Synthesis, Structural Characterization and Formation Mechanism of Ferroelectric Bismuth Vanadate Nanotubes

We report the synthesis and structural characterization of ferroelectric bismuth vanadate (Bi2VO5.5) (BVO) nanotubes within the nanoporous anodic aluminum oxide (AAO) templates via sol-gel method. The as-prepared BVO nanotubes were characterized by X-ray powder diffraction (XRD), Scanning Electron Microscope (SEM), High-Resolution Transmission Electron Microscope (HRTEM) and the stoichiometry of the nanotubes was established by energy-dispersive X-ray spectroscopy (EDX). Postannealed (675 degrees C for 1 h), BVO nanotubes were a polycrystalline and the XRD studies confirmed the crystal structure to be orthorhombic. The uniformity in diameter and length of the nanotubes as reveled by the TEM and SEM suggested that these were influenced to a guest extent by the thickness and pore diameter of the nanoporous AAO template. EDX analysis demonstrated the formation of stoichiometric Bi2VO5.5 phase. HRTEM confirmed that the obtained BVO nanotubes were made up of nanoparticles of 5-9 nm range. The possible formation mechanism of nanotubes was elucidated.

Structure and Function of Hemoglobin Confined Inside Silica Nanotubes

Investigations on the structure and function of hemoglobin (Hb) confined inside sol-gel template synthesized silica nanotubes (SNTs) have been discussed here. Immobilization of hemoglobin inside SNTs resulted in the enhancement of direct electron transfer during an electrochemical reaction. Extent of influence of nanoconfinement on protein activity is further probed via ligand binding and thermal stability studies. Electrochemical investigations show reversible binding of n-donor liquid ligands, such as pyridine and its derivatives, and predictive variation in their redox potentials suggests an absence of any adverse effect on the structure and function of Hb confined inside nanometer-sized channels of SNTs. Immobilization also resulted in enhanced thermal stability of Hb. The melting or denaturation temperature of Hb immobilized inside SNTs increase by approximately 4 degrees C as compared with that of free Hb in solution.

Ultrasound-Triggered Controlled Drug Delivery and Biosensing Using Silica Nanotubes

Silica nanotubes (SNTs) have been demonstrated here as a versatile host for controlled drug delivery and biosensing. The sol-gel template synthesized SNTs have a slow rate of drug release. Application of an external stimulus in the form of ultrasound to or chemical functionalization of synthesized SNT results in higher yield of drug release as well as yield of drug release varying linearly with time. In case of controlled drug delivery triggered by ultrasound, drug yield as function of time is found to be heavily dependent on the ultrasound impulse protocol. Impulses of shorter duration (similar to 0.5 min) and shorter time intervals between successive impulses resulted in higher drug yields. Confinement of hemoglobin (Hb) inside nanometer sized channels of SNT does not have any detrimental effect on the native protein structure and function. Observance of significant enhancement in direct electron transfer of Hb makes the SNTs also promising for application in biosensors.

Surface spin glass behavior in sol–gel derived La0.7Ca0.3MnO3 nanotubes

We report the fabrication of La0.7Ca0.3MnO3 nanotubes (LCMONTs) with a diameter of about 200 nm, by a modified sol-gel method utilizing nanochannel alumina templates. High resolution transmission electron microscopy confirmed that the obtained LCMONTs are made up of nanoparticles (8-12 nm), which are randomly aligned in the wall of the nanotubes. The strong irreversibility between zero field cooling (ZFC) and field cooling (FC) magnetization curves as well as a cusplike peak in the ZFC curve gives strong support for surface spin glass behavior.

Unraveling the packing pattern leading to gelation using SS NMR and X-ray diffraction: direct observation of the evolution of self-assembled fibers

A detailed understanding of the mode of packing patterns that leads to the gelation of low molecular mass gelators derived from bile acid esters was carried out using solid state NMR along with complementary techniques such as powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and polarizing optical microscopy (POM). Solid state C-13{H-1} cross polarization (CP) magic angle spinning (MAS) NMR of the low molecularmass gel in its native state was recorded for the first time. A close resemblance in the packing patterns of the gel, xerogel and bulk solid states was revealed upon comparing their C-13{H-1} CPMAS NMR spectral pattern. A doublet resonance pattern of C-13 signals in C-13{H-1}CPMAS NMR spectra were observed for the gelator molecules, whereas the non-gelators showed simple singlet resonance or resulted inthe formation of inclusion complexes/solvates. PXRD patterns revealed a close isomorphous nature of the gelators indicating the similarity in the mode of the packing pattern in their solid state. Direct imaging of the evolution of nanofibers (sol-gel transition) was carried out using POM, which proved the presence of self-assembled fibrillar networks (SAFINs) in the gel. Finally powder X-ray structure determination revealed the presence of two non-equivalent molecules in an asymmetric unit which is responsible for the doublet resonance pattern in the solid state NMR spectra.

Solvation dynamics in dipolar liquids

The time dependent response of a polar solvent to a changing charge distribution is studied in solvation dynamics. The change in the energy of the solute is measured by a time domain Stokes shift in the fluorescence spectrum of the solute. Alternatively, one can use sophisticated non-linear optical spectroscopic techniques to measure the energy fluctuation of the solute at equilibrium. In both methods, the measured dynamic response is expressed by the normalized solvation time correlation function, S(t). The latter is found to exhibit uniquefeatures reflecting both the static and dynamic characteristics of each solvent. For water, S(t) consists of a dominant sub-50 fs ultrafast component, followed by a multi-exponential decay. Acetonitrile exhibitsa sub-100 fs ultrafast component, followed by an exponential decay. Alcohols and amides show features unique to each solvent and solvent series. However, understanding and interpretation of these results have proven to be difficult, and often controversial. Theoretical studiesand computer simulations have greatly facilitated the understanding ofS(t) in simple systems. Recently solvation dynamics has been used extensively to explore dynamics of complex systems, like micelles and reverse micelles, protein and DNA hydration layers, sol-gel mixtures and polymers. In each case one observes rich dynamical features, characterized again by multi-exponential decays but the initial and final time constants are now widely separated. In this tutorial review, we discuss the difficulties in interpreting the origin of the observed behaviour in complex systems.

Suppression of charge order, disappearance of antiferromagnetism, and emergence of ferromagnetism in Nd0.5Ca0.5MnO3 nanoparticles

Nd0.5Ca0.5MnO3 nanoparticles (average diameter similar to 20 and 40 nm) are synthesized by the polymeric precursor sol-gel method and characterized by various physico-chemical techniques. Quite strikingly, in the 20 nm particles, the charge-ordered (CO) and the antiferromagnetic phases observed in the bulk below 250 K and 160 K, respectively, are completely absent. Instead, a ferromagnetic (FM) transition is observed at 95 K followed by an insulator-to-metal transition at 75 K. The 40 nm particles show a residual CO phase but a transition to the FM state also occurs, at a slightly higher temperature of 110 K.

Low Temperature Synthesis of Nano-Crystalline CaCu3Ti4O12 Through aFuel Mediated Auto-Combustion Pathway

A novel, cost effective,environment-friendly and energetically beneficial alternative method for the synthesis of giant dielectric pseudo-perovskite material CaCu3Ti4O12 (CCTO) is presented. The method involved auto-combustion of an aqueous precursor solution in oxygen atmosphere with the help of external fuels and is capable of producing high amount of CCTO at ultra-low temperature, in the combustion residue itself. The amount of phase generated was observed to be highly dependent on the combustion process i.e. on the nature and amount of external-fuels added for combustion. Two successful fuel combinations capable of producing reasonably higher amount of the desired compound were investigated. On a structural characterization grain size was observed to decrease drastically to nano-dimension compared to submicron-size that was obtained in a traditional sol-gel combustion and subsequent cacination method. Therefore, the method reported can produce nano-crystalline CaCu3Ti4O12 ceramic matrix at an ultra-low temperature and is expected to be applicable for other multifunctional perovskite oxide materials.

Dielectric properties of electron irradiated PbZrO3 thin films

The present paper deals with the study of the effects of electron (8 MeV) irradiation on the dielectric and ferroelectric properties of PbZrO3 thin films grown by sol-gel technique. The films were (0.62 mu m thick) subjected to electron irradiation using Microtron accelerator (delivered dose 80, 100, 120 kGy). The films were well crystallized prior to and after electron irradiation. However, local amorphization was observed after irradiation. There is an appreciable change in the dielectric constant after irradiation with different delivered doses. The dielectric loss showed significant frequency dispersion for both unirradiated and electron irradiated films. T (c) was found to shift towards higher temperature with increasing delivered dose. The effect of radiation induced increase of E >'(T) is related to an internal bias field, which is caused by radiation induced charges trapped at grain boundaries. The double butterfly loop is retained even after electron irradiation to the different delivered doses. The broader hysteresis loop seems to be related to radiation induced charges causing an enhanced space charge polarization. Radiation-induced oxygen vacancies do not change the general shape of the AFE hysteresis loop but they increase P (s) of the hysteresis at the electric field forced AFE to FE phase transition. We attribute the changes in the dielectric properties to the structural defects such as oxygen vacancies and radiation induced charges. The shift in T (C), increase in dielectric constant, broader hysteresis loop, and increase in P (r) can be related to radiation induced charges causing space charge polarization. Double butterfly and hysteresis loops were retained indicative of AFE nature of the films.

Magnetic, electric, and dielectric properties of FeCo alloy nanoparticles dispersed in amorphous matrix

Nanocrystalline Fe53Co47 alloy was synthesized by a single-step transmetallation chemical method at room temperature. The Fe53Co47 alloy nanoparticles of 77 and 47 wt% were dispersed in silica matrix by the sol-gel process using tetraethyl orthosilcate. Structural studies reveal that the as-prepared alloy powders are in bcc phase and silica is in an amorphous state. The phase-transition temperature and Mossbauer spectra analysis of the Fe-Co alloy establishes the homogeneous alloy formation. A saturation magnetization of 218 emu/g was obtained for pure FeCo alloy at room temperature. Scanning electron microscopic analysis demonstrates the hollow-sphere morphology for FeCo alloy particles. Magnetic nanocomposite consisting of 47 wt% FeCo-silica shows enhanced thermal stability over the native FeCo alloy. Electrical and dielectric properties of 47 wt% FeCo-silica nanocomposites were investigated as a function of frequency and temperature. It was found that the dielectric constants and dielectric loss were stable throughout the measured temperature (310-373 K). Our results indicate that FeCo-silica nanocomposite is a promising candidate for high-frequency applications. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Mesoporous Carbon and Poly(3,4-ethylenedioxythiophene) Composite as Catalyst Support for Polymer Electrolyte Fuel Cells

In situ polymerization of 3,4-ethylenedioxythiophene with sol-gel-derived mesoporous carbon (MC) leading to a new composite and its subsequent impregnation with Pt nanoparticles for application in polymer electrolyte fuel cells (PEFCs) is reported. The composite exhibits good dispersion and utilization of platinum nanoparticles akin to other commonly used microporous carbon materials, such as carbon black. Pt-supported MC-poly(3,4-ethylenedioxythiophene) (PEDOT) composite also exhibits promising electrocatalytic activity toward oxygen reduction reaction, which is central to PEFCs. The PEFC with Pt-loaded MC-PEDOT support exhibits 75% of enhancement in its power density in relation to the PEFC with Pt-loaded pristine MC support while operating under identical conditions. It is conjectured that Pt-supported MC-PEDOT composite ameliorates PEFC performance/durability on repetitive potential cycling. (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3486172] All rights reserved.

Direct Growth of Gold Nanorods on Gold and Indium Tin Oxide Surfaces: Spectral, Electrochemical, and Electrocatalytic Studies

The surfactant-assisted seed-mediated growth method was used for the formation of gold nanorods (GNRs) directly on gold (Au) and indium tin oxide (ITO) surfaces. Citrate-stabilized similar to 2.6 nm spherical gold nanoparticles (AuNPs) were first self-assembled on ITO or Au surfaces modified with (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film and then immersed in a cationic surfactant growth solution to form GNRs. The growth of GNRs on the MPTS sol gel film modified ITO surface was monitored by UV-visible spectroscopy. The ITO surface with the attached spherical AuNPs shows a surface plasmon resonance band at 550 nm. The intensity of this absorption band increases while increasing the immersion time of the AuNP-modified ITO surface into the growth solution, and after 5 h, an additional shoulder band around 680 nm was observed. The intensity of this shoulder band increases, and it was shifted to longer wavelength as the immersion time of the AuNP-modified ITO surface into the growth solution increases. After 20 h, a predominant wave at 720 nm was observed along with a band at 550 nm. Further immersion of the modified ITO surface into the growth solution did not change the absorption characteristics. The bands observed at 550 and 720 nm were characteristics of GNRs, corresponding to transverse and longitudinal waves, respectively. The AFM images showed the presence of GNRs on the surface of the MPTS sol gel modified ITO surface with a typical length of similar to 100-120 nm and a width of similar to 20-22 nm in addition to a few spherical AuNPs, indicating that seeded spherical AuNPs were not completely involved in the GNRs' formation. Finally, the electrocatalytic activity of the surface-grown GNRs on the MPTS sol gel film modified Au electrode toward the oxidation of ascorbic acid (AA) was studied. Unlike a polycrystalline Au electrode, the surface-grown GNR-modified electrode shows two well-defined voltammetric peaks for AA at 0.01 and 0.35 V in alkaline, neutral, and acidic pHs. The cause for the observed two oxidation peaks for AA was due to the presence of both nanorods and spherical nanoparticles on the electrode surface. The presence of spherical AuNPs on the MPTS sol gel film oxidized AA at more positive potential, whereas the GNRs oxidized AA at less positive potential. The observed 340 mV less positive potential shift in the oxidation of AA suggested that GNRs are better electrocatalysts for the oxidation of AA than the spherical AuNPs.

A PEFC With Pt-TiO2/C as Oxygen-Reduction Catalyst

Carbon-supported Pt-TiO2 (Pt-TiO2/C) catalyst with varying atomic ratio of Pt to Ti, namely, 1: 1, 2: 1, and 3: 1, is prepared by sol-gel method and its electrocatalytic activity toward oxygen-reduction reaction (ORR) is evaluated for the application in polymer electrolyte fuel cells (PEFCs). The optimum atomic ratio of Pt to Ti in Pt-TiO2/C and annealing temperature are established by cyclic voltammetry and fuel-cell-polarization studies. Pt-TiO2/C annealed at 750 degrees C with Pt and Ti in atomic ratio of 2: 1, namely, 750 Pt-TiO2/C (2: 1), shows enhanced electrocatalytic activity toward ORR. It is found that the incorporation of TiO2 with Pt ameliorates both electrocatalytic activity and stability of cathode in relation to pristine Pt cathode, currently being used in PEFCs. A power density of 0.75 W/cm(2) is achieved at 0.6 V for the PEFC with 750 Pt-TiO2/C (2: 1) as compared with 0.62 W/cm(2) at 0.6 V achieved with the PEFC comprising Pt/C as cathode catalyst while operating under identical conditions. Interestingly, carbon-supported Pt-TiO2 cathode exhibits only 6% loss in electrochemical surface area after 5000 potential cycles while it is as high as 25% for Pt/C. DOI: 10.1115/1.4002466]

Spectrally broadened excitonic absorption and enhanced optical nonlinearities in Dy3+-doped ZnO nanoparticles

We have synthesized Dy3+-doped ZnO nanoparticles at room temperature through the sol-gel method. X-ray diffraction and Scanning electron microscopic studies confirm the crystalline nature of the particles. Excitonic absorption of ZnO shows three different bands, and we observe that incorporation of Dy3+ results in the shifting and broadening of the n=1 absorption band of ZnO. Photoluminescence studies done at the excitation wavelength of 335 nm show broad emission containing five different bands. Open-aperture z-scan studies done at 532 nm using 5 ns laser pulses show an optical limiting behavior, which numerically fits to a three-photon type absorption process. The nonlinearity is essentially resonant, as it is found to increase consistently with Dy3+ concentration. This feature makes Dy3+-doped ZnO a flexible optical limiter for potential device applications.

Reduction behaviour of Fe3+/Al2O3 obtained from the mixed oxalate precursor and the formation of the Fe0-Al2O3 metal-ceramic composite

Reduction behaviour of Fe3+/Al2O3 obtained by the decomposition of the oxalate precursor has been investigated by employing X-ray diffraction (XRD), Mössbauer spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. Calcination of Fe3+/Al2O3 at or below 1070 K yields mainly a poorly ordered, fine particulate form of ?-Al2�xFexO3. Calcination at or above 1220 K yields ?-Al2�xFexO3. Reduction of Fe3+/Al2O3 samples calcined at or below 1070 K gives the FeAl2O4 spinel on reduction at 870 K; samples calcined at or above 1220 K give Al2-xFexO3 with a very small proportion of metallic iron. Fe3+/Al2O3 samples calcined at 1220 K or above yield metallic iron and a very small proportion of the spinel on reduction below 1270 K. In the samples reduced at or above 1270 K, the main product is metallic iron in both ferromagnetic and superparamagnetic forms. The oxalate precursor route yields more metallic iron than the sol�gel route.