFAH, respectively) have been used successfully in tissue engineering. The aim of this study was to investigate the possibility of improving the structural and biomechanical properties of FAH and NFAH by using 0.25% and 0.5% (v/v) glutaraldehyde (GA) as a cross-linker. These non-cross-linked and cross-linked hydrogels were subjected to structural, rheological and ex vivo biocompatibility analyses. Our results showed that GA cross-linking induced structural changes and significantly improved the rheological properties of FAH and NFAH. In addition, ex vivo biocompatibility analyses demonstrated viable cells in all conditions, although viability was more compromised when 0.5% GA was used. Our study demonstrates that it is possible to control fiber density and hydrogel porosity of FAH and NFAH by using nanostructuration or GA cross-linking techniques. In conclusion, hydrogels cross-linked with 0.25% GA showed promising structural, biochemical and biological properties for use in tissue engineering.

Biocompatible magnetic core-shell nanocomposites for engineered magnetic tissues.

The inclusion of magnetic nanoparticles into biopolymer matrixes enables the preparation of magnetic field-responsive engineered tissues. Here we describe a synthetic route to prepare biocompatible core-shell nanostructures consisting of a polymeric core and a magnetic shell, which are used for this purpose. We show that using a core-shell architecture is doubly advantageous. First, gravitational settling for core-shell nanocomposites is slower because of the reduction of the composite average density connected to the light polymer core. Second, the magnetic response of core-shell nanocomposites can be tuned by changing the thickness of the magnetic layer. The incorporation of the composites into biopolymer hydrogels containing cells results in magnetic field-responsive engineered tissues whose mechanical properties can be controlled by external magnetic forces. Indeed, we obtain a significant increase of the viscoelastic moduli of the engineered tissues when exposed to an external magnetic field. Because the composites are functionalized with polyethylene glycol, the prepared bio-artificial tissue-like constructs also display excellent ex vivo cell viability and proliferation. When implanted in vivo, the engineered tissues show good biocompatibility and outstanding interaction with the host tissue. Actually, they only cause a localized transitory inflammatory reaction at the implantation site, without any effect on other organs. Altogether, our results suggest that the inclusion of magnetic core-shell nanocomposites into biomaterials would enable tissue engineering of artificial substitutes whose mechanical properties could be tuned to match those of the potential target tissue. In a wider perspective, the good biocompatibility and magnetic behavior of the composites could be beneficial for many other applications.

Generation and Characterization of Novel Magnetic Field-Responsive Biomaterials.

We report the preparation of novel magnetic field-responsive tissue substitutes based on biocompatible multi-domain magnetic particles dispersed in a fibrin-agarose biopolymer scaffold. We characterized our biomaterials with several experimental techniques. First we analyzed their microstructure and found that it was strongly affected by the presence of magnetic particles, especially when a magnetic field was applied at the start of polymer gelation. In these samples we observed parallel stripes consisting of closely packed fibers, separated by more isotropic net-like spaces. We then studied the viability of oral mucosa fibroblasts in the magnetic scaffolds and found no significant differences compared to positive control samples. Finally, we analyzed the magnetic and mechanical properties of the tissue substitutes. Differences in microstructural patterns of the tissue substitutes correlated with their macroscopic mechanical properties. We also found that the mechanical properties of our magnetic tissue substitutes could be reversibly tuned by noncontact magnetic forces. This unique advantage with respect to other biomaterials could be used to match the mechanical properties of the tissue substitutes to those of potential target tissues in tissue engineering applications.

Effect of the hydration on the biomechanical properties in a fibrin-agarose tissue-like model.

The effect of hydration on the biomechanical properties of fibrin and fibrin-agarose (FA) tissue-like hydrogels is reported. Native hydrogels with approximately 99.5% of water content and hydrogels with water content reduced until 90% and 80% by means of plastic compression (nanostructuration) were generated. The biomechanical properties of the hydrogels were investigated by tensile, compressive, and shear tests. Experimental results indicate that nanostructuration enhances the biomechanical properties of the hydrogels. This improvement is due to the partial draining of the water that fills the porous network of fibers that the plastic compression generates, which produces a denser material, as confirmed by scanning electron microscopy. Results also indicate that the characteristic compressive and shear parameters increase with agarose concentration, very likely due to the high water holding capacity of agarose, which reduces the compressibility and gives consistency to the hydrogels. However, results of tensile tests indicate a weakening of the hydrogels as agarose concentration increases, which evidences the anisotropic nature of these biomaterials. Interestingly, we found that by adjusting the water and agarose contents it is possible to tune the biomechanical properties of FA hydrogels for a broad range, within which the properties of many native tissues fall.

Optimizing the magnetic response of suspensions by tailoring the spatial distribution of the particle magnetic material.

We report an experimental enhancement of the magnetic susceptibility of suspensions of particles that is related to the spatial distribution of the magnetic phase in the particles. At low field, the susceptibility of suspensions of nickel-coated diamagnetic spheres was approximately 75% higher than that of suspensions of solid nickel spheres with the same nickel content. This result was corroborated by magnetostatics theory and simulation. The distribution of the magnetic phase in a shell also led to an improvement of the field-induced rheological response of the suspensions.

Cryopreservation of an artificial human oral mucosa stroma. A viability and rheological study.

The aim of this study was to evaluate the viability and biomechanical properties of artificial human oral mucosa stroma (HOMS) subjected to cryopreservation with different cryoprotectant solutions. Artificial HOMS based on a fibrin-agarose matrix with human gingival fibroblasts cultured 7 days in vitro were cryopreserved with three cryoprotectant solutions: (A) TC-199 Medium, DMSO 15%, albumin; (B) DMEM, FCS, DMSO 10%; (C) QC Medium, glycerol. As controls, artificial HOMS not subjected to cryopreservation (CF) and HOMS cryopreserved without cryoprotectant solution (CS) were used. Histological analysis by light microscopy showed that solutions A and B preserved a pattern of porosity similar to values in CF. Based on the number of intact cells in the fibrin-agarose matrix, substitutes preserved with solution B showed the best results. Cell proliferation detected with PCNA immunochemical methods showed that the cell proliferation index was highest in substitutes cryopreserved with solution B. The reculture method and cell viability analyses with Live & Dead(®) revealed increased number of viable in cells preserved with solution B. Artificial stroma substitutes in CS control samples showed the greatest alterations in microstructure and cell proliferation. Analysis of the biomechanical properties showed that substitutes cryopreserved with different solutions had adequate rheological parameters (yield stress, elastic modulus and viscous modulus) and were therefore suitable for use in regenerative medicine. These results establish effective methods of cryopreservation for all experimental situations and suggest that solution B (DMEM, FCS, DMSO 10%) was the best cryoprotectant for the cryopreservation of an artificial oral human mucosa substitute based on a fibrin-agarose matrix.

Colloids on the frontier of ferrofluids. Rheological properties.

This paper is devoted to the steady-state rheological properties of two new kinds of ferrofluids. One of these was constituted by CoNi nanospheres of 24 nm in diameter, whereas the other by CoNi nanofibers of 56 nm in length and 6.6 nm in width. These ferrofluids were subjected to shear rate ramps under the presence of magnetic fields of different intensity, and the corresponding shear stress values were measured. From the obtained rheograms (shear stress vs shear rate curves) the values of both the static and the dynamic yield stresses were obtained as a function of the magnetic field. The magnetoviscous effect was also obtained as a function of both the shear rate and the magnetic field. The experimental results demonstrate that upon magnetic field application these new ferrofluids develop yield stresses and magnetoviscous effects much greater than those of conventional ferrofluids, based on nanospheres of approximately 10 nm in diameter. Besides some expected differences, such as the stronger magnetorheological effect in the case of ferrofluids based on nanofibers, some intriguing differences are found between the rheological behaviors of nanofiber ferrofluids and nanosphere ferrofluid. First, upon field application the rheograms of nanofiber ferrofluids present N-shaped dependence of the shear stress on the shear rate. The decreasing part of the rheograms takes place at low shear rate. These regions of negative differential viscosity, and therefore, unstable flow is not observed in the case of nanosphere ferrofluids. The second intriguing difference concerns the curvature of the yield stress vs magnetic field curves. This curvature is negative in the case of nanosphere ferrofluid, giving rise to saturation of the yield stress at medium field, as expected. However, in the case of nanofiber ferrofluid this curvature is positive, which means a faster increase of the yield stress with the magnetic field the higher the magnitude of the latter. These interesting differences may be due to the existence of strong interparticle solid friction in the case of nanofiber ferrofluids. Finally, theoretical models for the static yield stress of the ferrofluids were developed. These models consider that upon field application the ferrofluid nanoparticles are condensed in drops of dense phase. These drops tend to be aligned along the field direction, opposing the flow of the ferrofluids and being responsible for the static quasielastic deformation and the yield-stress phenomena. By considering the existence of interparticle dry friction only in the case of nanofiber ferrofluids, the developed models predicted quite well not only the magnitude of the static yield stress but also the differences in curvature of the yield stress vs magnetic field curves.

Stability and magnetorheological behaviour of magnetic fluids based on ionic liquids.

This paper reports the preparation of magnetic fluids consisting of magnetite nanoparticles dispersed in an ionic liquid. Different additives were used in order to stabilize the fluids. Colloidal stability was checked by magnetic sedimentation, centrifugation and direct observation. The results of these tests showed that a true ferrofluid was only obtained when the nanoparticles were coated with a layer of surfactant compatible with the ionic liquid. These experiments also showed that stability could not be reached just by electrostatic repulsion. The conclusions of the stability tests were confirmed by calculations of the interparticle energies of interaction. The rheological behaviour of the magnetic fluids upon magnetic field application was also investigated. The experimental magnetoviscous response was fitted by a microstructural model. The model considered that the fluids consisted of two populations of particles, one with a magnetic core diameter of 9 nm, and another with a larger diameter. Upon field application chain-like structures are supposed to be induced. According to estimations particles of 9 nm are too small to aggregate upon field application. The results of the calculations showed that the intensity of the magnetoviscous response depends on the concentration and size of the large particles, and on the thickness of the surfactant layers.

Steric repulsion as a way to achieve the required stability for the preparation of ionic liquid-based ferrofluids.

With this work we would like to emphasize the necessity of steric repulsion to stabilize novel ionic liquid-based ferrofluids. For this purpose, we prepared a suspension of magnetite nanoparticles coated with a double layer of oleic acid, dispersed in 1-ethyl-3-methylimidazolium ethylsulphate ([EMIM][EtSO(4)]). For comparison, a suspension of bare magnetite nanoparticles in [EMIM][EtSO(4)] was also prepared. The stability of these suspensions was checked by magnetic sedimentation and centrifugation processes. Furthermore, their yield stress was measured as a function of the applied magnetic field, which gave additional information on their stability. The results of these experiments showed that the suspension of bare nanoparticles was rather unstable, whereas the suspension of double layer coated nanoparticles gave rise to a true (stable) ferrofluid.

Effect of polar interactions on the magnetorheology of silica-coated magnetite suspensions in oil media.

This work deals with the role of nonmagnetic interactions on the magnetorheological (MR) response of suspensions of magnetic particles in nonaqueous carriers (MR fluids). Although electrostatic interactions between particles are negligible, van der Waals and, eventually, polar forces might be present. Nevertheless, they are typically neglected when compared to magnetic or hydrodynamic ones. In order to perform a comparative evaluation of the contributions of these interactions, we carried out an MR investigation on two samples of silica-coated magnetite: one (MagSilica 50-H8) is hydrophobic and the other (MagSilica 50-85) is hydrophilic. We describe a careful surface thermodynamic characterization of the two kinds of silicas, confirming their very different hydrophobicities. MR measurements show that only the suspensions of 50-85 particles change from Newtonian to pseudoplastic when a magnetic field is applied, with a yield stress increasing with field strength H, and saturating when H approximately = 100 kA/m. The experimental values of yield stress are compared to theoretical predictions based on the chain model, and it is found that the theory overestimates the experimental values. It is suggested that the nonnegligible interfacial interactions are responsible for both the absence of MR effect in 50-H8 samples and the low yield stress in 50-85 suspensions.

Preparation and characterization of iron-based magnetorheological fluids stabilized by addition of organoclay particles.

Suspensions of micrometer-sized iron particles (10 vol %) dispersed in kerosene and stabilized by addition of organoclay particles were prepared. The magnetization curves of these suspensions were measured, and their sedimentation and redispersion behaviors were analyzed as a function of clay concentration by means of optical and rheological methods. Furthermore, their magnetorheological properties were investigated using a controlled rate magnetorheometer and the effect of clay concentration on these properties was also analyzed. These experiments showed that the addition of clay slows down iron particle settling and eases the redispersion of the iron-based suspensions without masking their magnetorheological properties. Two mechanisms were found to be involved in this behavior: (i) the formation of a clay gel network and (ii) the presence of heterogeneous iron-clay adhesion.