Size-dependent magnetic properties of iron oxide nanoparticles

Uniform iron oxide nanoparticles in the size range from 10 to 24 nm and polydisperse 14 nm iron oxide particles were prepared by thermal decomposition of Fe(III) carboxylates in the presence of oleic acid and co-precipitation of Fe(II) and Fe(III) chlorides by ammonium hydroxide followed by oxidation, respectively. While the first method produced hydrophobic oleic acid coated particles, the second one formed hydrophilic, but uncoated, nanoparticles. To make the iron oxide particles water dispersible and colloidally stable, their surface was modified with poly(ethylene glycol) and sucrose, respectively. Size and size distribution of the nanoparticles was determined by transmission electron microscopy, dynamic light scattering and X-ray diffraction. Surface of the PEG-functionalized and sucrose-modified iron oxide particles was characterized by Fourier transform infrared (FT-IR) and Raman spectroscopy and thermogravimetric analysis (TGA). Magnetic properties were measured by means of vibration sample magnetometry and specific absorption rate in alternating magnetic fields was determined calorimetrically. It was found, that larger ferrimagnetic particles showed higher heating performance than smaller superparamagnetic ones. In the transition range between superparamagnetism and ferrimagnetism, samples with a broader size distribution provided higher heating power than narrow size distributed particles of comparable mean size. Here presented particles showed promising properties for a possible application in magnetic hyperthermia.     

Size-dependent electron-electron interactions in metal nanoparticles

The internal thermalization dynamics of the conduction electrons is investigated in silver nanoparticles with radius ranging from 13 to 1.6 nm using a femtosecond IR pump-UV probe absorption saturation technique. A sharp increase of the electron energy exchange rate is demonstrated for nanoparticles smaller than 5 nm. The results are consistent with electron-electron scattering acceleration due to surface induced reduction of the Coulomb interaction screening by the conduction and core electrons.     

Size-dependent properties of Eu chalcogenide nanoparticles

The size effects on different properties, such as magnetization M, Curie temperature T_C and band gap E_g of ferromagnetic semiconducting EuS nanoparticles are studied based on the d-f model and using a Green's function technique. We have shown that M and T_C are decreased compared with the bulk material, whereas E_g is increased. The results are in qualitative agreement with the experimental data.     

Size-dependent effects in solutions of small metal nanoparticles

A new theoretical approach for the calculation of optical properties of complex solutions is proposed. It is based on a dielectric matrix ε_m with included small metallic inclusions (less than 3 nm) of spherical shape. We take into account the mutual interactions between the inclusions and the quantum finite-size effects. On the basis of the effective medium model, TDLDA and Kohn-Sham theories, some analytical expressions for the effective dielectric permittivity of the solution are obtained.     

Luminescence of yttrium oxide

Pulsed cathodoluminescence of pure and neodymium-activated Y₂O₃ ceramic and materials used for its synthesis (commercial Y₂O₃ micropowder and nanopowder obtained from it by laser evaporation) is investigated in a wavelength range of 350–850 nm. In the micropowder, four series of narrow electron-vibration bands of intrinsic luminescence centers are detected. In a ceramic with the same lattice, only one series is left, while the remaining series degenerate into broad bands. In the neodymium-activated ceramic, luminescence bands of the Na³⁺ ion located in the monoclinic lattice of the γ-Y₂O₃ phase are detected.     

Size-dependent density of nanoparticles and nanostructured materials

We discuss the size-dependent density of nanoparticles and nanostructured materials keeping the recent experimental results in mind. The density is predicted to increase with decreasing size for nanoparticles but it can decrease with size for nanostructured materials that corroborates the experimental results reported in the literature.     

Synthesis,characterization, and cytotoxicity of glutathione-PEG-iron oxide magnetic nanoparticles

Recently, increasing interest is spent on the synthesis of superparamagnetic iron oxide nanoparticles, followed by their characterization and evaluation of cytotoxicity towards tumorigenic cell lines. In this work, magnetite (Fe₃O₄) nanoparticles were synthesized by the polyol method and coated with polyethylene glycol (PEG) and glutathione (GSH), leading to the formation of PEG-Fe₃O₄ and GSH-PEG-Fe₃O₄ nanoparticles. The nanoparticles were characterized by state-of-the-art techniques: dynamic light scattering (DLS), atomic force microscopy (AFM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and superconducting quantum interference device (SQUID) magnetic measurements. PEG-Fe₃O₄ and GSH-PEG-Fe₃O₄ nanoparticles have crystallite sizes of 10 and 5 nm, respectively, indicating compression in crystalline lattice upon addition of GSH on the nanoparticle surface. Both nanoparticles presented superparamagnetic behavior at room temperature, and AFM images revealed the regular spherical shape of the nanomaterials and the absence of particle aggregation. The average hydrodynamic sizes of PEG-Fe₃O₄ and GSH-PEG-Fe₃O₄ nanoparticles were 69 ± 37 and 124 nm ± 75 nm, respectively. The cytotoxicity of both nanoparticles was screened towards human prostatic carcinoma cells (PC-3). The results demonstrated a decrease in PC-3 viability upon treatment with PEG-Fe₃O₄ or GSH-PEG-Fe₃O₄ nanoparticles in a concentration-dependent manner. However, the cytotoxicity was not time-dependent. Due to the superparamagnetic behavior of PEG-Fe₃O₄ or GSH-PEG-Fe₃O₄ nanoparticles, upon the application of an external magnetic field, those nanoparticles can be guided to the target site yielding local toxic effects to tumor cells with minimal side effects to normal tissues, highlighting the promising uses of iron oxide nanoparticles in biomedical applications.     

尺寸相关的CdS纳米颗粒的拉曼散射特性

采用反胶束法,合成了具有不同尺寸的CdS纳米颗粒。利用透射电镜(TEM)和高分辨透射电镜(HR-TEM)以及紫外-可见光吸收谱(UV/vis)对这些纳米颗粒的结构特性进行了表征和分析。利用拉曼光谱仪测量了这些具有不同尺寸的CdS纳米颗粒的拉曼特性。研究结果表明：当纳米颗粒尺寸小于一定值时,拉曼峰出现了蓝移,大于一定值时出现了红移,这些不同的结果是与纳米颗粒的尺寸效应以及纳米颗粒结构中具有各向异性的电子－声子耦合作用有关。     

Size-dependent single electron tunneling effect in Au nanoparticles

We investigated single electron tunneling (SET) behavior of dodecanethiol-coated Au nanoparticles of two different sizes (average sizes are 5 nm and 2 nm) using nanogap electrodes, which have a well-defined gap size, at various temperatures. The Coulomb staircases and the Coulomb gap near-zero bias voltage caused by the suppression of the tunneling electrons due to the Coulomb blockade effect were observed in the current-voltage (I-V) curves of both sizes of nanoparticles at a low temperature (10 K). At room temperature, the Coulomb gap was observed only in the I-V curve of the smaller nanoparticles. This result indicates that the charging energy of the smaller nanoparticles is enough to overcome the thermal energy at room temperature. This suggests that it is possible to operate the SET devices at room temperature using the smaller nanoparticles as a Coulomb island.     

Spectra of europium-doped yttrium oxide and yttrium vanadate phosphors

The spectral distributions of the visible absorption and fluorescence emission under electron beam excitation of Eu³⁺-doped (Y₂O₃) and (YVO₄) powders have been detected and analyzed. (Y₂O₃: Eu³⁺) has a cubicC crystal structure with a unit cell dimension a=10·61 Å. Its observed transitions from⁷ F ₀ to many upper states have been recognized; the observed number of Stark components is in agreement with that based on theC ₂ site symmetry of the Eu³⁺ ion in Y₂O₃. Eu³⁺-doped yttrium vanadate has a typical zircon tetragonal crystal structure with unit cell dimensions ofc=6·29 Å anda=7·11 Å. The observed transitions in (Eu³⁺: YVO₄) have been identified and assigned in accordance with theD _2d site symmetry of the Eu³⁺ ion in this lattice.The authors would like to express their deep gratitude to Professor G. F. J.Garlick, University of Hull, England, for offering experimental facilities in his Physics Department.     

Cathodoluminescence of yttrium oxide and yttrium and zinc silicate films

We have studied the cathodoluminescent properties of Y₂SiO₅:Ce, Zn₂SiO₄:Ti, Zn₂SiO₄:Mn, Y₂O₃:Eu thin films obtained by high-frequency magnetron sputtering. Based on measurements of the luminescence spectra, we have shown that the films can be used as luminophores with blue emission (Y₂SiO₅:Ce, Zn₂SiO₄:Ti), green emission (Zn₂SiO₄:Mn), and red emission (Y₂O₃:Eu). We have studied the dependences of the luminescence intensity on the energy of the exciting electrons, the electron beam current density, and the exposure time. We hypothesize that the decrease in the luminescence intensity during electron bombardment is connected with formation of new oxide layers as a result of an electron-stimulated surface chemical reaction.     

On the luminescent behaviour of europium in yttrium oxide and yttrium vanadate hosts

Europium-doped Y₂O₃ and YVO₄ were excited by ultraviolet and 10 kV electrons to give the red emission of Eu³⁺. Increase in the fluorescence output with temperature under uv excitation results from an increased absorption and a more efficient energy transfer to the Eu³⁺ ions from charge-transfer states involving the Y-O and V-O componensts of the lattices. The absence of thermal quenching of fluorescence for (Y₂O₃Eu) is attributed to the high energy of its charge-transfer states which forbids the⁵ D ₀ state to come into thermal contact with them. Complete quenching would occur above 2000 K as predicted from an estimated activation energy of 24 417 cm^–1. Quenching of cathodoluminescence of (YVO₄Eu) commences at 150 K due to the lower energy of its charge-transfer states. The experimentally-deduced temperature for complete quenching of cathodoluminescence for (YVO₄Eu) is lower than that predicted from an estimated thermal activation energy of 14 217 cm^–1; the difference being attributed to localized heating effects induced by electron bombardment. It is suggested that europium ions do not take part in thermoluminescence processes. Electron-hole recombinations occur at host sites to give the observed glow peaks which have been ascribed to traps produced by lattice defects and uncontrollable impurities in the undoped hosts.     

Size-dependent nanoparticle reaction enthalpy: Oxidation of aluminum nanoparticles

Here we present a model describing the particle size dependence of the oxidation enthalpy of aluminum nanoparticles. The model includes the size dependence of the cohesive energy of the reactant particles, the size dependence of the product lattice energy, extent of product agglomeration, and surface capping effects. The strongest effects on aluminum nanoparticle energy release occur for particle diameters below 10 nm, with enhanced energy release for agglomerated oxide products and decreased energy release for nanoscale oxide products. An unusual effect is observed with all nanoparticle reaction enthalpies converging to the bulk value when agglomeration of the products approaches the transition between nanoparticle→nanoparticle and nanoparticle→bulk energetics. Optimal energy output for Al NP oxidation should occur for sub-10-nm particles reacting with significant agglomeration.     

Size-dependent nonlinear optical properties and thermal lens in silver nanoparticles

We have investigated the nonlinear response of the silver nanoparticle samples in a low-power regime of electromagnetic field based on nonlocal thermo-optic models. In this work, the experimental investigation of the thermo-optic nonlinear response of Ag colloids containing different size of silver nanoparticles is reported. The colloidal nanoparticle samples were synthesized by nanosecond pulsed laser ablation of Ag bulk in acetone. The sample containing Ag was characterized by linear absorption spectroscopy and transmission electron microscopy. Using the z-scan technique, the behavior of thermal nonlinear refractive index of colloid was studied at different concentrations of silver nanoparticles. Observation of asymmetrical configurations of the z-scan data indicates that nonlinear refraction occurring in the Ag samples is related to the thermo-optical process. The optical limiting here is due to nonlinear refraction of the samples arising from thermal lens formation under low-power CW excitation. When the laser power is low, the self-defocusing effect is mainly dominated by surface plasmon resonance effect. Results show that with increasing concentration of nanoparticles in acetone, the nonlinear refractive index increases while the threshold power of optical limiting decreases.     

Size-dependent melting of nanoparticles: Hundred years of thermodynamic model

Thermodynamic model first published in 1909, is being used extensively to understand the size-dependent melting of nanoparticles. Pawlow deduced an expression for the size-dependent melting temperature of small particles based on the thermodynamic model which was then modified and applied to different nanostructures such as nanowires, prism-shaped nanoparticles, etc. The model has also been modified to understand the melting of supported nanoparticles and superheating of embedded nanoparticles. In this article, we have reviewed the melting behaviour of nanostructures reported in the literature since 1909. This article is dedicated to Indian Institute of Science which is also celebrating its centenary this year.     

Size-dependent exchange bias in single phase Mn_3O_4 nanoparticles

Glassy magnetic behavior and exchange bias phenomena are observed in single phase Mn_3O_4 nanoparticles.Dynamics scaling analysis of the ac susceptibility and the Henkel plot indicate that the observed glassy behavior at low temperature can be understood by taking into account the intrinsic behavior of the individual particles consisting of a ferrimagnetic(FIM) core and a spin-glass surface layer.Field-cooled magnetization hysteresis loops display both horizontal and vertical shifts.Dependence of the exchange bias field(H_E) on the cooling field shows an almost undamped feature up to 70 kOe,indicating the stable exchange bias state in Mn_3O_4.H_E increases as the particle size decreases due to the higher surface/volume ratio.The occurrence of the exchange bias can be attributed to the pinning effect of the frozen spin-glass surface layer upon the FIM core.     

Mechanical twinning of yttrium oxide single crystals

The deformation structure of an yttrium oxide single crystal under point load was studied by microhardness and electron microscopy. It was concluded that mechanical twinning is the main mechanism of plastic deformation of these single crystals. A twin was simulated by rotating the structure around the three-fold axis. It was shown that the average change of the distance between anions was about 5% and that between cations was 15%. The comparison with the structure of the regions of the fluorite single crystals and optical ceramics deformed in the analogous manner was performed.