Bismuth labeling for the CT assessment of local administration of magnetic nanoparticles.

Many therapeutic applications of magnetic nanoparticles involve the local administration of nanometric iron oxide based materials as seeds for magnetothermia or drug carriers. A simple and widespread way of controlling the process using x-ray computed tomography (CT) scanners is desirable. The combination of iron and bismuth in one entity will increase the atenuation of x-rays, offering such a possibility. In order to check this possibility core-shell nanocrystals of iron oxide@bismuth oxide have been synthesized by an aqueous route and stabilized in water by polyethylene glycol (PEG), and we have evaluated their ability to generate contrast by CT and magnetic resonance imaging (MRI) to measure the radiopacity and proton relaxivities using phantoms. High-resolution scanning transmission electron microscopy (STEM) revealed that the material consists of a highly crystalline 8 nm core of maghemite and a 1 nm shell of bismuth atoms either isolated or clustered on the nanocrystal's surface. The comparison of µCT and MRI images of mice acquired in the presence of the contrast shows that when local accumulations of the magnetic nanoparticles take place, CT images are more superior in the localization of the magnetic nanoparticles than MRI images, which results in magnetic field inhomogeneity artifacts.

Structural determination of Bi-doped magnetite multifunctional nanoparticles for contrast imaging.

To determine with precision how Bi atoms are distributed in Bi-doped iron oxide nanoparticles their structural characterization has been carried out by X-ray absorption spectroscopy (XAS) recorded at the K edge of Fe and at the L3 edge of Bi. The inorganic nanoparticles are nominally hybrid structures integrating an iron oxide core and a bismuth oxide shell. Fe K-edge XAS indicates the formation of a structurally ordered, non-stoichiometric magnetite (Fe3-δO4) phase for all the nanoparticles. The XAS spectra show that, in the samples synthesized by precipitation in aqueous media and laser pyrolysis, the Bi atoms neither enter into the iron oxide spinel lattice nor form any other mixed Bi-Fe oxides. No modification of the local structure around the Fe atoms induced by the Bi atoms is observed at the Fe K edge. In addition, contrary to expectations, our results indicate that the Bi atoms do not form a well-defined Bi oxide structure. The XAS study at the Bi L3 edge indicates that the environment around Bi atoms is highly disordered and only a first oxygen coordination shell is observed. Indefinite [BiO6-x(OH)x] units (isolated or aggregated forming tiny amorphous clusters) bonded through hydroxyl bridges to the nanoparticle, rather than a well defined Bi2O3 shell, surround the nanoparticle. On the other hand, the XAS study indicates that, in the samples synthesized by thermal decomposition, the Bi atoms are embedded in a longer range ordered structure showing the first and second neighbors.

Functionalisation of glass with iron oxide nanoparticles produced by laser pyrolysis.

In the present work, a new process for depositing nanoparticle layers onto glass has been developed by using one of the most interesting nanoparticle generation technologies at the moment, which is based on the pyrolysis induced by laser of vapours combined with CVD of the particles onto glass. Nanoparticles prepared by this method were deposited into a hot silica substrate obtaining new nanocomposites with unique properties. The coated glasses present new specific functionalities such as colour, and interesting magnetic and optical properties. Control of the thickness and the iron oxide phase, either magnetic or not, has been achieved by adjusting the experimental conditions. Thus, thickness is controlled by the glass and the precursor temperature, while the iron phase is controlled by the precursor temperature and the nature and the flow of the carrier gas. This process is inexpensive, adaptable to current glass production technologies and takes place at atmospheric pressure.

Surface anisotropy broadening of the energy barrier distribution in magnetic nanoparticles.

The effect of surface anisotropy on the distribution of energy barriers in magnetic fine particles of nanometer size is discussed within the framework of the Tln(t/τ(0)) scaling approach. The comparison between the distributions of the anisotropy energy of the particle cores, calculated by multiplying the volume distribution by the core anisotropy, and of the total anisotropy energy, deduced by deriving the master curve of the magnetic relaxation with respect to the scaling variable Tln(t/τ(0)), enables the determination of the surface anisotropy as a function of the particle size. We show that the contribution of the particle surface to the total anisotropy energy can be well described by a size-independent value of the surface energy per unit area which permits the superimposition of the distributions corresponding to the particle core and effective anisotropy energies. The method is applied to a ferrofluid composed of non-interacting Fe(3-x)O(4) particles of 4.9 nm average size and x about 0.07. Even though the size distribution is quite narrow in this system, a relatively small value of the effective surface anisotropy constant K(s) = 2.9 × 10(-2) erg cm(-2) gives rise to a dramatic broadening of the total energy distribution. The reliability of the average value of the effective anisotropy constant, deduced from magnetic relaxation data, is verified by comparing it to that obtained from the analysis of the shift of the ac susceptibility peaks as a function of the frequency.

Stabilization of aluminum hydroxide gel by specifically adsorbed carbonate.

Ion-free aluminum hydroxide gel, prepared by the hydrolysis of aluminum tri-sec-butoxide, was observed by IR, X-ray analysis, and pH-stat titration to undergo rapid structural changes leading to the formation of pseudoboehmite and bayerite. The rate of development of order was directly related to the water-aluminum molar ratio. The Al--O bands at 625 and 470 cm-1 were the most sensitive indicators of the development of order in the gel structure. Direct evidence for the stabilizing effect of specifically adsorbed carbonate was obtained when carbon dioxide was introduced during the hydrolysis of aluminum tri-sec-butoxide. The resulting aluminum hydroxycarbonate gel possessed excellent antacid properties, retained its amorphous nature upon aging, and contained no cations other than aluminum. Hydrolysis of aluminum tri-sec-butoxide in the presence of stoichiometric amounts of sodium bicarbonate resulted in the immediate formation of crystalline sodium aluminum hydroxycarbonate (dawsonite).

Factors affecting homogeneous precipitation of aluminum hydroxide gel.

The variables affecting homogeneous precipitation in the hydrolysis of aluminum nitrate by sodium carbonate were studied. Increased temperature, decreased concentration of reactants, and decreased rate of addition of titrant favor conditions that achieve homogeneous precipitation. During acid hydrolysis, the nitrate anion was the major anion associated with the gel and only small amounts of carbonate were observed. It is recommended that homogeneous conditions be achieved during the precipitation of aluminum hydroxide gel to improve reporducibility.

Mechanism of adsorption of clindamycin and tetracycline by montmorillonite.

IR and X-ray analyses of the interaction of clindamycin with montmorillonite indicate that clindamycin is adsorbed by a cation-exchange mechanism under pH conditions favoring the cationic form of the drug and by physical adsorption when the unionized drug is present. This physical adsorption is relatively weak since the drug is readily desorbed by alkaline washing. Tetracycline is adsorbed by cation exchange at low pH values where the +00 species predominates. Complexation with divalent interlayer cations contributes significantly to adsorption at higher pH values where the +-0 and +-- species exist. In a strongly alkaline solution, the 0-- species was not adsorbed in the interlayer space of montmorillonite but rather produced an external calcium-tetracycline complex. This study illustrates the utility of X-ray and IR analyses in elucidating the mechanisms responsible for clay-drug interactions.

Nature of amorphous aluminum hydroxycarbonate.

The titration of sodium carbonate with aluminum nitrate is shown to produce amorphous aluminum hydroxycarbonate. This compound is not stoichiometric, although the maximum carbonate to aluminum ratio appears to be 0.5. The pH conditions for achieving the maximum carbonate content are concentration dependent. A model for the particle surface at the solution interface is proposed. This model accounts for the presence of carbonate directly coordinated to the aluminum and carbonate adsorbed by electrostatic forces. Sodium is present in the diffuse layer and is, therefore, not an integral part of the structure.

Structural survey of carbonate-containing antacids.

A series of carbonate-containing antacids was examined by IR and X-ray analysis to establish the role of carbonate and to compare the structure of the antacids to naturally occurring carbonate minerals. Based on IR analysis, the relative degree of perturbation of carbonate increases in the order calcium carbonate, carbonate-containing aluminum hydroxide gel, and dihydroxyaluminum sodium carbonate. The crystalline carbonate-containing antacids were poorly organized forms of the minerals calcite, CaCO3; dawsonite, NaAl(OH)2CO3; and hydrotalcite, Mg6Al2CO3(OH)16-4H2O. Amorphous carbonate-containing aluminum hydroxide gel can be classified mineralogically as amorphous aluminum hydroxycarbonate. IR and X-ray evidence indicates that magaldrate has a hydrotalcite-like structure with sulfate as the major interlayer anion and carbonate also present in the interlayer space.