I.V. Byzov

Effects of Copper(II) Ions and Copper Oxide Nanoparticles on Elodea densa Planch.

Effects of copper ions and copper oxide nanoparticles on lipid peroxidation rate, activities of anti-oxidant enzymes (superoxide dismutase, catalase, and peroxidase), and photosynthesis have been studied in experiments with Elodea densa Planch. The results show that nanoparticles are more actively accumulated by plants. Both copper ions and nanoparticles activate lipid peroxidation (to 120 and 180% of the control level, respectively). Catalase and superoxide dismutase activities in plants treated with nanoparticles increase by a factor of 1.5–2.0. Copper ions suppress photosynthesis at a concentration of 0.5 mg/l, whereas nanoparticles produce such an effect only at 1.0 mg/l. The observed effects of different forms of copper on E. densa are discussed in a comparative aspect.

Magnetic field-enhanced sedimentation of nanopowder magnetite in water flow

Sedimentation dynamics of magnetite (γ-Fe3O4) nanopowder (10–20 nm) in water in a gradient magnetic field Bmax = 0.3 T, (dB/dz)max = 0.13 T/cm was studied for different water flow speeds and starting particle concentrations (0.1 and 1.0 g/l). The aggregates formation in water was monitored under the same conditions. In cyclical water flow, the velocity of particle sedimentation increases significantly in comparison to its rate in still water, which corresponds to the intensified aggregate formation. However, at a water flow speed more than 0.1 cm/s sedimentation velocity slows down, which might be connected to aggregate destruction in a faster water flow. Correlation between sedimentation time and the nanoparticle concentration in water does not follow the trend expected for spherical superparamagnetic particles. In our case sedimentation time is shorter for c = 0.1 g/l in comparison with that for c = 1 g/l. We submit that such a feature is caused by particle self-organization in water into complex structures of fractal type. This effect is unexplained in the framework of existing theoretical models of colloids systems, so far. Provisional recommendations are suggested for the design of a magnetic separator on the permanent magnets base. The main device parameters are magnetic field intensity B ≥ 0.1 T, magnetic field gradient (dB/dz)max ≈ (0.1–0.2) T/cm, and water flow speed V < 0.15 cm/s. For particle concentration c = 1 g/l, purification of water from magnetite down to ecological and hygienic standards is reached in 80 min, for c = 0.1 g/l the time is reduced down to 50 min.

Heterogeneous magnetic state in nanocrystalline cupric oxide CuO

This paper presents the results of investigations of the structural state and magnetic properties of nanocrystalline cupric oxide samples with average particle sizes of approximately 40 and 13 nm, which were synthesized by the electric explosion and gas phase methods, respectively. The samples have been studied using X-ray diffraction, neutron diffraction, magnetic measurements, high-resolution transmission electron microscopy, and copper nuclear magnetic resonance. It has been shown that, in the initial state, regardless of the synthesis method, CuO nanoparticles are characterized by a heterogeneous magnetic state, i.e., by the existence of long-range antiferromagnetic order, spontaneous magnetization, especially at low temperatures, and paramagnetic centers in the material. The ferromagnetic contribution is probably caused by the formation of magnetic polaron states due to the phase separation induced in the system by excess charge carriers as a result of the existence of point defects (vacancies in the anion sublattice) in the nanocrystalline state. In this state, there is an inhomogeneously broadened nuclear magnetic resonance spectrum, which is a superposition of the spectrum of the initial antiferromagnetic matrix and the spectrum of ferromagnetically ordered regions. At high concentrations of ferromagnetically ordered regions, the antiferromagnetic matrix exhibits a nuclear magnetic resonance spectrum of CuO nanoparticles, predominantly from regions with the ferromagnetic phase. The appearance of magnetization can also be partly due to the frustration of spins in CuO, and this state is presumably localized near the most imperfect surface of the nanoparticles. The magnetic susceptibility of nanoparticles in the initial state in strong magnetic fields is significantly higher than that for the annealed samples, which, most likely, is associated with the influence of the high concentration of magnetic polarons. No correlation between the ferromagnetic contribution and the size of particles is found. In the CuO samples annealed at 400°C in air, when the average size of CuO nanoparticles remains unchanged, the ferromagnetic contribution completely disappears, and the magnetic behavior of the nanoparticles becomes qualitatively similar to the magnetic behavior of bulk CuO.

Application of NMR relaxometry for determining the concentration of nanopowder magnetite in aqueous media

The use of the effect of a decrease in the transverse relaxation time T2 of the NMR signal of water protons in the presence of magnetic particles has been suggested for the quantitative estimation of the concentration of magnetite (Fe3O4) nanopowder in water. A calibration dependence of the relaxivity T2−1 on the iron concentration has been obtained for model suspensions of magnetite nanoparticles with sizes of approximately 20 nm in the concentration range of 0.15–70 mg/L. For comparison, the concentration dependences of T2−1 for aqueous solutions of Fe(NO3)3 · 9H2O and FeSO4 · 7H2O and paramagnetic salts Ni(NO3)2 · 9H2O, Cr(NO3)3 · 9H2O, and CuSO4 · 5H2O have been studied to show that they correlate with their paramagnetic susceptibilities.

Anomalous magnetism of the nanocrystalline oxide TiO2 surface

The magnetic properties of an oxygen-deficient nanocrystalline undoped titanium dioxide synthesized by the gas-phase, electric-explosion, and chemical method have been studied. The defect state was controlled using reduction treatments in vacuum or in a hydrogen atmosphere. It is shown that the defect state of the surface of nanocrystalline oxides (for example, the existence of vacancies in the anion sublattice and other defects) has a dominant influence on the formation of the magnetic properties of the samples under study. The main contributions to the magnetism of TiO2 nanoparticles after the reduction treatments are the paramagnetic contribution of the matrix, the paramagnetic Curie–Weiss contribution, and the contribution of the spontaneous magnetic moment provided by the existence of regions with different spin ordering. A heterogeneous magnetic state is found to exist in the TiO2 nanopowders; for example, at low temperatures, shifted hysteresis loops are observed as a result of a possible set of magnetic states with different spin orders. It is shown that a soft compaction or grinding of nanopowders in an agate mortar lead to substantial increase in the magnetization, sometimes, by a factor of more than two, regardless of the nanopowder synthesis method and the initial phase state of TiO2 (anatase or rutile structures). This experimental fact proves the key role of the surface defects and the magnetic moment carriers with different spin configurations localized mainly on the nanoparticle surface. The compaction changes the magnetization only in the case when the initial magnetic state has a nonlinear “quasi-superparamagnetic” character of the magnetization curve. As a result of predominant exchange interaction between the nanoparticles with a frustrated character of spin ordering on the nanoparticles surface, the ferromagnetic contribution increases as nanoparticles contact.