Oleylamine as a reducing agent in syntheses of magic-size clusters and monodisperse quantum dots: optical and photoconductivity studies.

Separation of magic size clusters (MSCs) from monodisperse quantum dots (QDs) has generally been a difficult task while employing the commonly used synthesis procedure, where for preparation of PbSe QDs, Se-TOP (TOP = trioctylphosphine) is injected into Pb-oleate in 1-octadecene medium. In this study, we report for the first time a simple method to prepare MSCs, QDs and particles close to the bulk of PbSe using oleylamine (OAM) as the reducing agent, where the individual entities are efficiently separated. The chemical yield is found to be 95%. Studies on optical properties revealed the absorption and emission peaks of MSCs at fixed positions of 600 and 780 nm, respectively, while QDs exhibit significant shift to longer wavelengths for both the cases, depending on the particle size. Shift of the emission peak position for QDs is observed to be larger for initial stages of the waiting time as compared to those for longer waiting times. This can be attributed to two factors: faster growth in particle size is favoured kinetically in the initial stages, while thermodynamic stability occurs in the later stages, and reduction in surface to core contribution with increase of waiting time. QDs were found to emit at only one particular wavelength while they absorbed at two or more wavelengths. The quantum yields (QYs) of particles of sizes 4.1 and 5.1 nm are found to be 80 and 30%, respectively. The lifetime values are found to be 1.0-1.3 µs for QDs having an emission peak in the range of 1300-1500 nm. The hybrid device of PbSe (5 nm size) and MEHPPV (2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene) shows increased conductivity both in the dark and in light, due to absorption in the region of NIR photons in the former and additionally in the visible region in the latter.

Enhanced up-conversion and temperature-sensing behaviour of Er(3+) and Yb(3+) co-doped Y2Ti2O7 by incorporation of Li(+) ions.

Y2Ti2O7:Er(3+)/Yb(3+) (EYYTO) phosphors co-doped with Li(+) ions were synthesized by a conventional solid-state ceramic method. X-ray diffraction studies show that all the Li(+) co-doped EYYTO samples are highly crystalline in nature with pyrochlore face centred cubic structure. X-ray photon spectroscopy studies reveal that the incorporation of Li(+) ions creates the defects and/or vacancies associated with the sample surface. The effect of Li(+) ions on the photoluminescence up-conversion intensity of EYYTO was studied in detail. The up-conversion study under ∼976 nm excitation for different concentrations of Li(+) ions showed that the green and red band intensities were significantly enhanced. The 2 at% Li(+) ion co-doped EYYTO samples showed nearly 15- and 8-fold enhancements in green and red band up-converted intensities compared to Li(+) ion free EYYTO. The process involved in the up-conversion emission was evaluated in detail by pump power dependence, the energy level diagram, and decay analysis. The incorporation of Li(+) ions modified the crystal field around the Er(3+) ions, thus improving the up-conversion intensity. To investigate the sensing application of the synthesized phosphor materials, temperature-sensing performance was evaluated using the fluorescence intensity ratio technique. Appreciable temperature sensitivity was obtained using the synthesized phosphor material, indicating its applicability as a high-temperature-sensing probe. The maximum sensitivity was found to be 0.0067 K(-1) at 363 K.

Disappearance and recovery of luminescence in Bi3+, Eu3+ codoped YPO4 nanoparticles due to the presence of water molecules up to 800 °C.

YPO(4) nanoparticles codoped with Eu(3+) (5 at. %) and Bi(3+) (2-10 at. %) have been synthesized by a simple coprecipitation method using a polyethylene glycol-glycerol mixture, which acts as capping agent. It has been found that the incorporation of Bi(3+) ions into the YPO(4):Eu(3+) lattice induces a phase transformation from tetragonal to hexagonal, and also a significant decrease in Eu(3+) luminescence intensity was observed. This is related to the association of the water molecules in the hexagonal phase of YPO(4) in which the nonradiative process from the surrounding water molecules around Eu(3+) is dominating over the radiative process. On annealing above 800 °C, luminescence intensity recovers due to significant removal of water. 900 °C annealed Bi(3+) codoped YPO(4):Eu(3+) shows enhanced luminescence (2-3 times) as compared to that of YPO(4):Eu(3+). When sample was prepared in D(2)O (instead of H(2)O), 4-fold enhancement in luminescence was observed, suggesting the extent of reduction of multiphonon relaxation in D(2)O. This study illustrates the stability of water molecules even at a very high temperature up to 800 °C in Eu(3+) and Bi(3+) codoped YPO(4) nanoparticles.

Effects of Ce3+ codoping and annealing on phase transformation and luminescence of Eu3+-doped YPO4 nanorods: D2O solvent effect.

Ce(3+)- and Eu(3+)-doped YPO(4) nanorods have been prepared at relatively low temperature (120 degrees C). A detailed investigation of the role of Ce(3+) concentration up to 10 atom % on the luminescence intensity of Eu(3+) in Ce(3+)- and Eu(3+)-doped YPO(4) has been carried out. Phase transformation from a tetragonal to a hexagonal structure occurs with increasing Ce(3+) concentrations, and water molecules are also associated during phase transformation. Thermal study shows that water can be retained up to 800 degrees C in the hexagonal structure. Interestingly, the hexagonal structure returns to the tetragonal structure on annealing above 900 degrees C. As-prepared and 500 degrees C heated samples show uniform sized nanorods, whereas a 900 degrees C heated sample shows distorted nanorods in which pores are present. Initially, the luminescence intensity decreases sharply with increasing Ce(3+) concentrations, even for 2 atom %. This is related to the enhanced nonradiative rate as compared to the radiative rate, since multiphonon relaxation to surrounding water molecules increases. This is not due to the possible oxidation-reduction process between Eu(3+) and Ce(3+) to give Eu(2+) and Ce(4+), as confirmed by X-ray photoelectron spectroscopy and luminescence studies. Then, a significant enhancement of luminescence intensity occurs on annealing above 900 degrees C. This can be ascribed to the loss of water molecules during a phase transformation from the hydrated hexagonal to the dehydrated tetragonal phase. To the authors' knowledge, we for the first time performed a luminescent study with a change of solvent from H(2)O to D(2)O, and significant enhancement in luminescence is found.

Excess enthalpy and luminescence studies of SnO2 nanoparticles.

The extra reactivity of nano materials is attributed to the excess surface energy stored in the sample. The excess enthalpy of SnO2 nano-particles were measured as a function of particle size using a calvet calorimeter. SnO2 with particle size 11, 27, 47 nm and bulk samples (1 microm) were dropped from room temperature to 987, 936 and 885 K and their H(T)-H298 values were determined. The excess enthalpies for SnO2 samples with particle sizes 11, 27 and 47 nm compared to the bulk sample calculated from the difference between H(T)-H298 values of the nano and the bulk samples were found to be 15.06, 3.05, 2.21 kJ x mol(-1) respectively. Luminescence experiments reveal that the surface trap electron density decreases with increase of particle size. The excess enthalpy is related to the surface trap intensity.

Raman spectroscopic investigations of nanoparticles of Sn(x)Ti(1-x)O2 solid solution.

SnO2 nanoparticles dispersed in TiO2 matrix are prepared at a relatively low temperature of approximately 185 degrees C. Nanoparticles of Sn(x)Ti(1-x)O2 solid solution without significant aggregation have been prepared by annealing them at approximately 500 and 900 degrees C. X-ray diffraction and high-resolution transmission electron microscopy studies have clearly established the nano-size nature of the samples. Raman spectroscopic investigations of these samples show mixed vibrational modes, some of them being similar to TiO2 (A(1g), E(g)), while some of them are similar to SnO2 (B(2g)). The E(g) mode shows significant red shift and B(2g) mode shows significant blue shift. Unlike this A(1g) mode remains unaffected. These results are explained based on the combined effects of random alloy formation and the nano-size nature of samples.

Luminescence studies on low temperature synthesized ZnGa2O4:Ln3+ (Ln = Tb and Eu) nanoparticles.

ZnGa2O4 nanoparticles doped with lanthanide ions (Tb3+ and Eu3+) were prepared at a low temperature of 120 degrees C based on urea hydrolysis in ethylene glycol medium. X-ray diffraction studies have confirmed that strain associated with nanoparticles changes as Tb3+ gets incorporated in the ZnGa2O4 lattice. Based on steady state emission and excitation studies of ZnGa2O4:Tb nanoparticles, it has been inferred that ZnGa2O4 host is characterized by a broad emission around 427 nm and there exists energy transfer between the host and Tb3+ ions. Unlike this, for ZnGa2O4:Eu nanoparticles, very poor energy transfer between the host and Eu3+ ions is observed. These nanoparticles when coated with ligands like oleic acid results in their improved dispersion in organic solvents like chloroform and dichloromethane.

Luminescence properties of SnO2 nanoparticles dispersed in Eu3+ doped SiO2 matrix.

SnO2 nanoparticles dispersed in Eu3+ doped silica (SnO2-SiO2:Eu3+) were prepared at a low temperature (185 degrees C) in ethylene glycol medium. Transmission electron microscopy studies on as-prepared samples have established that SnO2 nanoparticles having size of 4.6 nm are uniformly covered by the SiO2 matrix. Significant extent of exciton mediated energy transfer between SnO2 and Eu3+ ions in heat treated SnO2-SiO2:Eu3+ samples has been attributed to the diffusion of Eu3+ ions from the SiO2 matrix to the near vicinity of SnO2 nanoparticles and its incorporation in the SnO2 matrix. On the other hand, very weak energy transfer exists for SnO2:Eu3+ nanoparticles heated at different temperatures due to the phase segregation of Eu3+ ions from the matrix.

Re-dispersible Li+ and Eu3+ co-doped nanocrystalline ZnO: luminescence and EPR studies.

Nano-crystals of ZnO, Eu3+ doped ZnO, and Li+, Eu3+ co-doped ZnO have been prepared by urea hydrolysis in ethylene glycol medium at 150 degrees C. Ethylene glycol acts as capping agent for nanoparticles. Three colors 437 (blue), 540 (green) and 615 nm (red) from 2 at.% Li+ and 5 at.% Eu3+ co-doped ZnO have been observed from luminescence studies compared to that from 5 at.%. Eu3+ doped ZnO, which shows emission at 437 and 615 nm. It is established that green light is originated from the oxygen vacancy brought by Li+ incorporation into ZnO. Particles are redispersible in organic solvent such as ethanol, and are able to incorporate into polymer-based material such as SiO2 matrix.

Synthesis and characterization of monodispersed water dispersible Fe3O4 nanoparticles and in vitro studies on human breast carcinoma cell line under hyperthermia condition.

Monodispersed Fe3O4 magnetic nanoparticles (MNPs) having size of 7 nm have been prepared from iron oleate and made water dispersible by functionalization for biomedical applications. Three different reactions employing thioglycolic acid, aspartic acid and aminophosphonate were performed on oleic acid coated Fe3O4. In order to achieve a control on particle size, the pristine nanoparticles were heated in presence of ferric oleate which led to increase in size from 7 to 11 nm. Reaction parameters such as rate of heating, reaction temperature and duration of heating have been studied. Shape of particles was found to change from spherical to cuboid. The cuboid shape in turn enhances magneto-crystalline anisotropy (Ku). Heating efficacy of these nanoparticles for hyperthermia was also evaluated for different shapes and sizes. We demonstrate heat generation from these MNPs for hyperthermia application under alternating current (AC) magnetic field and optimized heating efficiency by controlling morphology of particles. We have also studied intra-cellular uptake and localization of nanoparticles and cytotoxicity under AC magnetic field in human breast carcinoma cell line.

Structural, magnetic, and electron transport studies on nanocrystalline layered manganite La1.2Ba1,8Mn2O7 system.

The structure property relationship for Ru doped La1.2Ba1.8Mn2-RuxO7 system has been studied systematically. The system crystallizes in the single-phase tetragonal structure with space group of 14/mmm. The unit cell volume is found to increase with Ru doping. The sheet type microstructure could be seen in this system, which is important for anisotropic nature of layered structure. The crystallite size is found to be 25 nm indicating nanocrystalline nature of the system. Ferromagnetic to paramagnetic (Tc) transition above the room temperature is observed in all except the highest doped Ru (x = 1.0) where the Tc is 254 K using a.c. susceptibility measurement. The large values of magnetoresistance for the x = 0.0 sample at 10 K is found to be 57% and 64% at applied fields of 5 and 10 T, respectively.

Covalent bridging of surface functionalized Fe3O4 and YPO4:Eu nanostructures for simultaneous imaging and therapy.

Magnetic luminescent hybrid nanostructures (MLHN) have received a great deal of attention due to their potential biomedical applications such as thermal therapy, magnetic resonance imaging, drug delivery and intracellular imaging. We report the development of bifunctional Fe3O4 decorated YPO4:Eu hybrid nanostructures by covalent bridging of carboxyl PEGylated Fe3O4 and amine functionalized YPO4:Eu particles. The surface functionalization of individual nanoparticulates as well as their successful conjugation was evident from Fourier transform infrared (FTIR) spectroscopy, dynamic light scattering (DLS), zeta-potential and transmission electron microscopy (TEM) studies. X-ray diffraction (XRD) analysis reveals the formation of highly crystalline hybrid nanostructures. TEM micrographs clearly show the binding/anchoring of 10 nm Fe3O4 nanoparticles onto the surface of 100-150 nm rice grain shaped YPO4:Eu nanostructures. These MLHN show good colloidal stability, magnetic field responsivity and self-heating capacity under an external AC magnetic field. The induction heating studies confirmed localized heating of MLHN under an AC magnetic field with a high specific absorption rate. Photoluminescence spectroscopy and fluorescence microscopy results show optical imaging capability of MLHN. Furthermore, successful internalization of these MLHN in the cells and their cellular imaging ability are confirmed from confocal microscopy imaging. Specifically, the hybrid nanostructure provides an excellent platform to integrate luminescent and magnetic materials into one single entity that can be used as a potential tool for hyperthermia treatment of cancer and cellular imaging.

Synthesis, characterization and biocompatibility of chitosan functionalized superparamagnetic nanoparticles for heat activated curing of cancer cells.

Surface functionalization, colloidal stability and biocompatibility of magnetic nanoparticles are crucial for their biological applications. Here, we report a synthetic approach for the direct preparation of superparamagnetic nanoparticles consisting of a perovskite LSMO core modified with a covalently linked chitosan shell that provides colloidal stability in aqueous solutions for cancer hyperthermia therapy. The characterization of the core-shell nanostructure using Fourier transform infrared spectroscopy; thermo-gravimetric analysis to assess the chemical bonding of chitosan to nanoparticles; field-emission scanning electron microscopy and transmission electron microscopy for its size and coating efficiency estimation; and magnetic measurement for their magnetization properties was performed. Zeta potential and light scattering studies of the core shell revealed it to possess good colloidal stability. Confocal microscopy and MTT assay are performed for qualitative and quantitative measurement of cell viability and biocompatibility. In depth cell morphology and biocompatibility is evaluated by using multiple-staining of different dyes. The magnetic@chitosan nanostructure system is found to be biocompatible up to 48 h with 80% cell viability. Finally, an in vitro cancer hyperthermia study is done on the MCF7 cell line. During in vitro hyperthermia treatment of cancer cells, cell viability is reduced upto 40% within 120 min with chitosan coated nanoparticles. Our results demonstrate that this simplified and facile synthesis strategy shows potential for designing a colloidal stable state and biocompatible core shell nanostructures for cancer hyperthermia therapy.

Enhanced photoluminescence in CaMoO4:Eu3+ by Gd3+ co-doping.

We have studied the luminescence property of CaMoO4:Eu(3+). The emission peaks at 590 ((5)D0→(7)F1) and 613 nm ((5)D0→(7)F2) for Eu(3+) are observed after excitation at 266 nm (i.e. Mo-O charge transfer band). The peak intensity of the latter dominates over the former indicating an asymmetric environment of Eu(3+) in EuO8 polyhedron or parity mixing. Luminescence intensity increases significantly with co-doping of Gd(3+). This is ascribed to energy transfer from Mo-O/Gd(3+) to Eu(3+). Luminescence intensity increases with annealing up to 900 °C due to the extent of decrease of non-radiative rates. Very high asymmetric values (A21) of 12-16 are found indicating a red emitter. As-prepared samples are dispersible in polar solvents like water, ethanol, methanol, dimethyl sulfoxide (DMSO) and ethylene glycol (EG); and among them, optimum luminescence is found in methanol. Polymer film shows red emission. The quantum yields of as-prepared 2 and 10 at% Gd(3+) co-doped CaMoO4:Eu(3+) under 277 nm (UV excitation) are 21 and 80%, respectively.

Influence of Gd3+ co-doping on structural property of CaMoO4:Eu nanoparticles.

A facile auto-combustion route is used for the synthesis of Gd(3+) (2, 5, 7 and 10 at%) co-doped CaMoO4:Eu nanoparticles. X-ray diffraction study suggests that as-prepared samples have extra impurity phases in addition to main tetragonal phase of CaMoO4, and such extra phases decrease as the annealing temperature increases from 600 to 900 °C. The crystal structure has been analysed using Rietveld program. It has space group I41/a (88) and Z = 4 (number of CaMoO4 formula units per unit cell). Average crystallite sizes of as-prepared, 600 and 900 °C annealed samples for 2 at% Gd(3+) are found to be ~33, 48 and 61 nm, respectively. The lattice strains of 5 at% Gd(3+) co-doped CaMoO4:Eu for as-prepared and 900 °C are 0.001 and 0.002, respectively. Fourier transform infrared spectroscopy gives the absorption bands at ~815 and 427 cm(-1), which are related to asymmetric stretching and bending vibrations of MoO4(2-) tetrahedron. Particle morphology is studied using scanning and transmission electron microscopy (SEM and TEM), and aggregation of particles is found. X-ray photoelectron spectroscopy (XPS) is utilized to examine the oxidation states of metal ions/oxygen and oxygen ion vacancies in Gd(3+) co-doped CaMoO4:Eu. With an increase in Gd(3+) concentration, peaks corresponding to the Gd(3+) (2p(3/2) and 2p(5/2)) binding energy could be detected.

Enhanced luminescence of CaMoO4:Eu by core@shell formation and its hyperthermia study after hybrid formation with Fe3O4: cytotoxicity assessment on human liver cancer cells and mesenchymal stem cells.

Highly water dispersible Eu³âº doped CaMoO4 nanoparticles (core) covered by CaMoO4 (shell) have been prepared using the polyol method. Significant enhancement in luminescence intensity by core@shell formation is observed due to the decrease of non-radiative rate arising from surface/defect of particles. Effect of 266 nm laser excitation (Mo-O charge transfer band) on the asymmetric ratio (A21 = intensity ratio of electric to magnetic dipole transitions) has been studied and compared with a xenon lamp source. Luminescence intensity increases with the increase of power at 532 nm laser excitation. In order to explore materials, which can show dual functionalities such as luminescence as well as magnetic properties (magnetization of ∼14.2 emu g⁻¹), water dispersible Fe3O4-CaMoO4:Eu hybrid magnetic nanoparticles (MN) have been prepared. This shows good heating ability up to ∼42 °C (hyperthermia) and luminescence in the red region (∼612 nm), which is in a biological window (optical imaging). Biocompatibility of the synthesized Fe3O4-CaMoO4:Eu hybrid magnetic nanoparticles has been evaluated in vitro by assessing their cytotoxicity on human liver cancer cells (HepG2 cells) and hTERT cells using the MTT assay and fluorescent microscopy studies.

Structured superparamagnetic nanoparticles for high performance mediator of magnetic fluid hyperthermia: synthesis, colloidal stability and biocompatibility evaluation.

Core-shell structures with magnetic core and metal/polymer shell provide a new opportunity for constructing highly efficient mediator for magnetic fluid hyperthermia. Herein, a facile method is described for the synthesis of superparamagnetic LSMO@Pluronic F127 core-shell nanoparticles. Initially, the surface of the LSMO nanoparticles is functionalized with oleic acid and the polymeric shell formation is achieved through hydrophobic interactions with oleic acid. Each step is optimized to get good dispersion and less aggregation. This methodology results into core-shell formation, of average diameter less than 40 nm, which was stable under physiological conditions. After making a core-shell formulation, a significant increase of specific absorption rate (up to 300%) has been achieved with variation of the magnetization (<20%). Furthermore, this high heating capacity can be maintained in various simulated physiological conditions. The observed specific absorption rate is almost higher than Fe3O4. MTT assay is used to evaluate the toxicity of bare and core-shell MNPs. The mechanism of cell death by necrosis and apoptosis is studied with sequential staining of acridine orange and ethidium bromide using fluorescence and confocal microscopy. The present work reports a facile method for the synthesis of core-shell structure which significantly improves SAR and biocompatibility of bare LSMO MNPs, indicating potential application for hyperthermia.

Counter ion induced irreversible denaturation of hen egg white lysozyme upon electrostatic interaction with iron oxide nanoparticles: a predicted model.

The effects of electrostatic interaction between the hen egg white lysozyme (HEWL) and the functionalized iron oxide nanoparticles (IONPs) have been investigated using several techniques, e.g., CD, DSC, ζ-potential, UV-visible spectroscopy, DLS, TEM. Nanoparticles (IONPs) were functionalized with three hydrophilic ligands, viz., poly(ethylene glycol) (PEG), trisodium citrate (TSC) and sodium triphosphate (STP); where both TSC and STP contain Na(+) counter ions. It has been observed that the secondary structure of HEWL was not affected by PEG functionalized IONPs, but was partially and almost completely perturbed by TSC and STP functionalized IONPs, respectively. The perturbation of the secondary structure was irreversible. We have predicted an interaction model to explain the origin of perturbation of HEWL structure. We have also investigated the stability of nanoparticles dispersions after interaction with HEWL and used the DLVO theory to explain results.

Functionalization of La(0.7)Sr(0.3)MnO3 nanoparticles with polymer: studies on enhanced hyperthermia and biocompatibility properties for biomedical applications.

Now-a-days surface functionalized La(0.7)Sr(0.3)MnO(3) (LSMO) nanoparticles by different biocompatible polymers are attracted considerable interest in various biomedical applications in general and magnetic fluid hyperthermia treatment of cancer in particular. In this paper La(0.7)Sr(0.3)MnO(3) nanoparticles are synthesized and functionalized with polymer (dextran, with mean particle size ~25 nm). Magnetic measurements of both coated and uncoated particles reveal the superparamagnetic nature at room temperature. The resulting coated particles form a stable suspension in an aqueous environment at physiological pH and possess a narrow hydrodynamic size distribution. In vitro cytotoxicity of the MNPs has been assessed under Trypan blue dye exclusion and MTT assay on HeLa and L929 cell lines. The results demonstrate that dextran functionalized nanoparticles have no significant effect on cell viability within the tested concentrations (0.2-1 mg/mL) as compared to bare LSMO. Magnetic fluid hyperthermia studies have been done in detail; the influence of an applied alternating current (AC) magnetic field on heat generation is presented in brief. Dextran functionalized LSMO has the higher Specific absorption rate (SAR) value than the bare LSMO. After functionalization with dextran the SAR values of LSMO nanoparticles increased from 25 to 51 W/g. The study shows that the rise in temperatures by these nanoparticles could be safely controlled around Curie temperature (T(c)).

Induction heating studies of dextran coated MgFe2O4 nanoparticles for magnetic hyperthermia.

MgFe(2)O(4) nanoparticles with sizes around 20 nm have been prepared by a combustion method and functionalized with dextran for their possible applications in magnetic particle hyperthermia. The induction heating study of these nanoparticles at different magnetic field amplitudes, from 6.7 kA m(-1) to 26.7 kA m(-1), showed self-heating temperature rise up to 50.25 °C and 73.32 °C (at 5 mg mL(-1) and 10 mg mL(-1) concentrations in water respectively) which was primarily thought to be due to hysteresis losses activated by an AC magnetic field. The dextran coated nanoparticles showed a maximum specific absorption rate (SAR) of about 85.57 W g(-1) at 26.7 kA m(-1) (265 kHz). Dextran coated nanoparticles at concentrations below 1.8 mg mL(-1) exhibit good viability above 86% on mice fibroblast L929 cells. The results suggest that combustion synthesized MgFe(2)O(4) nanoparticles coated with dextran can be used as potential heating agents in magnetic particle hyperthermia. Uncoated and dextran coated samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric-differential thermal analysis (TG-DTA) and zeta potential-DLS studies.