Enhancing Analytical Performance of (Mg,Fe)3O4/Glassy Carbon Electrodes by Tailoring Chemical Composition of (Mg,Fe)3O4 Nanoparticles.

A series of MgxFe3-xO4 (x ═ 0-1) nanoparticles was synthesized in order to prepare novel MgxFe3-xO4/glassy carbon modified electrodes. Effects of magnesium content (x) on the analytical performance of the modified electrodes in the detection of gallic acid were evaluated. It was found that magnesium concentration and crystallite/particle size of the prepared nanoparticles play significant roles in the sensing properties of modified electrodes. The increase of magnesium concentration up to the value of x ═ 0.4 in MgxFe3-xO4/glassy carbon paste was accompanied by an increase of the corresponding oxidation current of gallic acid. However, further growth of x value caused decline of the obtained oxidation current. An electroanalytical procedure was established, and the analytical performance of the proposed Mg0.4Fe2.6O4/glassy carbon paste electrode was monitored using previously optimized experimental conditions. A working linear range from 1-39 µM gallic acid was obtained with detection limit of 0.29 µM. According to these results, the developed procedure can be applied for detection of low concentrations of gallic acid with satisfactory selectivity in the presence of some common naturally occurring compounds. Experimental results indicate that the developed procedure could be a novel approach in the detection of antioxidant, overcoming some known disadvantages such as passivation, and could be a promising replacement for sophisticated chromatographic methods.

Complementary approaches for the evaluation of biocompatibility of 90Y-labeled superparamagnetic citric acid (Fe,Er)3O4 coated nanoparticles.

Magnetic nanoparticles (MNPs) are of immense interest for diagnostic and therapeutic applications in medicine. Design and development of new iron oxide-based MNPs for such applications is of rather limited breadth without reliable and sensitive methods to determine their levels in body tissues. Commonly used methods, such as ICP, are quite problematic, due to the inability to decipher the origin of the detected iron, i.e. whether it originates from the MNPs or endogenous from tissues and bodily fluids. One of the approaches to overcome this problem and to increase reliability of tracing MNPs is to partially substitute iron ions in the MNPs with Er. Here, we report on the development of citric acid coated (Fe,Er)3O4 nanoparticles and characterization of their physico-chemical and biological properties by utilization of various complementary approaches. The synthesized MNPs had a narrow (6-7nm) size distribution, as consistently seen in atomic pair distribution function, transmission electron microscopy, and DC magnetization measurements. The particles were found to be superparamagnetic, with a pronounced maximum in measured zero-field cooled magnetization at around 90K. Reduction in saturation magnetization due to incorporation of 1.7% Er3+ into the Fe3O4 matrix was clearly observed. From the biological standpoint, citric acid coated (Fe,Er)3O4 NPs were found to induce low toxicity both in human cell fibroblasts and in zebrafish (Danio rerio) embryos. Biodistribution pattern of the MNPs after intravenous administration in healthy Wistar rats was followed by the radiotracer method, revealing that 90Y-labeled MNPs were predominantly found in liver (75.33% ID), followed by lungs (16.70% ID) and spleen (2.83% ID). Quantitative agreement with these observations was obtained by ICP-MS elemental analysis using Er as the detected tracer. Based on the favorable physical, chemical and biological characteristics, citric acid coated (Fe,Er)3O4 MNPs could be further considered for the potential application as a diagnostic and/or therapeutic agent. This work also demonstrates that combined application of these techniques is a promising tool for studies of pharmacokinetics of the new MNPs in complex biological systems.

Synthesis, characterization, cytotoxicity and antiangiogenic activity of copper(II) complexes with 1-adamantoyl hydrazone bearing pyridine rings.

Three novel copper complexes with tridentate N2O ligand di(2-pyridil) ketone 1-adamantoyl hydrazone (Addpy) of the formula [Cu(II)2Cu(I)2(Addpy)2Br2(µ-Br4)] (1), catena-poly[CuCl(µ-Addpy)(µ-Cl)CuCl2]n (2) and [Cu(Addpy)(NCS)2] (3) were synthesized. Complexes are characterized by X-ray crystallography, spectral (UV-Vis, FTIR), electrochemical (CV) analyses, and magnetochemical measurements. Investigation of anticancer potential of Cu(II) complexes, mode of cell death, apoptosis, and inhibition of angiogenesis were performed. All tested malignant cell lines (HeLa, LS174, A549, K562, and MDA-MB-231) showed high sensitivity to the examined Cu(II) complexes. It has been shown that the complexes induce apoptosis in the caspase 3-dependent manner, whereas the anti-angiogenic effects of 1, 2, and 3 have been confirmed in EA.hy926 cells using a tube formation assay.

Preparation and in vivo evaluation of multifunctional 9°Y-labeled magnetic nanoparticles designed for cancer therapy.

Two different types of magnetic nanoparticles (MNPs) were synthesized in order to compare their efficiency as radioactive vectors, Fe3O4-Naked (80 ± 5 nm) and polyethylene glycol 600 diacid functionalized Fe3O4(Fe3O4-PEG600) MNPs (46 ± 0.6 nm). They were characterized based on the external morphology, size distribution, and colloidal and magnetic properties. The obtained specific power absorption value for Fe3O4-PEG600 MNPs was 200 W/g, indicated their potential in hyperthermia based cancer treatments. The labeling yield, in vitro stability and in vivo biodistribution profile of (90) Y-MNPs were compared. Both types of MNPs were (90)Y-labeled in reproducible high yield (>97%). The stability of the obtained radioactive nanoparticles was evaluated in saline and human serum media in order to optimize the formulations for in vivo use. The biodistribution in Wistar rats showed different pharmacokinetic behaviors of nanoparticles: a large fraction of both injected MNPs ended in the liver (14.58%ID/g for (90)Y-Fe3O4-Naked MNPs and 19.61%ID/g for (90)Y-Fe3O4-PEG600 MNPs) whereas minor fractions attained in other organs. The main difference between the two types of MNPs was the higher accumulation of (90)Y-Fe3O4-Naked MNPs in the lungs (12.14%ID/g vs. 2.00%ID/g for (90)Y-Fe3O4-PEG600 MNPs) due to their in vivo agglomeration. The studied radiolabeled magnetic complexes such as (90)Y-Fe3O4-PEG600 MNPs constitute a great promise for multiple diagnostic-therapeutic uses combining, for example, MRI-magnetic hyperthermia and regional radiotherapy.

An integrated study of thermal treatment effects on the microstructure and magnetic properties of Zn-ferrite nanoparticles.

The evolution of the magnetic state, crystal structure and microstructure parameters of nanocrystalline zinc-ferrite, tuned by thermal annealing of ∼4 nm nanoparticles, was systematically studied by complementary characterization methods. Structural analysis of neutron and synchrotron x-ray radiation data revealed a mixed cation distribution in the nanoparticle samples, with the degree of inversion systematically decreasing from 0.25 in an as-prepared nanocrystalline sample to a non-inverted spinel structure with a normal cation distribution in the bulk counterpart. The results of DC magnetization and Mössbauer spectroscopy experiments indicated a superparamagnetic relaxation in ∼4 nm nanoparticles, albeit with different freezing temperatures T(f) of 27.5 K and 46 K, respectively. The quadrupole splitting parameter decreases with the annealing temperature due to cation redistribution between the tetrahedral and octahedral sites of the spinel structure and the associated defects. DC magnetization measurements indicated the existence of significant interparticle interactions among nanoparticles ('superspins'). Additional confirmation for the presence of interparticle interactions was found from the fit of the T(f)(H) dependence to the AT line, from which a value of the anisotropy constant of K(eff) = 5.6 × 10(5) erg cm(-3) was deduced. Further evidence for strong interparticle interactions was found from AC susceptibility measurements, where the frequency dependence of the freezing temperature T(f)(f) was satisfactory described by both Vogel-Fulcher and dynamic scaling theory, both applicable for interacting systems. The parameters obtained from these fits suggest collective freezing of magnetic moments at T(f).