Exposure studies of core-shell Fe/Fe(3)O(4) and Cu/CuO NPs to lettuce (Lactuca sativa) plants: Are they a potential physiological and nutritional hazard?

Iron and copper nanomaterials are widely used in environmental remediation and agriculture. However, their effects on physiological parameters and nutritional quality of terrestrial plants such as lettuce (Lactuca sativa) are still unknown. In this research, 18-day-old hydroponically grown lettuce seedlings were treated for 15 days with core-shell nanoscale materials (Fe/Fe(3)O(4), Cu/CuO) at 10 and 20mg/L, and FeSO(4)·7H(2)O and CuSO(4)·5H(2)O at 10mg/L. At harvest, Fe, Cu, micro and macronutrients were determined by ICP-OES. Also, we evaluated chlorophyll content, plant growth, and catalase (CAT) and ascorbate peroxidase (APX) activities. Our results showed that iron ions/NPs did not affect the physiological parameters with respect to water control. Conversely, Cu ions/NPs reduced water content, root length, and dry biomass of the lettuce plants. ICP-OES results showed that nano-Cu/CuO treatments produced significant accumulation of Cu in roots compared to the CuSO(4)·5H(2)O treatment. In roots, all Cu treatments increased CAT activity but decreased APX activity. In addition, relative to the control, nano-Cu/CuO altered the nutritional quality of lettuce, since the treated plants had significantly more Cu, Al and S but less Mn, P, Ca, and Mg.

Evidence of low-temperature superparamagnetism in Mn3O4 nanoparticle ensembles.

Using ac-susceptibility, dc-magnetization, and transmission electron microscopy, we have investigated the magnetic behavior of Mn(3)O(4) nanoparticle ensembles at temperatures below the paramagnetic-to-ferrimagnetic transition of the title material (T(N) approximately equal 41 K). Our data show no evidence of the complex magnetic ordering exhibited by bulk Mn(3)O(4), or of a magnetic behavior around T(N) that has a dynamic (relaxation) origin. Instead, we find a low-temperature (at approximately 11 K) magnetic anomaly that manifests itself as a peak in the out-of-phase component of the ac-susceptibility. Analysis of the frequency and average-particle-size dependence of the peak temperature demonstrates that this behavior is due to the onset of superparamagnetic relaxation, and not to a previously hinted at spin-glass-like transition. Indeed, the relative peak temperature variation per frequency decade DeltaT/TDeltalog(f) is 0.11, an order of magnitude larger than the value expected for collective spin freezing, but within the range of values observed for superparamagnetic blocking. Furthermore, attempts to fit the frequency f/observation time tau = 1/2pif dependence of the peak temperature by a power law led to parameter values unexpected for a spin-glass transition. On the other hand, a Vogel-Fulcher law tau = tau(0)exp[E(B)/k(B)(T - T(0))]-where E(B) is the energy barrier to magnetization reversal, k(B) is the Boltzmann constant, tau(0) and T(0) are constants related to the attempt frequency and the interparticle interaction strength-correctly describes the peak shift and yields values consistent with the superparamagnetic behavior of a slightly interacting system of nanoparticles. In addition, the peak temperature T is sensitive to minute changes in the average particle size (D), and scales as (T - T(0) is proportional to(D)3, another signature of superparamagnetic relaxation.

Microwave Assisted Synthesis of Iron(III) Oxyhydroxides/Oxides Characterized Using Transmission Electron Microscopy, X-ray Diffraction, and X-ray Absorption Spectroscopy.

Microwave assisted synthesis of iron oxide/oxyhydroxide nanophases was conducted using iron(III) chloride titrated with sodium hydroxide at seven different temperatures from 100 degrees C to 250 degrees C with pulsed microwaves. From the XRD results, it was determined that there were two different phases synthesized during the reactions which were temperature dependent. At the lower temperatures, 100 degrees C and 125 degrees C, it was determined that an iron oxyhydroxide chloride was synthesized. Whereas, at higher temperatures, at 150 degrees C and above, iron(III) oxide was synthesized. From the XRD, we also determined the FWHM and the average size of the nanoparticles using the Scherrer equation. The average size of the nanoparticles synthesized using the experimental conditions were 17, 21, 12, 22, 26, 33, 28 nm, respectively for the reactions from 100 degrees C to 250 degrees C. The particles also had low anisotropy indicating spherical nanoparticles, which was later confirmed using TEM. Finally, XAS studies show that the iron present in the nanophase was present as iron(III) coordinated to six oxygen atoms in the first coordination shell. The higher coordination shells also conform very closely to the ideal or bulk crystal structures.

Phase separation and size effects in Pr(0.70)Ba(0.30)MnO(3+δ) perovskite manganites.

The crystal structure and magnetotransport properties of the A-site ionic ordered state in Pr(0.70)Ba(0.30)MnO(3+δ) (δ = 0, 0.025) have been investigated. It is shown that such a state can be formed in complex manganites with cation ratios [Formula: see text] by using a 'two-step' reduction-reoxidization method. The parent A-site ionic disordered Pr(0.70)Ba(0.30)MnO(3+δ) (δ = 0) compound is an orthorhombic (SG = Imma, Z = 4) ferromagnet with Curie temperature T(C)≈173 K and ground-state spontaneous magnetic moment σ(S)∼3.70 µ(B)/f.u. It exhibits two metal-insulator transitions, at T(I)∼128 K and T(II)∼173 K, as well as two peaks of magnetoresistance ∼74% and ∼79% in a field of 50 kOe. The parent A-site ionic disordered Pr(0.70)Ba(0.30)MnO(3+δ) (δ = 0) sample used in our studies has an average grain size [Formula: see text]. Successive annealing of this sample in vacuum P[O(2)]≈10(-4) Pa and then in air at T = 800 °C leads to the destruction of its initial grain structure and to its chemical separation into two phases: (i) oxygen stoichiometric A-site ordered PrBaMn(2)O(6) with a tetragonal (SG = P4/mmm, Z = 2) perovskite-like unit cell and Curie temperature T(C)≈313 K and (ii) oxygen superstoichiometric A-site disordered Pr(0.90)Ba(0.10)MnO(3.05) with an orthorhombic (SG = Pnma, Z = 4) perovskite-like unit cell and Curie temperature T(C)≈133 K. This processed sample has a spontaneous magnetic moment σ(S)∼2.82 µ(B)/f.u. in its ground state, and σ(S)∼0.59 µ(B)/f.u. at T∼300 K. It also exhibits a magnetoresistance of ∼14% at ∼313 K in a field of 50 kOe. This processed sample has a reduced average grain size [Formula: see text] nm. The two magnetic phases, Pr(0.90)Ba(0.10)MnO(3.05) and PrBaMn(2)O(6), are exchange-coupled. For Pr(0.90)Ba(0.10)MnO(3.05) the temperature hysteresis is ∼22 K in a field of 10 Oe and ∼5 K in a field of 1 kOe. The observed magnetic properties are interpreted in terms of chemical phase separation, grain size, and A-site ionic ordering effects.