R.K. Vatsa

Induction heating studies of Fe3O4 magnetic nanoparticles capped with oleic acid and polyethylene glycol for hyperthermia

Fe3O4 magnetic nanoparticles (Fe3O4-MN) capped with either oleic acid (Fe3O4-OA-MN) or polyethylene glycol (Fe3O4-PEG-MN) were prepared by a co-precipitation method. From X-ray diffraction studies, the average crystallite sizes of Fe3O4-MN, Fe3O4-OA-MN and Fe3O4-PEG-MN were found to be 12, 6 and 8 nm, respectively. A reduction in the agglomeration of particles was observed when the magnetic nanoparticles (MN) were capped with oleic acid (OA) and polyethylene glycol (PEG), as confirmed by a transmission electron microscopy study. Magnetization of these MN was almost zero at room temperature in the absence of an applied magnetic field, indicating their superparamagnetic behavior. Magnetization was lower and the superparamagnetic fraction was higher for Fe3O4-OA-MN and Fe3O4-PEG-MN compared to Fe3O4-MN studied using a Mossbauer spectrometer. Compared to the control, an increased killing (35%) was observed in human breast cancer cells (MCF7) after Fe3O4-OA-MN treatment, which was further enhanced (65%) under induction heating conditions. However, MCF7 cells treated with Fe3O4-MN or Fe3O4-PEG-MN showed 5–10% killing after induction heating. These results showed the characterization of MN with different lipophilicity and suggests their suitability for hyperthermia applications in cancer therapy.

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.

Lifetime and quantum yield studies of Dy3+ doped GdVO4 nanoparticles: Concentration and annealing effect

GdVO4 nanoparticles doped with Dy3+ have been prepared using urea hydrolysis method in ethylene glycol medium. Linear decrease in the unit cell volume indicates the quantitative substitution of Gd3+ lattice sites by Dy3+ in GdVO4. The luminescence intensity of electric dipole transition at 573 nm is more than that of magnetic dipole transition at 483 nm. This has been attributed to the asymmetric environment of Dy3+ ion in GdVO4. Luminescence intensity decreases with increasing Dy3+ concentrations due to concentration quenching. This is supported by lifetime decay studies. There is no particle size effect on the peak positions of Dy3+ emission. There is an increase in the decay lifetime for F49/2 level with increase in heat treatment from 500 to 900 °C. This is attributed to the reduction in nonradiative process arose from surface inhomogeneities. The decay lifetime data follow the biexponential to monoexponential nature with increase of Dy3+ concentrations. There is an increase in the quantum yield with ...

Synthesis of oleic acid functionalized Fe3O4 magnetic nanoparticles and studying their interaction with tumor cells for potential hyperthermia applications.

In the present study, oleic acid (OA) functionalized Fe3O4 magnetic nanoparticles (MN) were synthesized following modified wet method of MN synthesis. The optimum amount of OA required for capping of MN and the amount of bound and unbound/free OA was determined by thermogravimetric analysis (TGA). Further, we have studied the effect of water molecules, associated with MN, on the variation in their induction heating ability under alternating current (AC) magnetic field conditions. We have employed a new approach to achieve dispersion of OA functionalized MN (MN-OA) in aqueous medium using sodium carbonate, which improves their biological applicability. Interactions amongst MN, OA and sodium carbonate were studied by Fourier transform infrared spectroscopy (FT-IR). Intracellular localization of MN-OA was studied in mouse fibrosarcoma cells (WEHI-164) by prussian blue staining and confocal laser scanning microscopy (CLSM) using nile blue A as a fluorescent probe. Results showed MN-OA to be interacting mainly with the cell membrane. Their hyperthermic killing ability was evaluated in WEHI-164 cells by trypan blue method. Cells treated with MN-OA in combination with induction heating showed decreased viability as compared to respective induction heating controls. These results were supported by altered cellular morphology after treatment of MN-OA in combination with induction heating. Further, the magnitude of apoptosis was found to be ~5 folds higher in cells treated with MN-OA in combination with induction heating as compared to untreated control. These results suggest the efficacy of MN-OA in killing of tumor cells by cellular hyperthermia.

Luminescence, lifetime, and quantum yield studies of redispersible Eu3+-doped GdPO4 crystalline nanoneedles: Core-shell and concentration effects

Crystalline nanoneedles of Eu3+-doped GdPO4 and Eu3+-doped GdPO4 covered with GdPO4 shell (core shell) have been prepared at relatively low temperature of 150 °C in ethylene glycol medium. From luminescence study, asymmetric ratio of Eu3+ emission at 612 nm (electric dipole transition) to 592 nm (magnetic dipole transition) is found to be less than one. Maximum luminescence was observed from the nanoparticles with Eu3+ concentration of 5 at. %. For a fixed concentration of Eu3+ doping, there is an improvement in emission intensity for core-shell nanoparticles compared to that for core. This has been attributed to effective removal of surface inhomogeneities around Eu3+ ions present on the surface of core as well as the passivation of inevitable surface states, defects or capping ligand (ethylene glycol) of core nanoparticles by bonding to the shell. Lifetime for D50 level of Eu3+ was found to increase three times for core-shell nanoparticles compared to that for core confirming the more Eu3+ ions with sym...

Re-dispersion and film formation of GdVO4 : Ln3+ (Ln3+ = Dy3+, Eu3+, Sm3+, Tm3+) nanoparticles: particle size and luminescence studies

GdVO(4) : Ln(3+) (Ln(3+) = Dy(3+), Eu(3+), Sm(3+), Tm(3+)) nanoparticles are prepared by a simple chemical route at 140 °C. The crystallite size can be tuned by varying the pH of the reaction medium. Interestingly, the crystallite size is found to increase significantly when pH increases from 6 to 12. This is related to slower nucleation of the GdVO(4) formation with increase of VO(4)(3-) present in solution. The luminescence study shows an efficient energy transfer from vanadate absorption of GdVO(4) to Ln(3+) and thereby enhanced emissions are obtained. A possible reaction mechanism at different pH values is suggested in this study. As-prepared samples are well dispersed in ethanol, methanol and water, and can be incorporated into polymer films. Luminescence and its decay lifetime studies confirm the decrease in non-radiative transition probability with the increase of heat treatment temperature. Re-dispersed particles will be useful in potential applications of life science and the film will be useful in display devices.

Luminescence study of Eu3+ doped GdVO4 nanoparticles: Concentration, particle size, and core/shell effects

Nanoparticles of GdVO4 doped with Eu3+ and core/shell of GdVO4:Eu3+/GdVO4 are prepared by urea hydrolysis method using ethylene glycol as capping agent as well as reaction medium at 130 °C. Unit cell volume increases when GdVO4 is doped with Eu3+ indicating the substitution of Gd3+ lattice sites by Eu3+. From luminescence study, it is confirmed that there is no particle size effect on emission positions of Eu3+. Optimum luminescence intensity is found to be in 5–10 at. % Eu3+. Above these concentrations, luminescence intensity decreases due to concentration quenching effect. There is an enhancement in luminescence intensity of core/shell nanoparticles. This has been attributed to the reduction in surface inhomogenities of Eu3+ surroundings by bonding to GdVO4 shell. The lifetime for D50 level increases with annealing and core/shell formation.

Gd2O3:Eu3+ particles prepared by glycine-nitrate combustion: Phase, concentration, annealing, and luminescence studies

Eu3+ doped Gd2O3 particles have been prepared by glycine-nitrate combustion route. Eu–O charge transfer peak shifts to higher wavelength from 260 to 273 nm with increasing Eu3+ concentration, whereas the linewidth at half maximum intensity varies with Eu3+ concentrations and annealing temperatures as well. Lifetime for D50 level of Eu3+ increases with annealing temperature from 500 to 900 °C, and this is related to decreasing surface to volume atomic ratio of particles. Asymmetric ratio defined by the ratio of intensity of electrical dipole transition to that of magnetic dipole transition is found to be 10, which is more than the reported values (3–4) indicating enhancement in luminescence by this synthesis route.

Absolute primary H atom quantum yield measurements in the 193.3 and 121.6 nm photodissociation of acetylene

Absolute quantum yields for primary H atom formation (UH) were measured under collision-free conditions for the room-temperature gas-phase dissociation of acetylene (C2H2) after photoexcitation at 193.3 nm and at the H-atom Lyman-a wavelength (121.6 nm) by a pulsed laser photolysis (LP)–laser-induced fluorescence (LIF) ‘pump-and-probe’ technique. Using HCl and CH4 photolysis at 193.3 and 121.6 nm, respectively, as a reference, values of UH ð193: 3n mÞ¼0:94� 0:12 and UH ð121: 6n mÞ¼1:04� 0:16 were obtained which demonstrate that for both photolysis wavelengths the Hþ C2H product channel dominates the primary C2H2 photochemistry. 2002 Published by Elsevier Science B.V.

Multiphoton ionisation of acetone at 355 nm: a time-of-flight mass spectrometry study

Abstract Multiphoton ionisation/fragmentation of acetone has been studied at λ=355 nm using time-of-flight mass spectrometry. A broad peak at m/e=43 is observed which shows a three-photon laser power dependence. The results suggest that three-photon ionisation at 355 nm produces vibrationally excited acetone ions which undergo fast dissociation. The broadening of the m/e=43 peak is found to depend on the laser power in the low laser intensity region. Under high laser intensity conditions, a bimodal distribution of m/e=43 peak was observed which has been assigned to two different isomeric product channels. The results provide clear evidence for partial isomerisation of the keto form of the acetone radical cation to the enol form. On ionisation at 355 nm, CH3COC2H5 fragments into two channels corresponding to (CH3CO+) and (C2H5CO+) in the ratio of approximately 3:1.