Mandar M. Shirolkar

Curcumin-reduced graphene oxide sheets and their effects on human breast cancer cells

Curcumin (as a natural reductant material) was utilized for green reduction and functionalization of chemically exfoliated graphene oxide (GO) sheets. The π-π attachment of the curcumin molecules onto the curcumin-reduced graphene oxide (rGO) sheets was confirmed by Raman and Fourier transform infrared spectroscopies. Zeta potential of the GO sheets decreased from about -40 mV to -20 mV, after the green reduction and functionalization. The probable cytotoxicity of the curcumin-rGO sheets was studied through their interactions with two human breast cancer cell lines (MDA-MB-231 and SKBR3 cell lines) and a normal cell line (mouse fibroblast L929 cell line). The curcumin-rGO sheet with concentrations <70 μg/mL in the cell culture medium, not only exhibited no significant toxicity and/or cell morphological changes, but also caused some cell growths (~25% after 48 h incubation time). Nevertheless, at 70 μg/mL, initiation of some cell morphological changes was observed. At higher concentrations (e.g., 100 μg/mL), some slight cytotoxic effects (resulting in ~15-25% cell destruction) were detected by MTT assay. In addition, the interaction of the rGO sheets and cells resulted in apoptosis as well as morphological transformation of the cells (from elongated to roundup morphology). These results indicated the concentration-dependent toxicity of functionalized-rGO nanomaterials (here, curcumin-rGO) at the threshold concentration of ~100 μg/mL.

Influence of surface null potential on nonvolatile bistable resistive switching memory behavior of dilutely aluminum doped ZnO thin film

We report a correlation between surface null potential and bistable resistive switching effect in dilutely Al-doped ZnO nearly transparent thin film. The nearly symmetrical bistable resistive switching was observed at low operating potential (±1 V) with good repeatability and stability, driven by surface null potential. We report that above null potential, oxygen vacancies in the proximity of aluminum provide systematic development of conducting paths. While, the switching effect was also observed to be dopant driven in the proximity to ±1 V. The phenomenon was explained using migration of Al3+ in ZnO matrix, which dominates over oxygen vacancies.

Tunable room temperature magnetoelectric response of SmFeO3/poly(vinylidene fluoride) nanocomposite films

We report the results of our studies on the tailored magnetoelectric response of a polymer based nanocomposite system comprising of varying SmFeO3 filler volume percentage embedded in a poly(vinylidene fluoride) (PVDF) matrix. The ME induced voltage was observed to increase with an increase in the SmFeO3 filler concentration from 1% to 20%. For composite films with 20% SmFeO3 concentration an induced voltage of ∼5.2 mV cm−1 Oe−1 was obtained at 1 kHz. Such a large magnetoelectric response is attributed to intensive interfacial interaction caused by dense packing of magnetostrictive SmFeO3 in the piezoelectric matrix of PVDF. Further, poling of composite films by application of an electric field was observed to lead to a saturated magnetization hysteresis loop caused by reorientation of the magnetization of SmFeO3. This electric field mediated manipulation of magnetic properties in SmFeO3/PVDF holds great potential for low-energy-consuming spintronics devices.

Probing bismuth ferrite nanoparticles by hard x-ray photoemission: Anomalous occurrence of metallic bismuth

We have investigated bismuth ferrite nanoparticles (∼75 nm and ∼155 nm) synthesized by a chemical method, using soft X-ray (1253.6 eV) and hard X-ray (3500, 5500, and 7500 eV) photoelectron spectroscopy. This provided an evidence for the variation of chemical state of bismuth in crystalline, phase pure nanoparticles. X-ray photoelectron spectroscopy analysis using Mg Kα (1253.6 eV) source showed that iron and bismuth were present in both Fe3+ and Bi3+ valence states as expected for bismuth ferrite. However, hard X-ray photoelectron spectroscopy analysis of the bismuth ferrite nanoparticles using variable photon energies unexpectedly showed the presence of Bi0 valence state below the surface region, indicating that bismuth ferrite nanoparticles are chemically inhomogeneous in the radial direction. Consistently, small-angle X-ray scattering reveals a core-shell structure for these radial inhomogeneous nanoparticles.

Enhanced proton conduction by post-synthetic covalent modification in a porous covalent framework

A highly chemically stable porous covalent framework (PCF-1) based on ether linkages has been synthesized, which exhibits no loss up to ∼500 °C along with retention of integrity under acidic, basic and oxidative reagent conditions. Owing to its thermal and chemical stability, post-synthetic covalent modification was executed for the introduction of pendant sulphonic acid (–SO3H) groups. The covalently modified compound (PCF-1-SO3H) presents a remarkably high conductivity (ca. 0.026 S cm−1), with an ∼130 fold enhancement in proton conductivity over the parent compound. This value is comparable with those of commercially used Nafion-based proton conducting materials and stands as the highest known value in the regime of post-synthetically modified porous organic frameworks. It is noteworthy to mention that PCF-1 is stable in both acidic and alkaline media, which is not commonly observed for most of the porous materials trialed as proton conducting materials, including metal–organic frameworks.

Effects of cobalt addition on the catalytic activity of the Ni-YSZ anode functional layer and the electrochemical performance of solid oxide fuel cells.

The effects of cobalt (Co) addition in the Ni-YSZ anode functional layer (AFL) on the structure and electrochemical performance of solid oxide fuel cells (SOFCs) are investigated. X-ray diffraction (XRD) analyses confirmed that the active metallic phase is a Ni(1-x)Co(x) alloy under the operation conditions of the SOFC. Scanning electron microscopy (SEM) observations indicate that the grain size of Ni(1-x)Co(x) increases with increasing Co content. Thermogravimetric analyses on the reduction of the Ni(1-x)Co(x)O-YSZ powders show that there are two processes: the chemical-reaction-controlled process and the diffusion-controlled process. It is found that the reduction peak corresponding to the chemical-reaction-controlled process in the DTG curves moves toward lower temperatures with increasing Co content, suggesting that the catalytic activity of Ni(1-x)Co(x) is enhanced by the doping of Co. It is observed that the SOFC shows the best performance at x = 0.03, and the corresponding maximum power densities are 445, 651, and 815 mW cm(-2) at 700, 750, and 800 °C, respectively. The dependence of the SOFC performance on the Co content can be attributed to the competing results between the decreased three-phase-boundary length in the AFL and the enhanced catalytic activity of the Ni(1-x)Co(x) phase with increasing Co content.

Influences of defects evolvement on the properties of sputtering deposited ZnO:Al films upon hydrogen annealing

Understanding how the defects interact with each other and affect the properties of ZnO:Al films is very important for improving their performance as a transparent conductive oxide (TCO). In the present work, we studied the effects of hydrogen annealing on the structural, optical and electrical properties of ZnO:Al films prepared by magnetron sputtering. High resolution transmission electron microscopy observations reveal that annealing at ∼300 oC induces the formation of partial dislocations (PD) and stacking faults (SF), which disrupt the lattice periodicity leading to decreased grain size. Annealing at temperatures above ∼500 oC can remove the PD and SF, but large number of zinc vacancies will be generated. Our results show that when films are annealed at ∼500 oC, the oxygen-related defects (interstitials Oi, etc.) in the as-grown films can be remarkably removed or converted, which lead to increments in the carrier concentration, mobility, and the transmittance in the visible range. At annealing temperatures above 550 oC, the hydrogen etching effect becomes predominant, and Al donors are deactivated by zinc vacancies. We also find an abnormal endothermic process by thermal analysis and an abnormal increase in the resistivity during heating the sample under hydrogen atmosphere, based on which the interaction of Oi with the defects (mainly Al donors and PD) is discussed. It is also demonstrated that by annealing the as-grown AZO films at ∼500 oC under hydrogen atmosphere, high performance TCO films with a low resistivity of 4.48 × 10−4 Ωcm and high transmittance of above 90% in the visible light are obtained.

A high performance ZnO based photoelectrochemical cell type UV photodetector with [Co(bpy)3]3+/2+ electrolyte and PEDOT/ITO counter electrode

We fabricated a high performance self-powered photoelectrochemical cell (PECC) type UV photodetector with ZnO nanorod arrays (NRs) as the photoanode, [Co(bpy)3]3+/2+ as the electrolyte and ITO glass coated by polymer poly(3,4-ethylenedioxythiophene) (PEDOT), PEDOT/ITO, as the counter electrode (CE). The UV photodetector shows a good photovoltaic performance (VOC = 0.5 V, ISC = 6.2 μA) and a high photosensitivity of 263 under the illumination of 365 nm UV light with an intensity of 2 mW cm−2. The device also shows a high response speed (response time < 0.2 s). The high photosensitivity and rapid response speed are attributed to the good electrocatalytic activity of PEDOT towards Co-complex redox shuttle. The high performance of the detector, together with the Pt-free low cost CE and the facile fabricating method, makes the device promising in optoelectronic applications.

Observation of nanotwinning and room temperature ferromagnetism in sub-5 nm BiFeO3 nanoparticles: a combined experimental and theoretical study.

Particle size significantly affects the properties and therefore the potential applications of multiferroics. However, is there special particle size effect in BiFeO3, which has a spiral modulated spin structure? This is still under investigation for sub-5 nm BiFeO3. In this report, the structural, electronic and magnetic properties are investigated for chemically synthesized BiFeO3 nanoparticles with an average size of 3 nm. We observed nanotwinning features in the specific size regime of the nanoparticles (2-4 nm). A weak Bi-O-Fe coordination and weak covalent nature has been observed in the nanoparticles through high-resolution electron energy loss spectroscopy and theoretical analysis, confirming that BiFeO3 nanoparticles a retain rudimentary R3c phase even at sub-5 nm dimensions. The R3c phase of sub-5 nm BiFeO3 nanoparticles has also been confirmed using Raman spectroscopy and Raman mapping of the vibrational modes. The nanoparticles display cluster spin glass, room temperature ferromagnetism, and a metamictization-davidite phase. The observation of weak magnetic entropy features confirmed the presence of a weak correlation between the magnetic and ferroelectric components. To support our experimental observations, we have simulated a sub-5 nm BiFeO3 nanocluster. Using density functional theory, the ferromagnetic ground state and the presence of a weak covalent nature in the nanocluster is established considering the first Brillouin zone, thus confirming our experimental results. Finding of new physicochemical features in sub-5 nm BiFeO3 would be beneficial for the understanding of the fundamental physical and chemical science as well as potential device development.

Self-Assembled, Fluorine-Rich Porous Organic Polymers: A Class of Mechanically Stiff and Hydrophobic Materials

Fluorous organic building blocks were utilized to develop two self-assembled, hydrophobic, fluorinated porous organic polymers (FPOPs), namely, FPOP-100 and FPOP-101. Comprehensive mechanical analyses of these functionalised triazine network polymers marked the introduction of mechanical stiffness among all porous organic network materials; the recorded stiffnesses are analogous to those of their organic-inorganic hybrid polymer congeners, that is, metal-organic frameworks. Furthermore, this study introduces a new paradigm for the simultaneous installation of mechanical stiffness and high surface hydrophobicity into polymeric organic networks, with the potential for transfer among all porous solids. Control experiments with non-fluorinated congeners underlined the key role of fluorine, in particular, bis-trifluoromethyl functionalization in realizing the dual features of mechanical stiffness and superhydrophobicity.