The unpredictable carbon nanotube biocorona and a functionalization method to prevent protein biofouling.

BACKGROUND: The intrinsic physicochemical properties of carbon nanotubes (CNTs) make them unique tools in nanotechnology. Their elemental composition, resilience, thermal properties, and surface reactivity make CNTs also of undisputed interest in biotechnology. In particular, their extraordinary ability to capture biomolecules on their surface makes them essential in this field. The proteins adsorbed on the CNTs create a biological coating that endows them the ability to interact with some cell receptors, penetrate membranes or interfere with cell biomechanics, thus behaving as an active bio-camouflage. But some of these proteins unfold, triggering an immune response that unpredictably changes the biological activity of CNTs. For this reason, the control of the biocorona is fundamental in the nanobiotechnology of CNTs. RESULTS: Using TEM and AFM here we demonstrate a significant increase in CNTs diameter after protein functionalization. A quantitative analysis using TGA revealed that between 20 and 60% of the mass of functionalized nanotubes corresponds to protein, with single-walled CNTs capturing the highest amounts. To qualitatively/quantitatively characterize these biocoatings, we studied the biochemical "landscape" of the proteins captured by the different nanotubes after functionalization under various conditions. This study revealed a significant variability of the proteins in the corona as a function of the type of nanotube, the functionalization temperature, or the time after exposure to serum. Remarkably, the functionalization of a single type of CNT with sera from various human donors also resulted in different protein landscapes. Given the unpredictable assortment of proteins captured by the corona and the biological implications of this biocoating, we finally designed a method to genetically engineer and produce proteins to functionalize nanotubes in a controlled and customizable way. CONCLUSIONS: We demonstrate the high unpredictability of the spontaneous protein corona on CNTs and propose a versatile functionalization technique that prevents the binding of nonspecific proteins to the nanotube to improve the use of CNTs in biomedical applications.

Magnetic Microwires with Unique Combination of Magnetic Properties Suitable for Various Magnetic Sensor Applications.

There is a pressing demand to improve the performance of cost-effective soft magnetic materials for use in high performance sensors and devices. Giant Magneto-impedance effect (GMI), or fast single domain wall (DW) propagation can be observed in properly processed magnetic microwires. In this paper we have identified the routes to obtain microwires with unique combination of magnetic properties allowing observation of fast and single DW propagation and GMI effect in the same microwire. By modifying the annealing conditions, we have found the appropriate regimes allowing achievement of the highest GMI ratio and the fastest DW dynamics. The observed experimental results are discussed considering the radial distribution of magnetic anisotropy and the correlation of GMI effect, and DW dynamics with bulk and surface magnetization processes. Studies of both Fe- and Co-rich microwires, using the magneto-optical Kerr effect, MOKE, provide information on the magnetic structure in the outer shell of microwires. We have demonstrated the existence of the spiral helical structure in both studied microwires. At the same time, torsion mechanical stresses induce helical bistability in the same microwires, which allow us to consider these microwires as materials suitable for sensors based on the large Barkhausen jump.

Review of Domain Wall Dynamics Engineering in Magnetic Microwires.

The influence of magnetic anisotropy, post-processing conditions, and defects on the domain wall (DW) dynamics of amorphous and nanocrystalline Fe-, Ni-, and Co-rich microwires with spontaneous and annealing-induced magnetic bistability has been thoroughly analyzed, with an emphasis placed on the influence of magnetoelastic, induced and magnetocrystalline anisotropies. Minimizing magnetoelastic anisotropy, either by the selection of a chemical composition with a low magnetostriction coefficient or by heat treatment, is an appropriate route for DW dynamics optimization in magnetic microwires. Stress-annealing allows further improvement of DW velocity and hence is a promising method for optimization of DW dynamics in magnetic microwires. The origin of current-driven DW propagation in annealing-induced magnetic bistability is attributed to magnetostatic interaction of outer domain shell with transverse magnetization orientation and inner axially magnetized core. The beneficial influence of the stress-annealing on DW dynamics has been explained considering that it allows increasing of the volume of outer domain shell with transverse magnetization orientation at the expense of decreasing the radius of inner axially magnetized core. Such transverse magnetic anisotropy can similarly affect the DW dynamics as the applied transverse magnetic field and hence is beneficial for DW dynamics optimization. Stress-annealing allows designing the magnetic anisotropy distribution more favorable for the DW dynamics improvement. Results on DW dynamics in various families of nanocrystalline microwires are provided. The role of saturation magnetization on DW mobility improvement is discussed. The DW shape, its correlation with the magnetic anisotropy constant and the microwire diameter, as well as manipulation of the DW shape by induced magnetic anisotropy are discussed. The engineering of DW propagation through local stress-annealing and DW collision is demonstrated.

Development of an accurate method for dispersion and quantification of carbon nanotubes in biological media.

Understanding the biological effects triggered by nanomaterials is crucial, not only in nanomedicine but also in toxicology. The dose-response relation is relevant in biological tests due to its use for determining appropriate dosages for drugs and toxicity limits. Carbon nanotubes can trigger numerous unusual biological effects, many of which could have unique applications in biotechnology and medicine. However, their resuspension in saline solutions and the accurate determination of their concentration after dispersion in biological media are major handicaps to identify the magnitude of the response of organisms as a function of this exposure. This difficulty has led to inconsistent results and misinterpretations of their in vivo behavior, limiting their potential use in nanomedicine. The lack of a suitable protocol that allows comparing different studies of the content of carbon nanotubes and their adequate resuspension in culture cell media gives rise to this study. Here, we describe a methodology to functionalize, resuspend and determine the carbon nanotube concentration in biocompatible media based on UV-Vis spectroscopy. This method allows us to accurately estimate the concentration of these resuspended carbon nanotubes, after removing bundles and micrometric aggregates, which can be used as a calibration standard, for dosage-dependent studies in biological systems. This method can also be extended to any other nanomaterial to properly quantify the actual concentration.

Magnetoimpedance Response and Field Sensitivity in Stress-Annealed Co-Based Microwires for Sensor Applications.

Amorphous soft magnetic microwires have attracted much attention in the area of sensor applications due to their excellent properties. In this work, we study the influence of annealing treatments (stress and conventional) in the giant magnetoimpedance (GMI) response and the field sensitivity of the soft magnetic Co69.2Fe3.6Ni1B12.5Si11Mo1.5C1.2 glass-coated microwires. Here we report a remarkable and simultaneous enhancement of GMI effect and field sensitivity. The highest sensitivity of 104%/Oe and the GMI response of 234% were achieved for 300 °C stress-annealed samples at 472 and 236 MPa, respectively. Additionally, we found that stress-annealed microwires exhibit a frequency dependence on maximal GMI response and field sensitivity. These findings are obtained by fine-tuning their magnetoeslastic anisotropies through stress-annealing treatments of as-prepared microwires at the proper temperature and axial applied stress upon annealing. We hope that the results presented here widen the scope of investigations for the future design of soft magnetic materials for sensor purposes.

Optimization of magnetic properties and GMI effect of Thin Co-rich Microwires for GMI Microsensors.

Magnetic microwires can present excellent soft magnetic properties and a giant magnetoimpedance effect. In this paper, we present our last results on the effect of postprocessing allowing optimization of the magnetoimpedance effect in Co-rich microwires suitable for magnetic microsensor applications. Giant magnetoimpedance effect improvement was achieved either by annealing or stress-annealing. Annealed Co-rich presents rectangular hysteresis loops. However, an improvement in magnetoimpedance ratio is observed at fairly high annealing temperatures over a wide frequency range. Application of stress during annealing at moderate values of annealing temperatures and stress allows for a remarkable decrease in coercivity and increase in squareness ratio and further giant magnetoimpedance effect improvement. Stress-annealing, carried out at sufficiently high temperatures and/or stress allowed induction of transverse magnetic anisotropy, as well as magnetoimpedance effect improvement. Enhanced magnetoimpedance ratio values for annealed and stress-annealed samples and frequency dependence of the magnetoimpedance are discussed in terms of the radial distribution of the magnetic anisotropy. Accordingly, we demonstrated that the giant magnetoimpedance effect of Co-rich microwires can be tailored by controlling the magnetic anisotropy of Co-rich microwires, using appropriate thermal treatment.

Development of Magnetic Microwires for Magnetic Sensor Applications.

Thin magnetic wires can present excellent soft magnetic properties (with coercivities up to 4 A/m), Giant Magneto-impedance effect, GMI, or rectangular hysteresis loops combined with quite fast domain wall, DW, propagation. In this paper we overview the magnetic properties of thin magnetic wires and post-processing allowing optimization of their magnetic properties for magnetic sensor applications. We concluded that the GMI effect, magnetic softness or DW dynamics of microwires can be tailored by controlling the magnetoelastic anisotropy of as-prepared microwires or controlling their internal stresses and domain structure by appropriate thermal treatment.